JP4136679B2 - Photothermographic material - Google Patents

Description

[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a photothermographic material. More particularly, the present invention relates to a photothermographic material having high sensitivity, low fog, and excellent image storability such as raw storability and printout.
[0002]
[Prior art]
In recent years, in the medical field and the printing plate making field, dry development of photographic development processing is strongly desired from the viewpoint of environmental protection and space saving. In these areas, digitization has progressed, and image information is captured and stored on a computer, stored, and processed if necessary, and output to photosensitive materials by laser image setter or laser imager where necessary by communication. However, systems for developing and creating images on the spot are rapidly spreading. As a photosensitive material, it is necessary to form a clear black image that can be recorded by laser exposure with high illuminance and has high resolution and sharpness. As such digital imaging recording materials, various hard copy systems using pigments and dyes such as inkjet printers and electrophotography are distributed as general image forming systems, but the diagnostic ability is determined like medical images. It is unsatisfactory in terms of image quality (sharpness, graininess, gradation, color tone) and recording speed (sensitivity), and has not yet reached a level that can replace the conventional silver salt film for wet development.
[0003]
On the other hand, thermal image forming systems using organic silver salts are known (see, for example, Patent Documents 1 and 2 and Non-Patent Document 1). Photothermographic materials generally contain a catalytically active amount of a photocatalyst (eg, silver halide), a reducing agent, a reducible silver salt (eg, an organic silver salt), and, if necessary, a toning agent that controls the color tone of silver. A photosensitive layer dispersed in the matrix.
[0004]
The photothermographic material is heated to a high temperature (for example, 80 ° C. or higher) after image exposure, and is blackened by an oxidation-reduction reaction between silver halide or a reducible silver salt (functioning as an oxidizing agent) and a reducing agent. Form a silver image. The oxidation-reduction reaction is promoted by the catalytic action of the latent image of silver halide generated by exposure. Therefore, a black silver image is formed in the exposure region (see, for example, Patent Documents 3 and 4). Fuji Medical Dry Imager FM-DPL was released as a medical image forming system using a photothermographic material.
[0005]
For a photothermographic material using an organic silver salt, higher sensitivity is required to increase the image recording speed, and lower fog is required to improve medical diagnostic ability. Furthermore, it is extremely important to further improve the raw storability and image storability of such a photothermographic material in order to replace the conventional silver salt image recording material for wet development.
[0006]
In such an image forming system using an organic silver salt, since there is no fixing step, image storage stability after development processing, in particular, deterioration of printout when exposed to light has been a serious problem. As a means for improving this printout, a method using silver iodide formed by converting an organic silver salt is disclosed (for example, see Patent Document 5.6). However, the method of converting an organic silver salt as disclosed herein with iodine cannot obtain sufficient sensitivity, and it is difficult to construct an actual system. Other photosensitive materials using silver iodide are described in several patent documents (see, for example, Patent Documents 7 to 11), but none of them achieves sufficient sensitivity and fog level, and laser exposure. It did not endure practical use as a sensitive material.
[0007]
As means for increasing the sensitivity of the silver iodide photographic emulsion, in the technical literature, by immersion in a halogen acceptor such as sodium nitrite, pyrogallol, hydroquinone or an aqueous silver nitrate solution, or by sulfur sensitization with pAg 7.5, It has been known to sensitize (see, for example, Non-Patent Documents 2 to 4). However, as shown in the Examples, the sensitizing effect of these halogen acceptors was very small and extremely insufficient in the photothermographic material targeted by the present invention. Therefore, development of a technique capable of greatly increasing the sensitivity in a photothermographic material using high silver iodide has been eagerly desired.
[0008]
In a silver halide light-sensitive material subjected to liquid development processing, a method of sensitizing using a compound that generates two electrons with one photon is known (for example, see Patent Documents 12 to 15).
[0009]
However, a silver halide light-sensitive material for liquid development processing is a development in which silver halide is generally reduced by a developer (reducing agent) contained in the liquid processing solution to form a silver image or by-product. A color image is formed using an oxidized form of a medicine, and the basic reaction is reduction of silver halide with a developer. On the other hand, in the photothermographic material, the silver halide only forms a latent image by exposure, and the silver halide itself is not reduced by the reducing agent, but is reduced from the non-photosensitive organic silver salt. It is the silver ion supplied. In the case of liquid development processing, the reducing agent is also an ionic reducing agent such as hydroquinone or p-phenylenediamine, whereas in the case of a photothermographic material, a hindered material generally known as a radical reagent is used. It is a phenol derivative.
[0010]
As described above, the mechanism of the development reaction (reduction reaction) is completely different between the liquid development-processed photosensitive material and the heat-developable photosensitive material, and the compounds used are completely different. Therefore, it cannot be said that a compound effective in the liquid development processing is effective as it is in the photothermographic material as it is. It is completely unpredictable whether the compounds described in the above-mentioned U.S. Patents can be applied to a photothermographic material to obtain the same effect or a completely different effect. Furthermore, it was impossible to recall the photothermographic material using a high silver iodide emulsion, and the effect could not be estimated.
[0011]
[Patent Document 1]
U.S. Pat. No. 3,152,904
[Patent Document 2]
U.S. Pat. No. 3,457,075
[Patent Document 3]
US Patent 2,910,377
[Patent Document 4]
Japanese Patent Publication No.43-4924
[Patent Document 5]
U US Pat. No. 6,143,488
[Patent Document 6]
European Patent No. 0922995
[Patent Document 7]
WO97-48014
[Patent Document 8]
WO97-48015
[Patent Document 9]
US Pat. No. 6,165,705
[Patent Document 10]
JP-A-8-197345
[Patent Document 11]
Japanese Patent No. 2785129
[Patent Document 12]
US Pat. No. 5,747,235
[Patent Document 13]
US Pat. No. 5,747,236
[Patent Document 14]
US Pat. No. 6,054,260
[Patent Document 15]
US Pat. No. 5,994,051
[Non-Patent Document 1]
D. H. Klosterboer, “Thermally Processed Silver Systems” (Imaging Processes and Materials Neblette 8th Edition, Sturge, V. (Walworth, A. Shepp, edited, Chapter 9, 279, 1989)
[Non-Patent Document 2]
P.B. Gilman, Photographic Science and Engineering, 18 (5), 475 (issued in 1974)
[Non-Patent Document 3]
W.L. Gardner, Photographic Science and Engineering, 18 (5), 475 (issued in 1974)
[Non-Patent Document 4]
T.H. James, Photographic Science and Engineering, Volume 5, 216 (issued in 1961)
[0012]
[Problems to be solved by the invention]
SUMMARY OF THE INVENTION An object of the present invention is to provide a photothermographic material having high sensitivity, low fog, excellent raw storage and image printout resistance.
[0013]
[Means for Solving the Problems]
  The object of the present invention has been achieved by the following photothermographic materials.
<1> A photothermographic material having an image forming layer containing a photosensitive silver halide, a non-photosensitive organic silver salt, a reducing agent, and a binder on the same surface of a support,Represented by the following general formula (I)At least one development accelerator selected from a compound having an adsorbing group and a reducing group for photosensitive silver halide or a precursor thereof, and compounds represented by the following general formulas (1), (2) and (3) A photothermographic material comprising:
[Chemical 1]
(In general formula (1), Q¹Is a NHNH-R at a carbon atom¹Represents a 5- to 7-membered unsaturated ring bonded to R,¹Represents a carbamoyl group. In the general formulas (2) and (3), X²And X^ThreeEach independently represents a hydrogen atom or a substituent;^{twenty one}And R³¹~ R³²Each independently represents a hydrogen atom or a substituent. However, the compound of the general formula (2) has a carbamoyl group at the 2-position with respect to the OH group. m and p each independently represent an integer of 0 to 4, and n represents an integer of 0 to 2. );
  Formula (I)
        A- (W) n-B
(In the formula, A represents an atomic group containing a group capable of adsorbing to silver halide, W represents a divalent linking group, n represents 0 or 1, and B represents a reducing group derived from phenidones. To express.).
[0015]
<2> The adsorbing group to the silver halide is a dimercapto-substituted heterocyclic group <1The photothermographic material according to the item>.
<3> In the general formula (1), R¹Is -CO-NH-R^{1 '}A substituted carbamoyl group represented by^{1 '}Is an alkyl or aryl group having 1 to 10 carbon atoms <1The photothermographic material according to the item>.
[0017]
<4> The reducing agent is represented by the following general formula (7): <1> to <13> The photothermographic material according to any one of the above.
[0018]
[Formula 4]
[0019]
  (In the general formula (7), R⁷¹And R⁷¹'Each independently represents an alkyl group having 1 to 20 carbon atoms. R⁷²And R⁷²'Represents a hydrogen atom or a group capable of substituting for a benzene ring. X⁷¹And X⁷²'Represents a hydrogen atom or a group capable of substituting for a benzene ring. L is a -S- group or -CHR.⁷³-Represents the group R⁷³Represents a hydrogen atom or an alkyl group. )
<5> The silver iodide content of the photosensitive silver halide is 5 mol% or more and 100 mol% or less <1> to <1>4> The photothermographic material according to any one of the above.
<6> The silver iodide content of the photosensitive silver halide is 40 mol% or more and 100 mol% or less <1> to <1>5> The photothermographic material according to any one of the above.
<7<1> to <1, characterized by being exposed by a laser light source6> The photothermographic material according to any one of the above.
<8> The laser light source is a laser light source having a wavelength of 350 nm to 450 nm <7The photothermographic material according to the item>.
<9> The laser light source is a blue semiconductor laser<7>Or <8The photothermographic material according to the item>.
[0020]
DETAILED DESCRIPTION OF THE INVENTION
The present invention is described in detail below.
[0021]
(Photothermographic material)
The photothermographic material of the present invention has an image forming layer containing a photosensitive silver halide, a non-photosensitive organic silver salt, a reducing agent, and a binder on at least one surface of a support. The image forming layer may be a single layer or a plurality of layers. Further, an intermediate layer or a surface protective layer may be provided on the image forming layer, or a back layer or a back protective layer may be provided on the opposite surface.
[0022]
The configuration of each layer and preferred components thereof will be described in detail.
[0023]
  (Compound having an adsorbing group and a reducing group)
  The present inventionPhotothermographic materialContains a compound having an adsorbing group and a reducing group for silver halide in the molecule (also referred to as an adsorbing redox compound in this application).Do.
  The adsorptive redox compound used in the present invention is a compound represented by the following general formula (I).The
[0024]
    Formula (I)
      A- (W) n-B
  In the formula, A represents a group capable of adsorbing to silver halide (hereinafter referred to as an adsorbing group), W represents a divalent linking group, n represents 0 or 1, and B representsDerived from phenidonesRepresents a reducing group.
[0025]
Next, Formula (I) will be described in detail.
In the formula (I), the adsorptive group represented by A is a group that directly adsorbs to silver halide or a group that promotes adsorption to silver halide. Specifically, a mercapto group (or a salt thereof) , A thione group (—C (═S) —), a heterocyclic group, a sulfide group, a disulfide group, a cationic group, or an ethynyl group containing at least one atom selected from a nitrogen atom, a sulfur atom, a selenium atom, and a tellurium atom Etc.
[0026]
The mercapto group (or salt thereof) as the adsorptive group means the mercapto group (or salt thereof) itself, and more preferably, a heterocyclic group or aryl group substituted with at least one mercapto group (or salt thereof) or Represents an alkyl group. Here, the heterocyclic group is at least a 5- to 7-membered monocyclic or condensed aromatic or non-aromatic heterocyclic group such as an imidazole ring group, a thiazole ring group, an oxazole ring group, or a benzimidazole ring. Group, benzothiazole ring group, benzoxazole ring group, triazole ring group, thiadiazole ring group, oxadiazole ring group, tetrazole ring group, purine ring group, pyridine ring group, quinoline ring group, isoquinoline ring group, pyrimidine ring group, And triazine ring group. Further, it may be a heterocyclic group containing a quaternized nitrogen atom. In this case, the substituted mercapto group may be dissociated into a meso ion. Examples of such a heterocyclic group include an imidazolium ring group, Examples include a pyrazolium ring group, a thiazolium ring group, a triazolium ring group, a tetrazolium ring group, a thiadiazolium ring group, a pyridinium ring group, a pyrimidinium ring group, and a triazinium ring group. Among them, a triazolium ring group (for example, 1,2,4- Triazolium-3-thiolate ring group) is preferable. Examples of the aryl group include a phenyl group and a naphthyl group. Examples of the alkyl group include linear, branched or cyclic alkyl groups having 1 to 30 carbon atoms. When the mercapto group forms a salt, the counter ion is a cation such as an alkali metal, alkaline earth metal, or heavy metal (Li⁺, Na⁺, K⁺, Mg²⁺, Ag⁺, Zn²⁺Etc.), ammonium ions, quaternized heterocyclic groups containing nitrogen atoms, phosphonium ions and the like.
[0027]
Further, the mercapto group as the adsorptive group may be tautomerized into a thione group, specifically, a thioamide group (here, —C (═S) —NH— group), and the thioamide group. Examples thereof include a group containing a partial structure, that is, a chain or cyclic thioamide group, thioureido group, thiourethane group, or dithiocarbamate group. Examples of cyclic groups include thiazolidine-2-thione group, oxazolidine-2-thione group, 2-thiohydantoin group, rhodanine group, isorhodanine group, thiobarbituric acid group, 2-thioxo-oxazolidine-4-one group Is mentioned.
[0028]
The thione group as the adsorptive group means that the mercapto group cannot be tautomerized (having no hydrogen atom at the α-position of the thione group), including the case where the above-mentioned mercapto group is tautomerized into a thione group. Also included are cyclic or cyclic thioamide groups, thioureido groups, thiourethane groups, or dithiocarbamate groups.
[0029]
A heterocyclic group containing at least one atom selected from a nitrogen atom, a sulfur atom, a selenium atom and a tellurium atom as an adsorptive group is a -NH- group capable of forming imino silver (> NAg) as a partial structure of the heterocyclic ring. A nitrogen-containing heterocyclic group, or a “—S—” group, a “—Se—” group, a “—Te—” group, or a “═N—” group that can coordinate to a silver ion by a coordination bond A heterocyclic group having a partial structure of benzotriazole group, triazole group, indazole group, pyrazole group, tetrazole group, benzimidazole group, imidazole group, purine group, etc. , Thiazole group, oxazole group, benzothiophene group, benzothiazole group, benzoxazole group, thiadiazole group, oxadiazole , Triazine group, seleno azole group, benzoselenazole group, tellurium azole group, such as benzo tellurium azole group. The former is preferred.
[0030]
The sulfide group or disulfide group as the adsorptive group includes all groups having a partial structure of “—S—” or “—S—S—”, and preferably alkyl (or alkylene) -X-alkyl (or alkylene). ), Aryl (or arylene) -X-alkyl (or alkylene), aryl (or arylene) -X-aryl (or arylene) having a partial structure, wherein X is an —S— group or —SS— -Represents a group. Further, these sulfide groups or disulfide groups may form a cyclic structure. Specific examples of the cyclic structure include a thiolane ring, 1,3-dithiolane ring, 1,2-dithiolane ring, thiane ring. , A group containing a dithiane ring, a thiomorpholine ring, and the like. A group having a partial structure of alkyl (or alkylene) -S-alkyl (or alkylene) is particularly preferred as the sulfide group, and a 1,2-dithiolane ring group is particularly preferred as the disulfide group.
[0031]
The cationic group as the adsorptive group means a group containing a quaternized nitrogen atom, specifically, an ammonio group or a group containing a nitrogen-containing heterocyclic group containing a quaternized nitrogen atom. Here, the ammonio group is a trialkylammonio group, a dialkylarylammonio group, an alkyldiarylammonio group or the like, and examples thereof include a benzyldimethylammonio group, a trihexylammonio group, and a phenyldiethylammonio group. Examples of the nitrogen-containing heterocyclic group containing a quaternized nitrogen atom include a pyridinio group, a quinolinio group, an isoquinolinio group, an imidazolio group, and the like. A pyridinio group and an imidazolio group are preferable, and a pyridinio group is particularly preferable. These nitrogen-containing heterocyclic groups containing a quaternized nitrogen atom may have an arbitrary substituent, but in the case of a pyridinio group and an imidazolio group, the substituent is preferably an alkyl group, an aryl group, an acylamino group , A chloro atom, an alkoxycarbonyl group, a carbamoyl group and the like. In the case of a pyridinio group, a phenyl group is particularly preferred as a substituent.
An ethynyl group as an adsorptive group means a —C≡CH group, and the hydrogen atom may be substituted.
[0032]
The adsorbing group may have an arbitrary substituent. Examples of the substituent include a halogen atom (a fluorine atom, a chloro atom, a bromine atom, or an iodine atom), an alkyl group (a linear, branched, or cyclic alkyl group, including a bicycloalkyl group or an active methine group), an alkenyl group. , Alkynyl group, aryl group, heterocyclic group (regardless of the position of substitution), acyl group, alkoxycarbonyl group, aryloxycarbonyl group, heterocyclic oxycarbonyl group, carbamoyl group, N-hydroxycarbamoyl group, N-acylcarbamoyl Group, N-sulfonylcarbamoyl group, N-carbamoylcarbamoyl group, thiocarbamoyl group, N-sulfamoylcarbamoyl group, carbazoyl group, carboxy group or a salt thereof, oxalyl group, oxamoyl group, cyano group, carbonimidoyl group (Carbonimidoyl group) Group), formyl group, hydro Xyl group, alkoxy group (including groups containing repeating ethyleneoxy or propyleneoxy group units), aryloxy group, heterocyclic oxy group, acyloxy group, (alkoxy or aryloxy) carbonyloxy group, carbamoyloxy group, sulfonyloxy Group, amino group, (alkyl, aryl, or heterocyclic) amino group, acylamino group, sulfonamide group, ureido group, thioureido group, N-hydroxyureido group, imide group, (alkoxy or aryloxy) carbonylamino group, sulfo group Famoylamino group, semicarbazide group, thiosemicarbazide group, hydrazino group, ammonio group, oxamoylamino group, N- (alkyl or aryl) sulfonylureido group, N-acylureido group, N-acylsulfamo A ruamino group, a hydroxyamino group, a nitro group, a heterocyclic group containing a quaternized nitrogen atom (eg, pyridinio group, imidazolio group, quinolinio group, isoquinolinio group), isocyano group, imino group, mercapto group, (alkyl, aryl) , Or heterocyclic) thio group, (alkyl, aryl, or heterocyclic) dithio group, (alkyl or aryl) sulfonyl group, (alkyl or aryl) sulfinyl group, sulfo group or a salt thereof, sulfamoyl group, N-acylsulfa Examples include a moyl group, an N-sulfonylsulfamoyl group or a salt thereof, a phosphino group, a phosphinyl group, a phosphinyloxy group, a phosphinylamino group, and a silyl group. Here, the active methine group means a methine group substituted with two electron-withdrawing groups, and the electron-withdrawing group here means an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a carbamoyl group, An alkylsulfonyl group, an arylsulfonyl group, a sulfamoyl group, a trifluoromethyl group, a cyano group, a nitro group, and a carbonimidoyl group (Carbonimidoyl group) are meant. Here, the two electron-attracting groups may be bonded to each other to form a cyclic structure. The salt means a cation such as alkali metal, alkaline earth metal or heavy metal, or an organic cation such as ammonium ion or phosphonium ion.
[0033]
Furthermore, specific examples of the adsorbing group include those described in the specifications p4 to p7 of JP-A No. 11-95355.
[0034]
In the formula (I), more preferable as the adsorptive group represented by A is a mercapto-substituted heterocyclic group (for example, 2-mercaptothiadiazole group, 3-mercapto-1,2,4-triazole group, 5-mercaptotetrazole group). 2-mercapto-1,3,4-oxadiazole group, 2-mercaptobenzthiazole group, 2-mercaptobenzimidazole group, 1,5-dimethyl-1,2,4-triazolium-3-thiolate group, etc.) Dimercapto-substituted heterocyclic groups (for example, 2,4-dimercaptopyrimidine group, 2,4-dimercaptotriazine group, 3,5-dimercapto-1,2,4-triazole group, 2,5-dimercapto-1,3 -Thiazole group, etc.) or a nitrogen-containing compound having an -NH- group capable of forming imino silver (> NAg) as a partial structure of a heterocyclic ring A Hajime Tamaki (e.g., a benzotriazole group, benzimidazole group, indazole group), particularly preferred are dimercapto-substituted heterocyclic group.
[0035]
In formula (I), W represents a divalent linking group. Any linking group may be used as long as it does not adversely affect photographic properties. For example, a divalent linking group composed of a carbon atom, a hydrogen atom, an oxygen atom, a nitrogen atom, or a sulfur atom can be used. Specifically, an alkylene group having 1 to 20 carbon atoms (for example, a methylene group, an ethylene group, a trimethylene group, a tetramethylene group, a hexamethylene group, etc.), an alkenylene group having 2 to 20 carbon atoms, and an alkynylene group having 2 to 20 carbon atoms. An arylene group having 6 to 20 carbon atoms (for example, a phenylene group, a naphthylene group, etc.), -CO-, -SO₂-, -O-, -S-, -NR₁-, The combination of these coupling groups, etc. are mention | raise | lifted. Where R₁Represents a hydrogen atom, an aliphatic group, or an aryl group. R₁Is preferably a linear, branched or cyclic alkyl group, alkenyl group, alkynyl group, aralkyl group (e.g., methyl group) having 1 to 30 carbon atoms and having 1 to 20 carbon atoms. Group, ethyl group, isopropyl group, t-butyl group, n-octyl group, n-decyl group, n-hexadecyl group, cyclopropyl group, cyclopentyl group, cyclohexyl group, allyl group, 2-butenyl group, 3-pentenyl group Group, propargyl group, 3-pentynyl group, benzyl group, etc.), R₁Is preferably a monocyclic or condensed aryl group having 6 to 30 carbon atoms, more preferably 6 to 20 carbon atoms, and examples thereof include a phenyl group and a naphthyl group. The linking group represented by W may have an arbitrary substituent, and this arbitrary substituent is synonymous with that described as the substituent of the aforementioned adsorptive group.
[0036]
In formula (I), the reducing group represented by B represents a group capable of reducing silver ions. For example, a triple bond group such as formyl group, amino group, acetylene group or propargyl group, mercapto group, hydroxylamines. , Hydroxamic acids, hydroxyureas, hydroxyurethanes, hydroxysemicarbazides, reductones (including reductone derivatives), anilines, phenols (chroman-6-ols, 2,3-dihydrobenzofuran-5-ols, Derived from compounds selected from aminophenols, sulfonamidophenols, and hydroquinones, catechols, resorcinols, polyphenols such as benzenetriols, bisphenols), hydrazines, hydrazides, and phenidones Examples include residues.
[0037]
In formula (I), a preferred reducing group represented by B is represented by the following formula B₁Or B₁₃It is a residue derived from the compound represented by these.
[0038]
[Chemical formula 5]
[0039]
Formula (B₁) To (B₁₃), R_b1, R_b2, R_b3, R_b4, R_b5, R_b70, R_b71, R_b110, R_b111, R_b112, R_b113, R_b12, R_b13, R_N1, R_N2, R_N3, R_N4, R_N5Represents a hydrogen atom, an alkyl group, an aryl group, a heterocyclic group, and R_H3, R_H5, R '_H5, R_H12, R '_H12, R_H13Represents a hydrogen atom, an alkyl group, an aryl group, an acyl group, an alkylsulfonyl group or an arylsulfonyl group, of which R_H3May further be a hydroxy group. R_b100, R_b101, R_b102, R_b130~ R_b133Represents a hydrogen atom or a substituent. Y₇, Y₈Represents a substituent other than a hydroxy group, Y₉Represents a substituent, m_FiveIs 0 or 1, m₇Is an integer from 0 to 5, m₈Is an integer from 1 to 5, m₉Represents an integer of 0-4. Y₇, Y₈, Y₉May further be an aryl group condensed with a benzene ring (for example, a benzene condensed ring), which may further have a substituent. Z_TenRepresents a nonmetallic atomic group capable of forming a ring, and X₁₂Represents a hydrogen atom, an alkyl group, an aryl group, a heterocyclic group, an alkoxy group, an amino group (including an alkylamino group, an arylamino group, a heterocyclic amino group, or a cyclic amino group), or a carbamoyl group.
[0040]
Formula (B₆) X₆, X '₆Are hydroxy group, alkoxy group, mercapto group, alkylthio group, amino group (including alkylamino group, arylamino group, heterocyclic amino group, or cyclic amino group), acylamino group, sulfonamido group, alkoxycarbonylamino group, respectively. Represents a ureido group, an acyloxy group, an acylthio group, an alkylaminocarbonyloxy group, or an arylaminocarbonyloxy group. R_b60, R_b61Represents an alkyl group, an aryl group, an amino group, an alkoxy group, an aryloxy group, and R_b60And R_b61May be bonded to each other to form a cyclic structure.
[0041]
The above formula (B₁) To (B₁₃In the description of each group, the alkyl group means a linear, branched or cyclic, substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, and the aryl group means a phenyl group or a naphthyl group. Represents a substituted or unsubstituted aromatic hydrocarbon ring which is monocyclic or condensed, and the heterocyclic group is an aromatic or non-aromatic monocyclic or condensed ring containing at least one heteroatom. Means a substituted or unsubstituted heterocyclic group.
Also, the formula (B₁) To (B₁₃And the substituents mentioned in the explanation of each group are the same as the substituents of the aforementioned adsorbing group. These substituents may be further substituted with these substituents.
[0042]
Formula (B₁) To (B_Five) R_N1, R_N2, R_N3, R_N4, R_N5Is preferably a hydrogen atom or an alkyl group, wherein the alkyl group is preferably a linear, branched or cyclic, substituted or unsubstituted alkyl group having 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms. A linear or branched, substituted or unsubstituted alkyl group such as a methyl group, an ethyl group, a propyl group, or a benzyl group.
[0043]
Formula (B₁) R_b1Is preferably an alkyl group or a heterocyclic group, wherein the alkyl group is a linear, branched or cyclic, substituted or unsubstituted alkyl group, preferably having 1 to 30 carbon atoms, more preferably 1 to 1 carbon atoms. 18 alkyl groups. The heterocyclic group is a 5-membered or 6-membered monocyclic or condensed ring aromatic or non-aromatic heterocyclic group which may have a substituent. The heterocyclic group is preferably an aromatic heterocyclic group such as a pyridine ring group, a pyrimidine ring group, a triazine ring group, a thiazole ring group, a benzothiazole ring group, an oxazole ring group, a benzoxazole ring group, an imidazole ring group, or a benzimidazole. Examples thereof include a ring group, a pyrazole ring group, an indazole ring group, an indole ring group, a purine ring group, a quinoline ring group, an isoquinoline ring group, and a quinazoline ring group, and a triazine ring group and a benzothiazole ring group are particularly preferable. R_b1An alkyl group or a heterocyclic group represented by the formula --N (R_N1The case where one or more OH groups are further present is also a preferred example of the compound represented by the formula (B1).
[0044]
Formula (B₂) R_b2Is preferably an alkyl group, an aryl group, or a heterocyclic group, more preferably an alkyl group or an aryl group. Preferred range of alkyl group is R_b1This is the same as the description in FIG. The aryl group is preferably a phenyl group or a naphthyl group, and the phenyl group is particularly preferable and may have a substituent. R_b2The group represented by the formula: —CON (R_N2The case where there is one or more OH groups is also represented by the formula (B₂Is a preferred example of a compound represented by
[0045]
Formula (B_Three) R_b3Is preferably an alkyl group or an aryl group, these preferred ranges being R_b1And R_b2This is the same as the description in FIG. R_H3Is preferably a hydrogen atom, an alkyl group or a hydroxy group, more preferably a hydrogen atom. R_b3The group represented by the formula is -N (R_H3) CON (R_N3The case where one or more OH groups are further present is also a preferred example of the compound represented by the formula (B3). Also R_b3And R_N3May combine with each other to form a ring structure (preferably a 5- or 6-membered saturated heterocycle).
[0046]
Formula (B_Four) R_b4Is preferably an alkyl group, the preferred range of which is R_b1This is the same as the description in FIG. R_b4Is represented by —OCON (R_N4The case where there is one or more OH groups is also represented by the formula (B_FourIs a preferred example of a compound represented by
Formula (B_Five) R_b5Is preferably an alkyl group or an aryl group, more preferably an aryl group, these preferred ranges being R_b1And R_b2This is the same as the description in FIG. R_H5, R '_H5Is preferably a hydrogen atom or an alkyl group, more preferably a hydrogen atom.
[0047]
Formula (B₆) R_b60, R_b61Are preferably bonded to each other to form a ring structure. The cyclic structure formed here is a 5-membered to 7-membered non-aromatic carbocyclic or heterocyclic ring, which may be a monocyclic ring or a condensed ring. Specific examples of preferred ring structures include, for example, 2-cyclopenten-1-one ring, 2,5-dihydrofuran-2-one ring, 3-pyrrolin-2-one ring, 4-pyrazolin-3-one Ring, 2-cyclohexen-1-one ring, 5,6-dihydro-2H-pyran-2-one ring, 5,6-dihydro-2-pyridone ring, 1,2-dihydronaphthalen-2-one ring, coumarin Ring (benzo-α-pyran-2-one ring), 2-quinolone ring, 1,4-dihydronaphthalen-1-one ring, chromone ring (benzo-γ-pyran-4-one ring), 4-quinolone ring , Indene-1-one ring, 3-pyrroline-2,4-dione ring, uracil ring, thiouracil ring, dithiouracil ring and the like, more preferably 2-cyclopenten-1-one ring, 2,5-dihydro Flan-2-one , 3-pyrrolin-2-one ring, 4-pyrazolin-3-one ring, 1,2-dihydronaphthalen-2-one ring, coumarin ring (benzo-α-pyran-2-one ring), 2-quinolone ring 1,4-dihydronaphthalen-1-one ring, chromone ring (benzo-γ-pyran-4-one ring), 4-quinolone ring, inden-1-one ring, dithiouracil ring, etc., more preferably They are 2-cyclopenten-1-one ring, 2,5-dihydrofuran-2-one ring, 3-pyrrolin-2-one ring, inden-1-one ring and 4-pyrazolin-3-one ring.
[0048]
X₆, X '₆Represents a cyclic amino group, the cyclic amino group is a non-aromatic nitrogen-containing heterocyclic group bonded with a nitrogen atom, such as a pyrrolidino group, piperidino group, piperazino group, morpholino group, 1,4-thiazine- 4-yl group, 2,3,5,6-tetrahydro-1,4-thiazin-4-yl group, indolyl group and the like.
X₆, X '₆Preferred are a hydroxy group, a mercapto group, an amino group (including an alkylamino group, an arylamino group, or a cyclic amino group), an acylamino group, a sulfonamide group, an acyloxy group, and an acylthio group, and more preferably a hydroxy group Group, mercapto group, amino group, alkylamino group, cyclic amino group, sulfonamide group, acylamino group or acyloxy group, particularly preferably a hydroxy group, amino group, alkylamino group or cyclic amino group. X₆And X '₆At least one of them is preferably a hydroxy group.
[0049]
Formula (B₇) R_b70, R_b71Is preferably a hydrogen atom, an alkyl group or an aryl group, more preferably an alkyl group. Preferred range of alkyl group is R_b1This is the same as the description in FIG. R_b70, R_b71May be bonded to each other to form a cyclic structure (eg, pyrrolidine ring, piperidine ring, morpholino ring, thiomorpholino ring, etc.). Y₇Is preferably an alkyl group (its preferred range is R_b1, Alkoxy group, amino group, acylamino group, sulfonamido group, ureido group, acyl group, alkoxycarbonyl group, carbamoyl group, sulfamoyl group, chloro atom, sulfo group or salt thereof, carboxy group or salt thereof, etc. And m₇Preferably represents 0-2.
[0050]
Formula (B₈) M is preferably 1 to 4, and a plurality of Y₈May be the same or different. m₈Y when is 1₈Or m₈Multiple Y when is 2 or more₈At least one of them is preferably an amino group (including an alkylamino group and an arylamino group), a sulfonamide group, or an acylamino group. m₈When Y is 2 or more, Y remains₈Is preferably a sulfonamido group, an acylamino group, a ureido group, an alkyl group, an alkylthio group, an acyl group, an alkoxycarbonyl group, a carbamoyl group, a sulfo group or a salt thereof, a carboxy group or a salt thereof, or a chloro atom. Y here₈In the case where o ′-(or p ′-) hydroxyphenylmethyl group (which may further have a substituent) is substituted at the ortho-position or para-position of the hydroxy group as a substituent represented by Represents a group of compounds generally called bisphenols, and this case is also one of the preferred examples of the compound represented by the formula (B8). Y₈It is also very preferable that represents a benzene condensed ring and as a result, the formula (B8) represents a naphthol.
[0051]
Formula (B₉), The substitution positions of the two hydroxy groups may be ortho positions (catechols), meta positions (resorcinols) or para positions (hydroquinones). m₉Is preferably 1-2, and a plurality of Y₉May be the same or different. Y₉Preferably, the substituent represented by chloro atom, acylamino group, ureido group, sulfonamido group, alkyl group, alkylthio group, alkoxy group, acyl group, alkoxycarbonyl group, carbamoyl group, sulfo group or salt thereof, carboxy group Or the salt, a hydroxy group, an alkylsulfonyl group, an arylsulfonyl group etc. are mentioned. Y₉Represents a benzene condensed ring, and as a result, the formula (B₉It is also preferred if) represents 1,4-naphthohydroquinones. Formula (B₉) Represents catechols, Y₉Is particularly preferably a sulfo group or a salt thereof, or a hydroxy group.
[0052]
Formula (B_Ten) R_b100, R_b101, R_b102When represents a substituent, preferred examples of the substituent are Y₉This is the same as the preferred example. Of these, an alkyl group (particularly a methyl group) is preferred. Z_TenThe ring structure formed by is preferably a chroman ring or a 2,3-dihydrobenzofuran ring, and these ring structures may have a substituent or may form a spiro ring.
Formula (B₁₁) R_b110, R_b111, R_b112, R_b113As an alkyl group, an aryl group, or a heterocyclic group, these preferred ranges are R_b1And R_b2This is the same as the description in FIG. Of these, an alkyl group is preferred, and R_b110~ R_b113Two of these alkyl groups may be bonded to form a cyclic structure. Here, the cyclic structure is a 5-membered or 6-membered non-aromatic heterocycle, and examples thereof include a pyrrolidine ring, a piperidine ring, a morpholino ring, a thiomorpholino ring, and a hexahydropyridazine ring.
[0053]
Formula (B₁₂) R_b12As an alkyl group, an aryl group, or a heterocyclic group, these preferred ranges are R_b1And R_b2This is the same as the description in FIG. X₁₂Is preferably an alkyl group, an aryl group (particularly a phenyl group), a heterocyclic group, an alkoxy group, an amino group (including an alkylamino group, an arylamino group, a heterocyclic amino group, or a cyclic amino group), or a carbamoyl group. An alkyl group (especially an alkyl group having 1 to 8 carbon atoms is preferred), an aryl group (especially a phenyl group is preferred), and an amino group (including an alkylamino group, an arylamino group, or a cyclic amino group) are more preferred. R_H12, R '_H12Is preferably a hydrogen atom or an alkyl group, more preferably a hydrogen atom.
[0054]
Formula (B₁₃) R_b13Is preferably an alkyl group or an aryl group, and preferred ranges thereof are R_b1And R_b2This is the same as the description in FIG. R_b130, R_b131, R_b132, R_b133Is preferably a hydrogen atom, an alkyl group (particularly preferably having 1 to 8 carbon atoms), or an aryl group (particularly preferably a phenyl group). R_H13Is preferably a hydrogen atom or an acyl group, more preferably a hydrogen atom.
[0055]
  In the formula (I), a reducing group represented by BIsPhenidonesMore derived groupsIt is.
[0056]
In the formula (I), the reducing group represented by B shows its oxidation potential by Akira Fujishima “Electrochemical Measurement” (pages 150-208, published by Gihodo) and the “Chemical Laboratory of Chemistry” 4th edition (edited by the Chemical Society of Japan). Vol. 9, pp. 282-344, Maruzen). For example, by a rotating disk voltammetry technique, specifically, a sample is dissolved in a solution of methanol: pH 6.5 Briton-Robinson buffer = 10%: 90% (volume%), and nitrogen gas is used for 10 minutes. , A glassy rotating disk electrode (RDE) is used as a working electrode, a platinum wire is used as a counter electrode, a saturated calomel electrode is used as a reference electrode, 25 ° C., 1000 rev / min, 20 mV / sec. Can be measured at sweep speed. A half-wave potential (E1 / 2) can be obtained from the obtained voltammogram.
The reducing group represented by B of the present invention preferably has an oxidation potential in the range of about -0.3 V to about 1.0 V when measured by the above-described measurement method. More preferably, it is in the range of about -0.1V to about 0.8V, and particularly preferably in the range of about 0 to about 0.7V.
[0057]
Many of the reducing groups represented by B of the present invention are known compounds in the photographic industry, and examples thereof are also described in the following patents. For example, JP 2001-42466, JP 8-114884, JP 8-314051, JP 8-333325, JP 9-133983, JP 11-282117, JP 10-246931, JP-A-10-90819, JP-A-9-54384, JP-A-10-171060, JP-A-7-77783. Examples of the phenols also include compounds described in US Pat. No. 6,054,260.
[0058]
The compound of the formula (I) of the present invention may be one in which a ballast group or a polymer chain commonly used in an immobile photographic additive such as a coupler is incorporated. Examples of the polymer include those described in JP-A-1-100530.
[0059]
The compound of the formula (I) of the present invention may be a bis form or a tris form. The molecular weight of the compounds of the formula (I) according to the invention is preferably between 100 and 10000, more preferably between 120 and 1000, particularly preferably between 150 and 500.
[0060]
Examples of the compound of formula (I) of the present invention are shown below, but the present invention is not limited thereto. Moreover, the compound illustrated by Unexamined-Japanese-Patent No. 2000-330247 and Unexamined-Japanese-Patent No. 2001-42446 is also a preferable example.
[0061]
[Chemical 6]
[0062]
[Chemical 7]
[0063]
[Chemical 8]
[0064]
[Chemical 9]
[0065]
[Chemical Formula 10]
[0066]
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[0067]
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[0068]
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[0069]
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[0070]
The compounds of the present invention can be easily synthesized according to known methods.
As the compound of the formula (I) of the present invention, one kind of compound may be used alone, but it is also preferred to use two or more kinds of compounds at the same time. When two or more kinds of compounds are used, they may be added in the same layer or in different layers, and the addition method may be different.
[0071]
The compound of the formula (I) of the present invention is preferably added to the same layer as the silver halide emulsion, and can be added when preparing the silver halide emulsion or preparing the coating solution. It is more preferable to add at the time of preparing the silver halide emulsion. When added at the time of preparing the silver halide emulsion, it can be added at any time during the process. For example, the silver halide grain formation process, before the start of the desalting process, the desalting process, Examples include a step before chemical ripening, a step of chemical ripening, and a step before preparing a finished emulsion. Moreover, it can also add in several steps in these processes. Although it is preferably used for a silver halide emulsion layer, it may be added to the adjacent protective layer or intermediate layer together with the silver halide emulsion layer and diffused during coating.
The preferred addition amount largely depends on the above-mentioned addition method and the kind of compound to be added, but in general, 1 × 10 6 per mole of photosensitive silver halide.^-6~ 1 mole, preferably 1 x 10^-Five~ 5 × 10^-1Mole more preferably 1 × 10^-Four~ 1 × 10^-1Is a mole.
[0072]
The compound of the formula (I) of the present invention can be added after being dissolved in water, a water-soluble solvent such as methanol or ethanol, or a mixed solvent thereof. At this time, the pH may be appropriately adjusted with an acid or a base, and a surfactant may be allowed to coexist. Furthermore, it can also be dissolved in a high boiling point organic solvent and added as an emulsified dispersion. It can also be added as a solid dispersion.
[0073]
(Development accelerator)
The development accelerator used in the present invention will be described in detail.
The development accelerator used in the present invention is a photothermographic material having a photosensitive layer containing at least one layer of photosensitive silver halide, non-photosensitive organic silver salt, a reducing agent and a binder on a support. When the compound is substituted at a molar ratio of 10% with respect to the reducing agent (referred to as the main reducing agent), it is a compound whose sensitivity at a concentration = 1.0 is increased by 0.05 or more compared with the case where it is not substituted.
[0074]
The development accelerator is preferably a compound having an increase in sensitivity of 0.05 or more when substituted by 5 mol%, and more preferably a compound having an increase of sensitivity of 0.05 or more when substituted by 2 mol%.
[0075]
  As the development accelerator, any compound can be used as long as it is a compound that increases the sensitivity when substituted with the main reducing agent as described above in thermal development. It is preferable to use a so-called reducing agent. Specifically, compounds such as aminophenols, p-phenylenediamines, sulfonamidophenols, carbonamidophenols, 1-phenyl-5-pyrazolidones, ascorbic acid, hydrazines, phenols and naphthols are used. be able to. Among them, sulfonamidophenols (for example, compounds represented by the general formula (1) described in JP-A-10-221806, compounds represented by the formula (A) described in JP-A 2000-267222), hydrazines are included. preferable.
  In the present inventionIs a compound represented by the following general formulas (1) to (3)Contains at least one development accelerator selected from.
[0076]
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[0077]
(In general formula (1), Q¹Is a NHNH-R at a carbon atom¹Represents a 5- to 7-membered unsaturated ring bonded to R,¹Is carbamoylGroupTo express. In the general formulas (2) and (3), X²And X^ThreeEach independently represents a hydrogen atom or a substituent;^{twenty one}And R³¹~ R³²Each independently represents a hydrogen atom or a substituent.However, the compound of the general formula (2) has a carbamoyl group at the 2-position with respect to the OH group.m and p each independently represent an integer of 0 to 4, and n represents an integer of 0 to 2. ).
[0078]
The most preferred compound as a development accelerator in the present invention is a compound (hydrazine derivative) represented by the general formula (1). The photothermographic material of the invention preferably has a reducing compound represented by the general formula (1) on the same surface as the photosensitive silver halide and the non-photosensitive silver salt on the support.
[0079]
The reducing compound represented by the general formula (1) is a developing agent collectively referred to as a hydrazine developing agent. Where Q¹Is a NHNH-R at a carbon atom¹Represents a 5- to 7-membered unsaturated ring bonded to R,¹Is carbamoylGroupTo express.
[0080]
Q in general formula (1)¹Preferred examples of the 5- to 7-membered unsaturated ring represented by benzene ring, pyridine ring, pyrazine ring, pyrimidine ring, pyridazine ring, 1,2,4-triazine ring, 1,3,5-triazine ring Pyrrole ring, imidazole ring, pyrazole ring, 1,2,3-triazole ring, 1,2,4-triazole ring, tetrazole ring, 1,3,4-thiadiazole ring, 1,2,4-thiadiazole ring, 1 , 2,5-thiadiazole ring, 1,3,4-oxadiazole ring, 1,2,4-oxadiazole ring, 1,2,5-oxadiazole ring, thiazole ring, oxazole ring, isothiazole ring , Isoxazole rings, thiophene rings and the like, and condensed rings in which these rings are condensed with each other are also preferable.
[0081]
These rings may have a substituent, and when they have two or more substituents, these substituents may be the same or different. Examples of substituents include halogen atoms, alkyl groups, aryl groups, carbonamido groups, alkylsulfonamido groups, arylsulfonamido groups, alkoxy groups, aryloxy groups, alkylthio groups, arylthio groups, carbamoyl groups, sulfamoyl groups, cyano Groups, alkylsulfonyl groups, arylsulfonyl groups, alkoxycarbonyl groups, aryloxycarbonyl groups, and acyl groups.
[0082]
When these substituents are substitutable groups, they may further have substituents. Examples of preferred substituents include halogen atoms, alkyl groups, aryl groups, carbonamido groups, alkylsulfonamido groups, aryls. Sulfonamide group, alkoxy group, aryloxy group, alkylthio group, arylthio group, acyl group, alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl group, cyano group, sulfamoyl group, alkylsulfonyl group, arylsulfonyl group, and acyloxy group Can be listed.
[0083]
In the general formula (1), R¹The carbamoyl group represented by these has preferable C1-C50, and C6-C40 is more preferable. Specifically, unsubstituted carbamoyl group, methylcarbamoyl group, N-ethylcarbamoyl group, N-propylcarbamoyl group, N-sec-butylcarbamoyl group, N-octylcarbamoyl group, N-cyclohexylcarbamoyl group, N-tert- Butylcarbamoyl group, N-dodecylcarbamoyl group, N- (3-dodecyloxypropyl) carbamoyl group, N-octadecylcarbamoyl group, N- {3- (2,4-tert-pentylphenoxy) propyl} carbamoyl group, N- (2-hexyldecyl) carbamoyl group, N-phenylcarbamoyl group, N- (4-dodecyloxyphenyl) carbamoyl group, N- (2-chloro-5-dodecyloxycarbonylphenyl) carbamoyl group, N-naphthylcarbamoyl group, N-3-pyridylka Bamoiru group, N- benzylcarbamoyl group.
[0088]
  oneIn general formula (1), R¹In the group represented by¹May have the groups mentioned as examples of the substituents of the 5- to 7-membered unsaturated ring represented by the formula (1), and when they have two or more substituents, these substituents are the same. Or different.
[0089]
Among the compounds represented by the general formula (1), Q¹Is preferably a 5- or 6-membered unsaturated ring,¹Is a benzene ring, pyrimidine ring, 1,2,3-triazole ring, 1,2,4-triazole ring, tetrazole ring, 1,3,4-thiadiazole ring, 1,2,4-thiadiazole ring, 1,3, 4-oxadiazole ring, 1,2,4-oxadiazole ring, thiazole ring, oxazole ring, isothiazole ring, isoxazole ring, or a ring condensed with a benzene ring or an unsaturated heterocycle More preferably, Q¹Is particularly preferably a quinazoline ring. Q¹Preferably has at least one electron-withdrawing substituent. Preferred substituents include fluoroalkyl groups (for example, trifluoromethyl group, pentafluoroethyl group, 1,1-difluoroethyl group, difluoromethyl group, fluoromethyl group, heptafluoropropyl group, pentafluorophenyl group), cyano Group, halogen atom (fluoro, chloro, bromo, iodo), acyl group, alkoxycarbonyl group, carbamoyl group, alkylsulfonyl group, arylsulfonyl group, and trifluoromethyl group is particularly preferable.
[0090]
  In the general formula (1), R¹Is a carbamoyl groupYes, Particularly preferably R¹-CO-NH-R^{1 '}And a substituted carbamoyl group represented by:^{1 '}Particularly preferably represents an alkyl group having 1 to 10 carbon atoms or an aryl group.
  Specific examples of the reducing compound represented by the general formula (1) are as follows:And reference examplesHowever, the compounds used in the present invention are not limited by these specific examples.
[0091]
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[0092]
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[0093]
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[0094]
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[0095]
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[0096]
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[0097]
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[0098]
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[0099]
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[0100]
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[0101]
[Table 1]
[0102]
[Table 2]
[0103]
[Table 3]
[0104]
[Table 4]
[0105]
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[0106]
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[0107]
Synthesis of the reducing compound represented by the general formula (1) is described in JP-A-9-152702, JP-A-8-286340, JP-A-9-152700, JP-A-9-152701, and JP-A-9-152703. It can implement according to the method as described in gazette and the 9-152704 gazette.
Although the addition amount of the reducing compound represented by the general formula (1) is wide, it is preferably 0.01 to 100 mol times, more preferably 0.1 to 10 mol times with respect to silver ions.
[0108]
The reducing compound represented by the general formula (1) may be added to the coating solution by any method such as a solution, powder, solid fine particle dispersion, emulsion, or oil protect dispersion. Particularly when used together with the latex of the present invention, it is preferably added as solid fine particles. The solid fine particle dispersion is performed by a known finer means (for example, ball mill, vibrating ball mill, sand mill, colloid mill, jet mill, roller mill, etc.). A dispersion aid may be used when dispersing the solid fine particles.
[0109]
The compound represented by the following general formula (2) or (3) will be described.
In the general formulas (2) and (3), X²And X^ThreeEach independently represents a hydrogen atom or a substituent. X²And X^ThreeAs examples of the substituent represented by formula (1), a halogen atom (for example, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom), an aryl group (preferably having 6 to 30 carbon atoms, more preferably 6 to 20 carbon atoms, still more preferably 6). -12, for example, phenyl, p-methylphenyl, naphthyl, etc.), an alkoxy group (preferably having a carbon number of 1-20, more preferably 1-12, still more preferably 1-8, for example, methoxy, ethyne , Butoxy, etc.), an aryloxy group (preferably having 6 to 20 carbon atoms, more preferably 6 to 16, more preferably 6 to 12, such as phenyloxy, 2-naphthyloxy, etc.), an alkylthio group (preferably C1-C20, More preferably, it is 1-16, More preferably, it is 1-12, for example, methylthio, ethylthio, butyl O), an arylthio group (preferably having 6 to 20 carbon atoms, more preferably 6 to 16 carbon atoms, still more preferably 6 to 12 carbon atoms such as phenylthio, naphthylthio, etc.), an acyloxy group (preferably having 1 to 20 carbon atoms, More preferably, it is 2 to 16, more preferably 2 to 10, for example, acetoxy, benzoyloxy, etc.), an acylamino group (preferably having 2 to 20 carbon atoms, more preferably 2 to 16, more preferably 2 to 10). For example, N-methylacetylamino, benzoylamino, etc.), sulfonylamino groups (preferably having 1 to 20 carbon atoms, more preferably 1 to 16, more preferably 1 to 12, such as methanesulfonylamino, Benzenesulfonylamino, etc.), a carbamoyl group (preferably having 1 to 20 carbon atoms, more preferably 1 to 6, more preferably 1 to 12, for example, carbamoyl, N, N-diethylcarbamoyl, N-phenylcarbamoyl, etc.), acyl group (preferably having 2 to 20 carbon atoms, more preferably 2 to 16 carbon atoms, still more preferably 2 to 12, for example, acetyl, benzoyl, formyl, pivaloyl, etc.), an alkoxycarbonyl group (preferably having 2 to 20 carbon atoms, more preferably 2 to 16, more preferably 2 to 12, such as methoxycarbonyl Etc.), sulfo group, sulfonyl group (preferably having 1 to 20 carbon atoms, more preferably 1 to 16, more preferably 1 to 12, such as mesyl, tosyl, etc.), sulfonyloxy group (preferably having 1 carbon atom). To 20, more preferably 1 to 16, still more preferably 1 to 12, for example, methanesulfonylo And azo group, heterocyclic group, heterocyclic mercapto group, cyano group and the like. The heterocyclic group here represents a saturated or unsaturated heterocyclic group, for example, pyridyl group, quinolyl group, quinoxalinyl group, pyrazinyl group, benzotriazolyl group, pyrazolyl group, imidazolyl group, benzoimidazolyl group, tetrazolyl group. , A hyguntoin-1-yl group, a succinimide group, a phthalimide group, and the like.
[0110]
X in general formulas (2) and (3)²And X^ThreeThe substituent represented by is more preferably an alkoxy group or an aryloxy group. X²And X^ThreeThe substituent represented by may be further substituted with another substituent, and may be any generally known substituent as long as it does not deteriorate the photographic performance.
[0111]
-R in general formulas (2) and (3)^2l, R³¹, R³²Each independently represents a hydrogen atom or a substituent. m and p each independently represent an integer of 0 to 4, and n represents an integer of 0 to 2. R^2l, R³¹, R³²Any substituent may be used as long as it does not adversely affect photographic properties. For example, a halogen atom (for example, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom), a linear, branched, cyclic or a combination thereof (preferably having 1 to 20 carbon atoms, more preferably 1 to 16 carbon atoms, still more preferably Are, for example, methyl, ethyl, n-propyl, isopropyl, sec-butyl, tert-butyl, tert-octyl, n-amyl, tert-amyl, n-dodecyl, n-tridecyl, cyclohexyl Etc.), an alkenyl group (preferably having 2 to 20 carbon atoms, more preferably 2 to 16, more preferably 2 to 12, such as vinyl, allyl, 2-butenyl, 3-pentenyl, etc.), an aryl group (preferably Has 6 to 30 carbon atoms, more preferably 6 to 20 carbon atoms, still more preferably 6 to 12 carbon atoms such as phenyl, p- Tilphenyl, naphthyl and the like), an alkoxy group (preferably having 1 to 20 carbon atoms, more preferably 1 to 16 and further preferably 1 to 12, such as methoxy, ethyne, propoxy, butoxy, etc.), an aryloxy group (preferably Has 6 to 30 carbon atoms, more preferably 6 to 20 carbon atoms, still more preferably 6 to 12 carbon atoms, such as phenyloxy, 2-naphthyloxy, and the like, and an acyloxy group (preferably having 2 to 20 carbon atoms, more preferably 2 carbon atoms). -16, more preferably 2-12, for example, acetoxy, benzoyloxy, etc.), amino group (preferably 0-20 carbon atoms, more preferably 1-16, still more preferably 1-12, Dimethylamino group, diethylamino group, dibutylamino group, anilino group, etc.), acylamino group (preferably charcoal) The number is 2 to 20, more preferably 2 to 16, and further preferably 2 to 13. For example, acetylamino, tridecanoylamino, benzoylamino, etc.), a sulfonylamino group (preferably having 1 to 20 carbon atoms, more preferably Is 1 to 16, more preferably 1 to 12, for example, methanesulfonylamino, butanesulfonylamino, benzenesulfonylamino and the like, and a ureido group (preferably having 1 to 20 carbon atoms, more preferably 1 to 16, more preferably Are 1-12, for example, ureido, methylureido, phenylureido, etc.), carbamate groups (preferably having 2-20 carbon atoms, more preferably 2-16, still more preferably 2-12, for example, methoxycarbonyl Amino, phenyloxycarbonylamino, etc.), carboxyl group, carbamo An yl group (preferably having 1 to 20 carbon atoms, more preferably 1 to 16 carbon atoms, still more preferably 1 to 12 carbon atoms such as carbamoyl, N, N-diethylcarbamoyl, N-dodecylcarbamoyl, N-phenylcarbamoyl, etc.), An alkoxycarbonyl group (preferably having 2 to 20 carbon atoms, more preferably 2 to 16 carbon atoms, still more preferably 2 to 12 carbon atoms such as methoxycarbonyl, ethoxycarbonyl, butoxycarbonyl, etc.), an acyl group (preferably having 2 to 2 carbon atoms). 20, More preferably, it is 2-16, More preferably, it is 2-12, for example, acetyl, benzoyl, formyl, pivaloyl etc., a sulfo group, a sulfonyl group (preferably C1-C20, more preferably 1-16) And more preferably 1 to 12, for example, mesyl, tosyl, etc.), sulfa Yl group (preferably having 0 to 20 carbon atoms, more preferably 0 to 16 carbon atoms, still more preferably 0 to 12 carbon atoms such as sulfamoyl, methylsulfamoyl, dimethylsulfamoyl, phenylsulfamoyl, etc.) , A cyano group, a nitro group, a hydroxyl group, a mercapto group, an alkylthio group (preferably having a carbon number of 1-20, more preferably 1-16, still more preferably 1-12, such as methylthio, butylthio, etc.), a heterocyclic ring Groups (preferably having 2 to 20 carbon atoms, more preferably 2 to 16 carbon atoms, further preferably 2 to 12 carbon atoms such as pyridyl, imidazolyl, pyrrolidyl, etc.). These substituents may be further substituted with other substituents.
[0112]
-R in general formulas (2) and (3)^2l, R³¹, R³²Among the above, preferred as the substituent represented by halogen atom, alkyl group, aryl group, alkoxy group, aryloxy group, acyloxy group, anilino group, acylamino group, sulfonylamino group, carboxyl group, carbamoyl group, An acyl group, a sulfo group, a sulfonyl group, a sulfamoyl group, a cyano group, a hydroxyl group, a mercapto group, an alkylthio group, and a heterocyclic group.
[0113]
  Here, the compound represented by the general formula (2) is a carbamoyl group (preferably having a carbon number of 1 to 20, more preferably 1 to 16, more preferably 1 to 12, such as carbamoyl, N, N-diethylcarbamoyl, N-dodecylcarbamoyl, N-phenylcarbamoyl, N- (2-chlorophenyl) carbamoyl, N- (4-chlorophenyl) carbamoyl N- (2,4-dichlorophenyl) carbamoyl, N- (3 4-dichlorophenyl) carbamoyl etc.)Is a compound, An arylcarbamoyl group at the 2-position (preferably having 7 to 20 carbon atoms, more preferably 7 to 16 carbon atoms, further preferably 7 to 12 carbon atoms such as N-phenylcarbamoyl, N- (2-chlorophenyl) carbamoyl, N -(4-chlorophenyl) carbamoyl, N- (2,4-dichlorophenyl) carbamoyl, N- (3,4-dichlorophenyl) carbamoyl and the like are particularly preferable.
  Although the specific example of a compound represented by General formula (3) below is given, the compound used for this invention is not limited by these.
[0114]
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[0115]
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[0116]
The compounds represented by the general formulas (2) and (3) can be easily synthesized by methods known in the photographic industry.
The compounds represented by the general formulas (2) and (3) are water or an appropriate organic solvent such as alcohols (methanol, ethanol, propanol, fluorinated alcohol), ketones (acetone, methyl ethyl ketone), dimethylformamide, It can be used by dissolving in dimethyl sulfoxide, methyl cellosolve or the like.
[0117]
Alternatively, the emulsion is dispersed mechanically by using a well-known emulsification dispersion method using an oil such as dibutyl phthalate, tricresyl phosphate, glyceryl triacetate or diethyl phthalate, or an auxiliary solvent such as ethyl acetate or cyclohexanone. An object can be made and used. Alternatively, the compound powder can be dispersed in water and used by a ball mill, colloid mill, sand grinder mill, manton gourin, microfluidizer or ultrasonic wave according to well-known solid dispersion methods.
[0118]
The compounds represented by the general formulas (2) and (3) may be added to any layer on the support as long as the surface is the same as the photosensitive silver halide and the reducible silver salt. It is preferable to add to a layer containing silver halide or a layer adjacent thereto.
The addition amount of the compounds represented by the general formulas (2) and (3) is preferably 0.2 to 200 mmol, more preferably 0.3 to 100 mmol, and still more preferably 0.001 mol per mol of silver. 5-30 mmol. The compounds represented by the general formulas (2) and (3) may be used alone or in combination of two or more.
In particular, it is preferable to use the compound of the general formula (1) and the compound of the general formula (3) in combination.
[0119]
The compound represented by the general formula (2) is preferably a compound represented by the following general formula (4) or (5).
[0120]
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[0121]
In the general formula (4), R⁴¹, R⁴², R⁴³, X⁴¹And X⁴²Each independently represents a substituent bonded to the benzene ring by a hydrogen atom, a halogen atom, a carbon atom, an oxygen atom, a nitrogen atom, a sulfur atom or a phosphorus atom. X⁴¹And X⁴²At least one of -NR⁴⁴R⁴⁵It is group represented by these. R⁴⁴, R⁴⁵Each independently represents a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, a heterocyclic group, or —C (═O) —R, —C (═O) —C (═O) —R, —SO₂-R, -SO-R, -P (= O) (R)²Or it is group represented by -C (= NR ')-R. R and R ′ are each independently a group selected from a hydrogen atom, an alkyl group, an aryl group, a heterocyclic group, an amino group, an alkoxy group, and an aryloxy group. These substituents may be bonded to each other to form a ring.
[0122]
In general formula (5), X⁵¹Represents a substituent and X⁵²~ X⁵⁴Each independently represents a hydrogen atom or a substituent. X⁵¹~ X⁵⁴Is not a hydroxy group and X⁵³Is not a sulfonamide group. Also X⁵¹~ X⁵⁴The substituents represented by may be bonded to each other to form a ring. R⁵¹Represents a hydrogen atom, an alkyl group, an aryl group, a heterocyclic group, an amino group, or an alkoxy group.
[0123]
The development accelerator represented by the general formula (4) will be described.
In the general formula (4), R⁴¹~ R⁴³Each independently represents a substituent bonded to the benzene ring by a hydrogen atom, a halogen atom, a carbon atom, an oxygen atom, a nitrogen atom, a sulfur atom, or a phosphorus atom. Specific examples of the substituent bonded to the benzene ring at a carbon atom include linear, branched or cyclic alkyl groups (for example, methyl, ethyl, iso-propyl, tert-butyl, n-octyl, tert-amyl, 1, 3-tetramethylbutyl, cyclohexyl, etc.), alkenyl groups (for example, vinyl, allyl, 2-butenyl, 3-pentenyl, etc.), alkynyl groups (for example, propargyl group, 3-pentynyl group, etc.) An aryl group (for example, phenyl, p-methylphenyl, naphthyl, etc.), an acyl group (for example, acetyl, benzoyl, formyl, pivaloyl, etc.), an alkoxycarbonyl group (for example, , Methoxycarbonyl, ethoxycarbonyl, etc.), ants A ruoxycarbonyl group (for example, phenoxycarbonyl), a carbamoyl group (for example, carbamoyl, diethylcarbamoyl, phenylcarbamoyl, etc.), a cyano group, a carboxyl group, a heterocyclic group (for example, 3-pyrazolyl group, etc.) For example).
[0124]
Specific examples of the substituent bonded to the benzene ring with an oxygen atom include a hydroxyl group, an alkoxy group (for example, methoxy, ethoxy, butoxy and the like), an aryloxy group (for example, phenyloxy, 2-naphthyloxy and the like). ), A heterocyclic oxy group (for example, 4-pyridyloxy group and the like), an acyloxy group (for example, acetoxy, benzoyloxy and the like) and the like. Non-limiting specific examples of the substituent bonded to the benzene ring with a nitrogen atom include an amino group (for example, amino, methylamino, dimethylamino, diethylamino, dibenzylamino, etc.), a nitro group, a hydrazino group, A heterocyclic group (for example, 1-imidazolyl, morpholyl and the like), an acylamino group (for example, acetylamino, benzoylamino and the like), an alkoxycarbonylamino group (for example, methoxycarbonylamino and the like) can be mentioned. ), Aryloxycarbonylamino groups (for example, phenyloxycarbonylamino and the like), sulfonylamino groups (for example, methanesulfonylamino, benzenesulfonylamino and the like), sulfamoyl groups (for example, sulfamoyl, methyl) Sulfamoyl, dimethylsulfamoyl, phenylsulfamoyl, etc.), ureido groups (for example, ureido, methylureido, phenylureido, etc.), phosphorylamino groups (for example, diethylphosphorylamino, etc.) ) And imide groups (for example, succinimide, phthalimide, trifluoromethanesulfonimide, etc.). Non-limiting specific examples of the substituent bonded to the benzene ring with a sulfur atom include a mercapto group, a disulfide group, a sulfo group, a sulfino group, a sulfonylthio group, a thiosulfonyl group, an alkylthio group (for example, methylthio, ethylthio, etc.). ), Arylthio groups (for example, phenylthio and the like), sulfonyl groups (for example, mesyl, tosyl, phenylsulfonyl and the like), sulfinyl groups (for example, methanesulfinyl, benzenesulfinyl and the like). ), A heterocyclic thio group (for example, a 2-imidazolylthio group, etc.). Non-limiting specific examples of the substituent bonded to the benzene ring by a phosphorus atom include a phosphate group (for example, diethyl phosphate, diphenyl phosphate, etc.).
[0125]
R in the general formula (4)⁴¹~ R⁴³Preferred are hydrogen atom, halogen atom, linear, branched or cyclic alkyl group, aryl group, acyl group, alkoxycarbonyl group, aryloxycarbonyl group, cyano group, carboxyl group, heterocyclic group, hydroxyl group, alkoxy group. , Aryloxy group, heterocyclic oxy group, acyloxy group, amino group, nitro group, heterocyclic group, acylamino group, alkoxycarbonylamino group, aryloxycarbonylamino group, sulfonylamino group, imide group, sulfamoyl group, carbamoyl group, Examples include ureido groups, mercapto groups, disulfide groups, sulfo groups, sulfino groups, alkylthio groups, arylthio groups, sulfonyl groups, sulfinyl groups, and heterocyclic thio groups.
[0126]
R in the general formula (4)⁴¹~ R⁴³And more preferably a hydrogen atom, a halogen atom, a linear, branched or cyclic alkyl group, aryl group, acyl group, alkoxycarbonyl group, aryloxycarbonyl group, cyano group, carboxyl group, heterocyclic group, hydroxyl group, alkoxy group , Aryloxy group, acyloxy group, amino group, nitro group, heterocyclic group, acylamino group, alkoxycarbonylamino group, aryloxycarbonylamino group, sulfonylamino group, imide group, carbamoyl group, mercapto group, sulfo group, alkylthio group , An arylthio group and a sulfonyl group.
[0127]
R in the general formula (4)⁴¹~ R⁴³Particularly preferred are hydrogen atom, halogen atom, linear, branched or cyclic alkyl group, aryl group, acyl group, alkoxycarbonyl group, aryloxycarbonyl group, cyano group, carboxyl group, acyloxy group, acylamino group, alkoxycarbonyl. An amino group, an aryloxycarbonylamino group, a sulfonylamino group, a carbamoyl group, a sulfo group, an alkylsulfonyl group, and an arylsulfonyl group.
[0128]
X in the general formula (4)⁴¹, X⁴²Represents a substituent bonded to the benzene ring by a hydrogen atom, a halogen atom, a carbon atom, an oxygen atom, a nitrogen atom, a sulfur atom, or a phosphorus atom. Specific examples of the substituent bonded to the benzene ring at a carbon atom include linear, branched or cyclic alkyl groups (for example, methyl, ethyl, iso-propyl, tert-butyl, n-octyl, tert-amyl, 1, 3-tetramethylbutyl, cyclohexyl, etc.), alkenyl groups (for example, vinyl, allyl, 2-butenyl, 3-pentenyl, etc.), alkynyl groups (for example, propargyl group, 3-pentynyl group, etc.) An aryl group (for example, phenyl, p-methylphenyl, naphthyl, etc.), an acyl group (for example, acetyl, benzoyl, formyl, pivaloyl, etc.), an alkoxycarbonyl group (for example, , Methoxycarbonyl, ethoxycarbonyl, etc.), ants A ruoxycarbonyl group (for example, phenoxycarbonyl), a cyano group, a carboxyl group, a heterocyclic group (for example, 3-pyrazolyl group, etc.), a carbamoyl group (carbamoyl, diethylcarbamoyl, phenylcarbamoyl, etc.). Etc.).
[0129]
Non-limiting specific examples of the substituent bonded to the benzene ring with an oxygen atom in the general formula (4) include a hydroxyl group, an alkoxy group (for example, methoxy, ethoxy, butoxy, etc.), an aryloxy group (for example, Phenyloxy, 2-naphthyloxy, etc.), heterocyclic oxy groups (for example, 4-pyridyloxy group and the like), acyloxy groups (for example, acetoxy, benzoyloxy, etc.) and the like. .
[0130]
Specific examples of the substituent bonded to the benzene ring at the nitrogen atom in the general formula (4) include an amino group (for example, amino, methylamino, dimethylamino, diethylamino, dibenzylamino and the like), a nitro group, Hydroxam group, hydrazino group, heterocyclic group (for example, 1-imidazolyl, morpholyl, etc.), acylamino group (for example, acetylamino, benzoylamino, etc.), alkoxycarbonylamino group (for example, methoxycarbonyl) Amino, etc.), aryloxycarbonylamino group (for example, phenyloxycarbonylamino etc.), sulfonylamino group (for example, methanesulfonylamino, benzenesulfonylamino etc.), sulfamoyl group ( Eg to sulfamoyl, methylsulfamoyl, dimethylsulfamoyl, and the like phenylsulfamoyl.), Phosphorylamino group (e.g., diethyl phosphoryl amino, and the like.), And the like.
[0131]
Specific examples of the substituent bonded to the benzene ring by a sulfur atom in the general formula (4) include a mercapto group, a disulfide group, a sulfo group, a sulfino group, a sulfonylthio group, a thiosulfonyl group, an alkylthio group (for example, methylthio, ethylthio). ), Arylthio groups (for example, phenylthio and the like), sulfonyl groups (for example, mesyl, tosyl, phenylsulfonyl and the like), sulfinyl groups (for example, methanesulfinyl, benzenesulfinyl and the like). And a heterocyclic thio group (for example, a 2-imidazolylthio group and the like).
Non-limiting specific examples of the substituent bonded to the benzene ring by a phosphorus atom include a phosphate group (for example, diethyl phosphate, diphenyl phosphate, etc.).
[0132]
X in the general formula (4)⁴¹, X⁴²Preferred are hydrogen atom, halogen atom, linear, branched or cyclic alkyl group, aryl group, acyl group, alkoxycarbonyl group, aryloxycarbonyl group, cyano group, carboxyl group, heterocyclic group, hydroxyl group, alkoxy group. , Aryloxy group, heterocyclic oxy group, acyloxy group, amino group, nitro group, heterocyclic group, acylamino group, alkoxycarbonylamino group, aryloxycarbonylamino group, sulfonylamino group, imide group, sulfamoyl group, carbamoyl group, Examples include ureido groups, mercapto groups, disulfide groups, sulfo groups, alkylthio groups, arylthio groups, sulfonyl groups, and heterocyclic thio groups.
[0133]
X in the general formula (4)⁴¹, X⁴²And more preferably a hydrogen atom, a halogen atom, a linear, branched or cyclic alkyl group, aryl group, acyl group, alkoxycarbonyl group, aryloxycarbonyl group, cyano group, carboxyl group, hydroxyl group, alkoxy group, aryloxy group An acyloxy group, an amino group, an acylamino group, an alkoxycarbonylamino group, an aryloxycarbonylamino group, a sulfonylamino group, an imide group, a carbamoyl group, a sulfo group, and an arylsulfonyl group.
[0134]
X in the general formula (4)⁴¹, X⁴²Particularly preferred are hydrogen atom, halogen atom, linear, branched or cyclic alkyl group, aryl group, acyl group, alkoxycarbonyl group, aryloxycarbonyl group, cyano group, carboxyl group, alkoxy group, aryloxy group, An acyloxy group, an acylamino group, an alkoxycarbonylamino group, an aryloxycarbonylamino group, a sulfonylamino group, a carbamoyl group, a mercapto group, and an alkylthio group.
[0135]
X⁴¹, X⁴²At least one of -NR⁴⁴R⁴⁵It is group represented by these. R⁴⁴, R⁴⁵Each independently represents a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, a heterocyclic group, or —C (═O) —R, —C (═O) —C (═O) —R, —SO₂-R, -SO-R, -P (= O) (R)₂, -C (= NR ')-R. R and R ′ are each independently a group selected from a hydrogen atom, an alkyl group, an aryl group, a heterocyclic group, an amino group, an alkoxy group, and an aryloxy group.
[0136]
R⁴⁴, R⁴⁵Are a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, a heterocyclic group, they are, for example, a linear, branched or cyclic alkyl group (for example, methyl, ethyl, iso-propyl, tert-butyl, n-octyl, tert-amyl, 1,3-tetramethylbutyl, cyclohexyl, etc.), alkenyl groups (for example, vinyl, allyl, 2-butenyl, 3-pentenyl, etc.). , Alkynyl groups (for example, propargyl group, 3-pentenyl group and the like), aryl groups (for example, phenyl, p-methylphenyl, naphthyl and the like), heterocyclic groups (for example, 2-imidazolyl, 1-pyrazolyl group etc. are mentioned).
[0137]
R⁴⁴, R⁴⁵-C (= O) -R, -C (= O) -C (= O) -R, -SO₂-R, -SO-R, -P (= O) (R)₂, —C (═NR ′) — R, R and R ′ are each independently a hydrogen atom, an alkyl group (for example, methyl, ethyl, iso-propyl, tert-butyl, n -Octyl, tert-amyl, 1,3-tetramethylbutyl, cyclohexyl, etc.), aryl groups (eg, phenyl, p-methylphenyl, naphthyl etc.), heterocyclic groups (eg, 4-pyridyl) , 2-thienyl, 1-methyl-2-pyrrolyl and the like), amino group (for example, amino, dimethylamino, diphenylamino, phenylamino, 2-pyridylamino and the like), alkoxy group (for example, methoxy, Ethoxy, cyclohexyloxy and the like), aryloxy groups (for example, phenoxy, 2-naphthyl) Alkoxy, and the like) representing the like.
[0138]
R in the general formula (4)⁴⁴, R⁴⁵And preferred are a hydrogen atom, a linear, branched or cyclic alkyl group, an aryl group, an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a sulfamoyl group, a carbamoyl group, a sulfonyl group and a sulfinyl group. R⁴⁴, R⁴⁵And more preferably a hydrogen atom, a linear, branched or cyclic alkyl group, an aryl group, an acyl group, and a sulfonyl group. A particularly preferred combination is R⁴⁴, R⁴⁵One of these is a hydrogen atom, and the other is an alkylsulfonyl group or an arylsulfonyl group. These substituents may be further substituted with a substituent as described above. Moreover, if these substituents have a hydrogen atom with high acidity, the proton may dissociate to form a salt. As the counter cation, a metal ion, an ammonium ion, or a phosphonium ion is used. The state in which active hydrogen is dissociated in this way can be an effective countermeasure for cases where volatility during development of the compound becomes a problem. R⁴¹, R⁴², R⁴³, X⁴¹And X⁴²May be bonded to each other to form a ring.
Although the specific example of a compound represented by General formula (4) is shown below, the compound represented by General formula (4) which can be used for this invention is not limited to these.
[0139]
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[0140]
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[0141]
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[0142]
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[0143]
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[0144]
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[0145]
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[0146]
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[0147]
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[0148]
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[0149]
The development accelerator represented by the general formula (5) will be described.
In general formula (5), X⁵¹Represents a substituent (a substituent that can be substituted on the benzene ring and not a hydrogen atom). However, X⁵¹Is not a hydroxyl group. Specific examples of the substituent include a halogen atom, an alkyl group (including a cycloalkyl group and a bicycloalkyl group), an alkenyl group (including a cycloalkenyl group and a bicycloalkenyl group), an alkynyl group, an aryl group, a heterocyclic group, and a cyano group. Group, nitro group, carboxyl group, alkoxy group, aryloxy group, silyloxy group, heterocyclic oxy group, acyloxy group, carbamoyloxy group, alkoxycarbonyloxy group, aryloxycarbonyloxy group, acylamino group, aminocarbonylamino group, alkoxy Carbonylamino group, aryloxycarbonylamino group, sulfamoylamino group, alkyl and arylsulfonylamino group, mercapto group, alkylthio group, arylthio group, heterocyclic thio group, sulfamoyl group, sulfo group, al And arylsulfinyl groups, alkyl and arylsulfonyl groups, acyl groups, aryloxycarbonyl groups, alkoxycarbonyl groups, carbamoyl groups, aryl and heterocyclic azo groups, imide groups, phosphino groups, phosphinyl groups, phosphinyloxy groups, phosphine groups Examples include a finylamino group and a silyl group.
[0150]
More specifically, a halogen atom (a fluorine atom, a chlorine atom, a bromine atom, an iodine atom), an alkyl group [represents a linear, branched, or cyclic substituted or unsubstituted alkyl group. They are alkyl groups (preferably alkyl groups having 1 to 30 carbon atoms such as methyl group, ethyl group, n-propyl group, isopropyl group, tert-butyl group, n-octyl group, eicosyl group, 2-chloroethyl group, 2-cyanoethyl group, 2-ethylhexyl group), cycloalkyl group (preferably a substituted or unsubstituted cycloalkyl group having 3 to 30 carbon atoms, such as cyclohexyl group, cyclopentyl group, 4-n-dodecyl group) A cyclohexyl group), a bicycloalkyl group (preferably a substituted or unsubstituted bicycloalkyl group having 5 to 30 carbon atoms, that is, a monovalent group obtained by removing one hydrogen atom from a bicycloalkane having 5 to 30 carbon atoms). For example, bicyclo [1,2,2] heptan-2-yl group, bicyclo [2,2,2] octan-3-yl group), It is intended to encompass such tricyclo structure having many cyclic structures into. An alkyl group (for example, an alkyl group of an alkylthio group) in the substituents described below also represents such an alkyl group. ], An alkenyl group [represents a linear, branched or cyclic substituted or unsubstituted alkenyl group. They are an alkenyl group (preferably a substituted or unsubstituted alkenyl group having 2 to 30 carbon atoms, such as a vinyl group, an allyl group, a prenyl group, a geranyl group, an oleyl group), a cycloalkenyl group (preferably a carbon number of 3 A substituted or unsubstituted cycloalkenyl group having ˜30, that is, a monovalent group obtained by removing one hydrogen atom of a cycloalkene having 3 to 30 carbon atoms, such as a 2-cyclopenten-1-yl group, 2-cyclo Hexen-1-yl group), bicycloalkenyl group (substituted or unsubstituted bicycloalkenyl group, preferably a substituted or unsubstituted bicycloalkenyl group having 5 to 30 carbon atoms, that is, a bicycloalkene having one double bond. A monovalent group obtained by removing one hydrogen atom, for example, a bicyclo [2,2,1] hept-2-en-1-yl group, It is intended to include cyclo [2,2,2] oct-2-en-4-yl group). ], An alkynyl group (preferably a substituted or unsubstituted alkynyl group having 2 to 30 carbon atoms, such as an ethynyl group, a propargyl group, a trimethylsilylethynyl group),
[0151]
An aryl group (preferably a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, such as a phenyl group, a p-tolyl group, a naphthyl group, an m-chlorophenyl group, an o-hexadecanoylaminophenyl group), a heterocyclic group ( Preferably, it is a monovalent group obtained by removing one hydrogen atom from a 5- or 6-membered substituted or unsubstituted aromatic or non-aromatic heterocyclic compound, and more preferably 5 or 3 having 3 to 30 carbon atoms. 6-membered aromatic heterocyclic group, for example, 2-furyl group, 2-thienyl group, 2-pyrimidinyl group, 2-benzothiazolyl group), cyano group, nitro group, carboxyl group, alkoxy group (preferably C1-C30 substituted or unsubstituted alkoxy group, for example, methoxy group, ethoxy group, isopropoxy group, tert-butoxy group, n- Octyloxy group, 2-methoxyethoxy group), aryloxy group (preferably a substituted or unsubstituted aryloxy group having 6 to 30 carbon atoms, for example, phenoxy group, 2-methylphenoxy group, 4-tert-butylphenoxy group) , 3-nitrophenoxy group, 2-tetradecanoylaminophenoxy group), silyloxy group (preferably a silyloxy group having 3 to 20 carbon atoms, such as trimethylsilyloxy group, tert-butyldimethylsilyloxy group), heterocyclic oxy A group (preferably a substituted or unsubstituted heterocyclic oxy group having 2 to 30 carbon atoms, 1-phenylnaphtholazole-5-oxy group, 2-tetrahydropyranyloxy group), acyloxy group (preferably formyloxy group, C2-C30 substituted or unsubstituted alkylcarboni Oxy group, a substituted or unsubstituted arylcarbonyloxy group having 6 to 30 carbon atoms, e.g., formyloxy group, acetyloxy group, pivaloyloxy group, stearoyloxy group, benzoyloxy group, p- methoxyphenylcarbonyloxy group),
[0152]
A carbamoyloxy group (preferably a substituted or unsubstituted carbamoyloxy group having 1 to 30 carbon atoms such as N, N-dimethylcarbamoyloxy group, N, N-diethylcarbamoyloxy group, morpholinocarbonyloxy group, N, N -Di-n-octylaminocarbonyloxy group, Nn-octylcarbamoyloxy group), alkoxycarbonyloxy group (preferably a substituted or unsubstituted alkoxycarbonyloxy group having 2 to 30 carbon atoms, such as methoxycarbonyloxy group, Ethoxycarbonyloxy group, tert-butoxycarbonyloxy group, n-octylcarbonyloxy group), aryloxycarbonyloxy group (preferably a substituted or unsubstituted aryloxycarbonyloxy group having 7 to 30 carbon atoms such as pheno Cicarbonyloxy group, p-methoxyphenoxycarbonyloxy group, pn-hexadecyloxyphenoxycarbonyloxy group), acylamino group (preferably formylamino group, substituted or unsubstituted alkylcarbonylamino having 1 to 30 carbon atoms) Group, substituted or unsubstituted arylcarbonylamino group having 6 to 30 carbon atoms, such as formylamino group, acetylamino group, pivaloylamino group, lauroylamino group, benzoylamino group, 3,4,5-tri-n-octyl Oxyphenylcarbonylamino group), aminocarbonylamino group (preferably a substituted or unsubstituted aminocarbonylamino group having 1 to 30 carbon atoms, such as carbamoylamino group, N, N-dimethylaminocarbonylamino group, N, N -Diethylaminocal Nylamino group, morpholinocarbonylamino group), alkoxycarbonylamino group (preferably a substituted or unsubstituted alkoxycarbonylamino group having 2 to 30 carbon atoms, for example, methoxycarbonylamino group, ethynecarbonylamino group, tert-butoxycarbonylamino group) , N-octadecyloxycarbonylamino group, N-methyl-methoxycarbonylamino group), aryloxycarbonylamino group (preferably a substituted or unsubstituted aryloxycarbonylamino group having 7 to 30 carbon atoms, such as phenoxycarbonylamino Group, p-chlorophenoxycarbonylamino group, mn-octyloxyphenoxycarbonylamino group), sulfamoylamino group (preferably substituted or unsubstituted sulfamo having 0 to 30 carbon atoms) Ylamino group, for example, sulfamoylamino group, N, N-dimethylaminosulfonylamino group, Nn-octylaminosulfonylamino group),
[0153]
Alkyl and arylsulfonylamino groups (preferably substituted or unsubstituted alkylsulfonylamino groups having 1 to 30 carbon atoms, substituted or unsubstituted arylsulfonylamino groups having 6 to 30 carbon atoms such as methylsulfonylamino group, butylsulfonyl) Amino group, phenylsulfonylamino group, 2,3,5-trichlorophenylsulfonylamino group, p-methylphenylsulfonylamino group), mercapto group, alkylthio group (preferably substituted or unsubstituted alkylthio having 1 to 30 carbon atoms) Group such as methylthio group, ethylthio group, n-hexadecylthio group), arylthio group (preferably substituted or unsubstituted arylthio group having 6 to 30 carbon atoms such as phenylthio group, p-chlorophenylthio group, m-methoxyphenyl) Thio group) Heterocyclic thio group (preferably a substituted or unsubstituted heterocyclic thio group having 2 to 30 carbon atoms, such as 2-benzothiazolylthio group, 1-phenyltetrazol-5-ylthio group), sulfamoyl group (preferably carbon 0-30 substituted or unsubstituted sulfamoyl groups such as N-ethylsulfamoyl group, N- (3-dodecyloxypropyl) sulfamoyl group, N, N-dimethylsulfamoyl group, N-acetylsulfa Moyl group, N-benzoylsulfamoyl group, N- (N′-phenylcarbamoyl) sulfamoyl group), sulfo group, alkyl and arylsulfinyl group (preferably substituted or unsubstituted alkylsulfinyl group having 1 to 30 carbon atoms) 6-30 substituted or unsubstituted arylsulfinyl groups such as methylsulfur Nyl group, ethylsulfinyl group, phenylsulfinyl group, p-methylphenylsulfinyl group), alkyl and arylsulfonyl groups (preferably a substituted or unsubstituted alkylsulfonyl group having 1 to 30 carbon atoms, substituted or unsubstituted 6 to 30 carbon atoms) A substituted arylsulfonyl group, for example, a methylsulfonyl group, an ethylsulfonyl group, a phenylsulfonyl group, a p-methylphenylsulfonyl group), an acyl group (preferably a formyl group, a substituted or unsubstituted alkylcarbonyl group having 2 to 30 carbon atoms) A substituted or unsubstituted arylcarbonyl group having 7 to 30 carbon atoms, a heterocyclic carbonyl group bonded to a carbonyl group with a substituted or unsubstituted carbon atom having 4 to 30 carbon atoms, such as an acetyl group, a pivaloyl group, 2-chloroacetyl group, stearoyl group, benzoy Group, pn-octyloxyphenylcarbonyl group, 2-pyridylcarbonyl group, 2-furylcarbonyl group),
[0154]
Aryloxycarbonyl group (preferably a substituted or unsubstituted aryloxycarbonyl group having 7 to 30 carbon atoms, such as phenoxycarbonyl group, o-chlorophenoxycarbonyl group, m-nitrophenoxycarbonyl group, p-tert-butylphenoxy Carbonyl group), alkoxycarbonyl group (preferably a substituted or unsubstituted alkoxycarbonyl group having 2 to 30 carbon atoms, such as methoxycarbonyl group, ethoxycarbonyl group, tert-butoxycarbonyl group, n-octadecyloxycarbonyl group), carbamoyl A group (preferably a substituted or unsubstituted carbamoyl group having 5 to 30 carbon atoms, such as a carbamoyl group, an N-methylcarbamoyl group, an N, N-dimethylcarbamoyl group, an N, N-di-n-octylcarbamoyl group; N- (methylsulfonyl) carbamoyl group), aryl and heterocyclic azo groups (preferably substituted or unsubstituted arylazo groups having 6 to 30 carbon atoms, substituted or unsubstituted heterocyclic azo groups having 3 to 30 carbon atoms, such as , Phenylazo group, p-chlorophenylazo group, 5-ethylthio-1,3,4-thiadiazol-2-ylazo group), imide group (preferably N-succinimide group, N-phthalimide group), phosphino group (preferably A substituted or unsubstituted phosphino group having 2 to 30 carbon atoms, such as a dimethylphosphino group, a diphenylphosphino group, a methylphenoxyphosphino group, or a phosphinyl group (preferably a substituted or unsubstituted group having 2 to 30 carbon atoms) Phosphinyl group such as phosphinyl group, dioctyloxyphosphinyl group, Xyphosphinyl group), phosphinyloxy group (preferably a substituted or unsubstituted phosphinyloxy group having 2 to 30 carbon atoms such as diphenoxyphosphinyloxy group, dioctyloxyphosphinyloxy group), Finylamino group (preferably a substituted or unsubstituted phosphinylamino group having 2 to 30 carbon atoms, such as dimethoxyphosphinylamino group, dimethylaminophosphinylamino group), silyl group (preferably carbon Examples thereof include substituted or unsubstituted silyl groups having a number of 3 to 30, such as trimethylsilyl group, tert-butyldimethylsilyl group, and phenyldimethylsilyl group.
[0155]
In general formula (5), X⁵¹Preferred examples of the substituent represented by formula (1) include a halogen atom (fluorine atom, chlorine atom, bromine atom, iodine atom, preferably chlorine atom, bromine atom), acylamino group (preferably having 1 to 20 carbon atoms, more preferably carbon. 1 to 14, particularly preferably 1 to 8, for example, formylamino group, acetylamino group, benzoylamino group, etc., alkyl group (preferably 1 to 20 carbon atoms, more preferably 1 to 14 carbon atoms, Particularly preferably 1 to 8 carbon atoms, for example, a methyl group, an ethyl group, an isopropyl group, a cyclohexyl group, etc., an aryl group (preferably 6 to 20 carbon atoms, more preferably 6 to 14 carbon atoms, particularly preferably 6-8 carbon atoms, such as phenyl group, naphthyl group, p-methylphenyl group, etc., alkoxy groups (preferably carbon number 1-20, more preferred) Is carbon 1 to 14, particularly preferably carbon 1 to 8, such as methoxy group, ethoxy group, etc., aryloxy group (preferably 6 to 20 carbon atoms, more preferably 6 to 14 carbon atoms, particularly preferably carbon 6 to 8, for example, phenoxy group, 2-naphthyloxy group, etc.), acyloxy group (preferably 1 to 20 carbon atoms, more preferably 1 to 14 carbon atoms, particularly preferably 1 to 8 carbon atoms, for example, acetoxy group , A benzoyloxy group), a sulfonylamino group (preferably having 1 to 20 carbon atoms, more preferably 1 to 14 carbon atoms, particularly preferably 1 to 8 carbon atoms, such as a methanesulfonylamino group, a benzenesulfonylamino group, etc.), A carbamoyl group (preferably having 1 to 20 carbon atoms, more preferably 1 to 14 carbon atoms, particularly preferably 1 to 8 carbon atoms such as carbamoyl Group, N, N-dimethylcarbamoyl group, N-phenylcarbamoyl group, etc.), acyl group (preferably having 1 to 20 carbon atoms, more preferably 1 to 14 carbon atoms, particularly preferably 1 to 8 carbon atoms, such as formyl. Group, acetyl group, benzoyl group, etc.), alkoxycarbonyl group (preferably having 2 to 20 carbon atoms, more preferably 2 to 16 carbon atoms, still more preferably 2 to 12 carbon atoms, such as methoxycarbonyl group, ethyne group, etc. A carbonyl group, a butoxycarbonyl group, etc.), an aryloxycarbonyl group (preferably having 6 to 20 carbon atoms, more preferably 6 to 16 carbon atoms, still more preferably 6 to 12 carbon atoms, for example, phenoxycarbonyl group, 2-naphthyloxy group) Carbonyl group, etc.), cyano group, nitro group, more preferably halogen atom, acylamino group An alkyl group, particularly preferably a chlorine atom or a bromine atom.
[0156]
In general formula (5), X⁵³Each independently represents a hydrogen atom or a substituent. However, X⁵³Is not a hydroxyl group or a sulfonamide group. Specific examples of the substituent include X in the general formula (5).⁵¹Examples of the substituents mentioned above are the same (excluding the sulfonamide group). X⁵³As preferred, a hydrogen atom, a halogen atom (a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, preferably a chlorine atom or a bromine atom), an acylamino group (preferably having 1 to 20 carbon atoms, more preferably 1 to 1 carbon atom). 14, particularly preferably 1 to 8 carbon atoms, for example, formylamino group, acetylamino group, benzoylamino group, etc., alkyl group (preferably 1 to 20 carbon atoms, more preferably 1 to 14 carbon atoms, particularly preferably C1-C8, for example, a methyl group, an ethyl group, an isopropyl group, a cyclohexyl group, etc., an aryl group (preferably C6-C20, more preferably C6-C14, especially preferably C6-C6) To 8, for example, phenyl group, naphthyl group, p-methylphenyl group, etc.), alkoxy group (preferably having 1 to 20 carbon atoms, more preferably carbon 1 to 14, particularly preferably 1 to 8 carbon atoms, such as a methoxy group and an ethoxy group, and an aryloxy group (preferably 6 to 20 carbon atoms, more preferably 6 to 14 carbon atoms, and particularly preferably 6 carbon atoms). -8, such as phenoxy group, 2-naphthyloxy group, etc., acyloxy group (preferably having 1 to 20 carbon atoms, more preferably 1 to 14 carbon atoms, particularly preferably 1 to 8 carbon atoms, for example, acetoxy group, benzoyl Oxy group, etc.), carbamoyl group (preferably having 1 to 20 carbon atoms, more preferably 1 to 14 carbon atoms, particularly preferably 1 to 8 carbon atoms, such as carbamoyl group, N, N-dimethylcarbamoyl group, N-phenylcarbamoyl group) Fists, etc.), acyl groups (preferably having 1 to 20 carbon atoms, more preferably 1 to 14 carbon atoms, particularly preferably 1 to 8 carbon atoms, A rumil group, an acetyl group, a benzoyl group, etc.), an alkoxycarbonyl group (preferably having 2 to 20 carbon atoms, more preferably 2 to 16 carbon atoms, still more preferably 2 to 12 carbon atoms, such as methoxycarbonyl group, ethoxy A carbonyl group, a butoxycarbonyl group, etc.), an aryloxycarbonyl group (preferably having 6 to 20 carbon atoms, more preferably 6 to 16 carbon atoms, still more preferably 6 to 12 carbon atoms, for example, a phenoxycarbonyl group, 2-naphthyloxy, etc. A carbonyl group or the like, a cyano group, or a nitro group, more preferably a halogen atom, an acylamino group, or an alkyl group, and particularly preferably a chlorine atom or a bromine atom.
[0157]
In general formula (5), X⁵¹, X⁵³It is preferable that at least one of the substituents represented by is an electron withdrawing group. The electron withdrawing group is a substituent having a positive Hammett's substituent constant σρ value. Specific examples thereof include a halogen atom, a cyano group, a nitro group, an alkoxycarbonyl group, an aryloxycarbonyl group, an imino group, An imino group substituted with an N atom, a thiocarbonyl group, a perfluoroalkyl group, a sulfonamido group, a formyl group, a phosphoryl group, a carboxyl group, a carbamoyl group, an acyl group, a sulfo group (or a salt thereof), an alkylsulfonyl group, Examples thereof include an arylsulfonyl group, a sulfamoyl group, an acyloxy group, an acylthio group, a sulfonyloxy group, a heterocyclic group, or an aryl group substituted with these electron-withdrawing groups. X⁵¹, X⁵³Are more preferably both electron-withdrawing groups, more preferably both are halogen atoms, and particularly preferably both are chlorine atoms or bromine atoms.
[0158]
In general formula (5), X⁵², X⁵⁴Represents a hydrogen atom or a substituent. However, X⁵², X⁵⁴Is not a hydroxyl group. Specific examples of the substituent include X in the general formula (5).⁵¹Examples of the substituents are as follows. X⁵², X⁵⁴Preferred are hydrogen atom, halogen atom (fluorine atom, chlorine atom, bromine atom, iodine atom, preferably chlorine atom, bromine atom), acylamino group (preferably having 1 to 20 carbon atoms, more preferably 1 carbon atom). To 14, particularly preferably 1 to 8 carbon atoms, such as formylamino group, acetylamino group, benzoylamino group, etc., alkyl groups (preferably 1 to 20 carbon atoms, more preferably 1 to 14 carbon atoms, particularly preferably 1 to 8 carbon atoms, for example, a methyl group, an ethyl group, an isopropyl group, a cyclohexyl group, etc.), an aryl group (preferably having a carbon number of 6 to 20, more preferably a carbon number of 6 to 14, particularly preferably an anthrax number). 6 to 8, for example, phenyl group, naphthyl group, p-methylphenyl group, etc.), alkoxy group (preferably having 1 to 20 carbon atoms, more preferably carbon number) To 14, particularly preferably 1 to 8 carbon atoms, such as a methoxy group and an ethoxy group, and an aryloxy group (preferably 6 to 20 carbon atoms, more preferably 6 to 14 carbon atoms, and particularly preferably 6 to 8 carbon atoms). For example, phenoxy group, 2-naphthyloxy group, etc.), acyloxy group (preferably having 1 to 20 carbon atoms, more preferably 1 to 14 carbon atoms, particularly preferably 1 to 8 carbon atoms, for example, acetoxy group, benzoyloxy group, etc. ), A sulfonylamino group (preferably having 1 to 20 carbon atoms, more preferably 1 to 14 carbon atoms, particularly preferably 1 to 8 carbon atoms such as methanesulfonylamino group, benzenesulfonylamino group, etc.), carbamoyl group (preferably 1 to 20 carbon atoms, more preferably 1 to 14 carbon atoms, particularly preferably 1 to 8 carbon atoms, such as a carbamoyl group, N, N-dimethyl. Rucarbamoyl group, N-phenylcarbamoyl group, etc.), acyl group (preferably 1-20 carbon atoms, more preferably 1-14 carbon atoms, particularly preferably 1-8 carbon atoms, such as formyl group, acetyl group, benzoyl group, etc. ), An alkoxycarbonyl group (preferably having 2 to 20 carbon atoms, more preferably 2 to 16 carbon atoms, still more preferably 2 to 12 carbon atoms, such as a methoxycarbonyl group, an ethoxycarbonyl group, a butoxycarbonyl group, etc.), Aryloxycarbonyl group (preferably having 6 to 20 carbon atoms, more preferably 6 to 16 carbon atoms, still more preferably 6 to 12 carbon atoms, such as phenoxycarbonyl group, 2-naphthyloxycarbonyl group, etc.), cyano group, nitro group It is a group. More preferred are a hydrogen atom, an alkyl group, an aryl group, a halogen atom, and an acylamino group, and particularly preferred are a hydrogen atom, a methyl group, and an ethyl group.
[0159]
In general formula (5), X⁵¹~ X⁵⁴May be further substituted. Specific examples of the substituent include X in the general formula (5).⁵¹The substituents mentioned as examples of are also mentioned. X⁵¹~ X⁵⁴May be bonded to each other to form a ring.
[0160]
In the general formula (5), R⁵¹Is a hydrogen atom, an alkyl group (preferably 1-20 carbon atoms, more preferably 1-14 carbon atoms, particularly preferably 1-7 carbon atoms, such as a methyl group, an ethyl group, an isopropyl group, a cyclohexyl group, etc.) An aryl group (preferably having a carbon number of 6 to 20, more preferably a carbon number of 6 to 14, particularly preferably a carbon number of 6 to 8, such as a phenyl group, a naphthyl group, a p-methylphenyl group, etc.), a heterocyclic group (for example, , Pyridyl group, imidazolyl group, pyrrolidyl group), amino group (preferably having 0 to 20 carbon atoms, more preferably 0 to 14 carbon atoms, particularly preferably 0 to 8 carbon atoms, such as amino group, methylamino group, N, N-dimethylamino group, N-phenylamino group, etc.), alkoxy group (preferably having 1 to 20 carbon atoms, more preferably 1 to 14 carbon atoms, particularly preferably 1 to 8 carbon atoms, Example, if a methoxy group, an ethoxy group, etc.). Preferably, they are a hydrogen atom, an aryl group, a heterocyclic group, an amino group, an alkoxy group, and an alkyl group having 1 to 7 carbon atoms, more preferably an aryl group or an alkyl group having 1 to 7 carbon atoms, particularly preferably. An aryl group. R⁵¹May be further substituted. Specific examples of the substituent include X in the general formula (5).⁵¹Examples of the substituents are as follows.
[0161]
In general formula (5), X⁵¹~ X⁵⁴, R⁵¹The combination of X is preferably X⁵¹, X⁵³At least one of is a halogen atom, and X⁵², X⁵⁴Is a hydrogen atom or an alkyl group, R⁵¹Is an aryl group or an alkyl group having 1 to 7 carbon atoms. A more preferred combination is X⁵¹, X⁵³Are both chlorine or bromine atoms, and X⁵²Is a hydrogen atom or an alkyl group, and X⁵⁴Is a hydrogen atom and R⁵¹Is an aryl group.
[0162]
The preferable range of the total molecular weight of the compound represented by the general formula (5) is 170 to 800, more preferably 220 to 650, and particularly preferably 220 to 500.
[0163]
Specific examples of the compound represented by the general formula (5) are given below, but the present invention is not limited to these specific examples.
[0164]
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[0165]
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[0166]
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[0167]
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[0168]
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[0169]
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[0170]
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[0171]
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[0172]
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[0173]
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[0174]
The compound represented by the general formula (3) is more preferably a compound represented by the following general formula (6).
[0175]
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[0176]
Hereinafter, the compound represented by Formula (6) will be described.
In the general formula (6), R⁶¹Represents an alkyl group, an aryl group, an alkenyl group, an alkynyl group, and X⁶¹Represents an acyl group, an alkoxycarbonyl group, a carbamoyl group, a sulfonyl group, or a sulfamoyl group. Y⁶¹~ Y⁶⁵Each independently represents a hydrogen atom or a substituent.
[0177]
In the general formula (6), R⁶¹Is preferably a linear, branched, cyclic or a combination thereof having 1 to 30 carbon atoms, more preferably 1 to 16 carbon atoms, and still more preferably 1 to 13 carbon atoms. For example, methyl, Ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, t-butyl, n-hexyl, cyclohexyl, n-octyl, t-octyl, n-amyl, t-amyl, n-decyl, n -Dodecyl, n-tridecyl, benzyl, phenethyl and the like can be mentioned.
[0178]
In the general formula (6), R⁶¹Is preferably 6 to 30 carbon atoms, more preferably 6 to 20 carbon atoms, still more preferably 6 to 12 carbon atoms, such as phenyl, 4-methylphenyl, 2-chlorophenyl, 4-chlorophenyl. 2,4-dichlorophenyl, 3,4-dichlorophenyl, 2-methoxyphenyl, 4-methoxyphenyl, 4-hexyloxyphenyl, 2-dodecyloxyphenyl, naphthyl and the like.
[0179]
In the general formula (6), R⁶¹Is preferably 2 to 30 carbon atoms, more preferably 2 to 20 carbon atoms, still more preferably 2 to 12 carbon atoms, such as a vinyl group, an allyl group, an isopropenyl group, a butenyl group, and a cyclohexenyl group. And so on.
R⁶¹Is preferably 2-30 carbon atoms, more preferably 2-20 carbon atoms, still more preferably 2-12 carbon atoms, and examples thereof include an ethynyl group and a propynyl group.
[0180]
In the general formula (6), R⁶¹May further have a substituent, and examples of a preferable substituent include Y in the compound represented by the general formula (6) described later.⁶¹~ Y⁶⁵The substituent represented by these can be mentioned.
[0181]
In the general formula (6), R⁶¹More preferably represents an alkyl group or an aryl group, and particularly preferably represents an alkyl group.
[0182]
X in the general formula (6)⁶¹Represents an acyl group, an alkoxycarbonyl group, a carbamoyl group, a sulfonyl group or a sulfamoyl group.
X in the general formula (6)⁶¹Is preferably 2-20, more preferably 2-16, and even more preferably 2-12, such as acetyl, propionyl, butyryl, valeryl, hexanoyl, myristyl, palmitoyl, stearyl, Examples include oleyl, acryloyl, cyclohexanecarbonyl, benzoyl, formyl, bivaloyl and the like.
[0183]
X in the general formula (6)⁶¹Is preferably 2-20 carbon atoms, more preferably 2-16 carbon atoms, still more preferably 2-12 carbon atoms, and examples thereof include methoxycarbonyl, ethoxycarbonyl, butoxycarbonyl, phenoxycarbonyl and the like. .
[0184]
X in the general formula (6)⁶¹Is preferably 1 to 20 carbon atoms, more preferably 1 to 16 carbon atoms, still more preferably 1 to 12 carbon atoms, such as carbamoyl, N, N-diethylcarbamoyl, N-dodecylcarbamoyl, N- Decylcarbamoyl, N-hexadecylcarylvamoyl, N-phenylcarbamoyl, N- (2-chlorophenyl) carbamoyl, N- (4-chlorophenyl) carbamoyl, N- (2,4-dichlorophenyl) carbamoyl, N- (3, 4-dichlorophenyl) carbamoyl, N-pentachlorophenylcarbamoyl, N- (2-methoxyphenyl) carbamoyl, N- (4-methoxyphenyl) carbamoyl, N- (2,4-dimethoxyphenyl) carbamoyl, N- (2- Dodecyloxyphenyl) carbamoyl, N (4-dodecyloxy-off phenyl) carbamoyl, and the like.
[0185]
X in the general formula (6)⁶¹Is preferably 1 to 20 carbon atoms, more preferably 1 to 16 carbon atoms, still more preferably 1 to 12 carbon atoms, such as mesyl, ethanesulfonyl, cyclohexanesulfonyl, benzenesulfonyl, tosyl, 4-chlorobenzene. And sulfonyl.
X in the general formula (6)⁶¹Is preferably 0-20, more preferably 0-16, and still more preferably 0-12, and examples thereof include sulfamoyl, methylsulfamoyl, dimethylsulfamoyl and the like.
[0186]
X in the general formula (6)⁶¹May further have a substituent. Examples of preferred substituents include Y of the compound of the general formula (1) described later.⁶¹~ Y⁶⁵The substituent represented by these can be mentioned.
[0187]
X in the general formula (6)⁶¹Preferably represents a carbamoyl group, more preferably an alkylcarbamoyl group or an arylcarbamoyl group, and particularly preferably an arylcarbamoyl group.
[0188]
In general formula (6), Y⁶¹~ Y⁶⁵Each independently represents a hydrogen atom or a substituent.
Y⁶¹~ Y⁶⁵Any substituent may be used as long as it does not adversely affect photographic properties. For example, a halogen atom (for example, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom), a linear, branched, cyclic or a combination thereof (preferably having 1 to 20 carbon atoms, more preferably 1 to 16 carbon atoms, still more preferably Are, for example, methyl, ethyl, n-propyl, isopropyl, sec-butyl, t-butyl, t-octyl, n-amyl, t-amyl, n-dodecyl, n-tridecyl, cyclohexyl Etc.), an alkenyl group (preferably 2-20, more preferably 2-16, still more preferably 2-12, such as vinyl, allyl, 2-butenyl, 3-pentenyl, etc.), an aryl group (preferably Has 6 to 30 carbon atoms, more preferably 6 to 20 carbon atoms, still more preferably 6 to 12 carbon atoms such as phenyl, p-methylphenyl, Til, etc.), an alkoxy group (preferably having 1 to 20 carbon atoms, more preferably 1 to 16, more preferably 1 to 12, such as methoxy, ethoxy, propoxy, butoxy, etc.), an aryloxy group (preferably carbon The number is 6-30, more preferably 6-20, and even more preferably 6-12. For example, phenyloxy, 2-naphthyloxy, etc.), preferably an acyloxy group having 2-20 carbon atoms, more preferably 2-16. More preferably, it is 2-12, for example, acetoxy, benzoyloxy, etc.), an amino group (preferably C0-20, more preferably 1-16, still more preferably 1-12, for example, dimethylamino Group, diethylamino group, dibutylamino group, anilino group, etc.), acylamino group (preferably having 2 to 20 carbon atoms, and more) Mashiku 2 to 16, more preferably from 2 to 13, e.g., acetylamino, tri decanoyl, benzoylamino, etc.),
[0189]
A sulfonylamino group (preferably having 1 to 20 carbon atoms, more preferably 1 to 16, more preferably 1 to 12, such as methanesulfonylamino, butanesulfonylamino, benzenesulfonylamino, etc.), ureido group (preferably carbon The number is 1 to 20, more preferably 1 to 16, and further preferably 1 to 12. For example, ureido, methylureido, phenylureido, etc.), carbamate group (preferably having 2 to 20 carbon atoms, more preferably 2 to 16 carbon atoms). More preferably, it is 2-12, for example, methoxycarbonylamino, phenyloxycarbonylamino, etc., a carboxyl group, a carbamoyl group (preferably having 1 to 20 carbon atoms, more preferably 1 to 16, more preferably 1 to 12). For example, carbamoyl, N, N-diethylcarbamo , N-dodecylcarbamoyl, N-phenylcarbamoyl, etc.), an alkoxycarbonyl group (preferably having a carbon number of 2-20, more preferably 2-16, still more preferably 2-12, such as methoxycarbonyl, ethynecarbonyl, etc. , Butoxycarbonyl, etc.), an acyl group (preferably having 2 to 20 carbon atoms, more preferably 2 to 16, more preferably 2 to 12, such as acetyl, benzoyl, formyl, pivaloyl, etc.), sulfo group, sulfonyl group (Preferably having 1 to 20 carbon atoms, more preferably 1 to 16 carbon atoms, still more preferably 1 to 12 carbon atoms such as mesyl, tosyl, etc.), sulfamoyl groups (preferably having 0 to 20 carbon atoms, more preferably 0 to 16 carbon atoms). More preferably, it is 0-12, for example, sulfamoyl, methylsulfamoyl Dimethylsulfamoyl, phenylsulfamoyl, etc.), cyano group, nitro group, hydroxyl group, mercapto group, alkylthio group (preferably having 1 to 20 carbon atoms, more preferably 1 to 16, more preferably 1 to 12). , For example, methylthio, butylthio and the like), heterocyclic groups (preferably having 2 to 20 carbon atoms, more preferably 2 to 16 carbon atoms, and further preferably 2 to 12 carbon atoms such as pyridyl, imidazolyl, pyrrolidyl and the like). . These substituents may be further substituted with other substituents.
[0190]
In general formula (6), Y⁶¹~ Y⁶⁵Among the above, preferred as the substituent represented by halogen atom, alkyl group, aryl group, alkoxy group, aryloxy group, acyloxy group, anilino group, acylamino group, sulfonylamino group, carboxyl group, carbamoyl group, An acyl group, a sulfo group, a sulfonyl group, a sulfamoyl group, a cyano group, a hydroxyl group, a mercapto group, an alkylthio group, and a heterocyclic group.
[0191]
In the general formula (6), R⁶¹Is an alkyl group, X⁶¹Is a carbamoyl group, Y⁶¹~ Y⁶⁵A combination in which is a hydrogen atom is preferred.
[0192]
Hereinafter, although the specific example of a compound represented by General formula (6) is given, this invention is not limited by these specific examples.
[0193]
[Table 5]
[0194]
[Table 6]
[0195]
[Table 7]
[0196]
[Table 8]
[0197]
[Table 9]
[0198]
[Table 10]
[0199]
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[0200]
[Table 11]
[0201]
[Table 12]
[0202]
[Table 13]
[0203]
The development accelerators represented by the general formulas (1) to (6) may be added to the coating solution by any method such as a solution, a powder, a solid fine particle dispersion, an emulsion, and an oil protect dispersion. In particular, when used together with the latex of the present invention, it is preferably added as solid fine particles. The solid fine particle dispersion can be performed by a known finer means (for example, a ball mill, a vibrating ball mill, a sand mill, a colloid mill, a jet mill, or a roller mill). A dispersion aid may be used when dispersing the solid fine particles.
[0204]
<Reducing agent>
The reducing agent used in the present invention will be described.
The photothermographic material of the present invention contains a reducing agent. The reducing agent may be any substance (preferably an organic substance) that reduces silver ions to metallic silver. Such reducing agents are described in JP-A No. 11-65021, paragraphs 0043 to 0045, and European Patent Publication No. 0803764A1, page 7, line 34 to page 18, line 12.
In the present invention, as the reducing agent, a so-called hindered phenol reducing agent having a substituent at the ortho position of the phenolic hydroxyl group or a bisphenol reducing agent is preferable, and a compound represented by the following general formula (7) is more preferable.
[0205]
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[0206]
In the general formula (7), R⁷¹And R^{71 '}Each independently represents an alkyl group having 1 to 20 carbon atoms. R⁷²And R^{72 '}Each independently represents a hydrogen atom or a substituent that can be substituted on the benzene ring. L is a -S- group or -CHR.⁷³-Represents a group. R⁷³Represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms. X⁷¹And X^{71 '}Each independently represents a hydrogen atom or a group capable of substituting for a benzene ring.
[0207]
The general formula (7) will be described in detail.
In general formula (7), R⁷¹And R^{71 '}May have a substituent. The substituent is not particularly limited, but aryl group, hydroxy group, alkoxy group, aryloxy group, alkylthio group, arylthio group, acylamino group, sulfonamido group, sulfonyl group, phosphoryl group, acyl group, carbamoyl group An ester group, a ureido group, a urethane group, a halogen atom and the like are preferable.
[0208]
In general formula (7), R⁷¹And R^{71 '}Is preferably a secondary or tertiary alkyl group having 3 to 15 carbon atoms, and more preferably a tertiary alkyl group having 4 to 12 carbon atoms. Specific examples include isopropyl group, isobutyl group, t-butyl group, t-amyl group, t-octyl group, cyclohexyl group, cyclopentyl group, 1-methylcyclohexyl group, 1-methylcyclopropyl group and the like. A t-butyl group, a t-amyl group, and a 1-methylcyclohexyl group are preferable, and a t-butyl group is more preferable.
[0209]
In general formula (7), R⁷²And R^{72 '}Are each independently a hydrogen atom or a substituent that can be substituted on a benzene ring, and X⁷¹And X^{71 '}Each independently represents a hydrogen atom or a group capable of substituting for a benzene ring. The group that can be substituted on the benzene ring is preferably an alkyl group, an aryl group, a halogen atom, an alkoxy group, or an acylamino group.
[0210]
In general formula (7), R⁷²And R^{72 '}As, a C1-C20 alkyl group is preferable. Specifically, methyl group, ethyl group, propyl group, butyl group, isopropyl group, t-butyl group, t-amyl group, cyclohexyl group, 1-methylcyclohexyl group, benzyl group, methoxymethyl group, methoxyethyl group, etc. A methyl group, an ethyl group, a propyl group, an isopropyl group, and a t-butyl group are more preferable.
X in general formula (7)⁷¹And X^{71 '}Is preferably a hydrogen atom, a halogen atom or an alkyl group, more preferably a hydrogen atom.
[0211]
In the general formula (7), L represents an —S— group or —CHR.⁷³-Represents a group, -CHR⁷³-Is preferred.
R⁷³Is preferably a hydrogen atom or an alkyl group having 1 to 15 carbon atoms. Specifically, a hydrogen atom, a methyl group, an ethyl group, a propyl group, an isopropyl group, and a 2,4,4-trimethylpentyl group are preferable, and a hydrogen atom, a methyl group, a propyl group, and an isopropyl group are more preferable.
[0212]
R⁷³Is a hydrogen atom, R⁷²And R^{72 '}Is preferably an alkyl group having 2 to 5 carbon atoms, more preferably an ethyl group or a propyl group, and most preferably an ethyl group.
On the other hand, R⁷³Is a primary or secondary alkyl group having 1 to 8 carbon atoms, R⁷²And R^{72 '}Is preferably a methyl group. In this case, R¹³The primary or secondary alkyl group having 1 to 8 carbon atoms is preferably a methyl group, an ethyl group, a propyl group, or an isopropyl group, and more preferably a methyl group, an ethyl group, or a propyl group.
[0213]
R⁷¹, R^{71 '}, R⁷², R^{72 '}Are all methyl groups, R⁷³Is preferably a secondary alkyl group. In this case R⁷³As the secondary alkyl group, isopropyl group, isobutyl group, and 1-ethylpentyl group are preferable, and isopropyl group is more preferable.
The reducing agent is R⁷¹, R^{71 '}, R⁷², R^{72 '}And R⁷³Depending on the combination, the heat developability, developed silver color tone and the like are different. Since these can be adjusted by combining two or more kinds of reducing agents, it is preferable to use two or more kinds in combination depending on the purpose.
[0214]
Although the specific example of a compound represented by General formula (7) which is a reducing agent of this invention below is shown, this invention is not limited to these.
[0215]
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[0216]
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[0217]
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[0218]
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[0219]
In the present invention, the reducing agent is added in an amount of 0.1 to 3.0 g / m.²Is preferably 0.2 to 1.5 g / m.²More preferably, 0.3 to 1.0 g / m²More preferably. Further, it is preferably contained in an amount of 5 to 50% by mole, more preferably 8 to 30% by mole, and further preferably 10 to 20% by mole based on 1 mole of silver on the surface having the image forming layer.
The reducing agent is preferably contained in the image forming layer.
[0220]
The reducing agent may be contained in the coating solution by any method such as a solution form, an emulsified dispersion form, or a solid fine particle dispersion form, and may be contained in the photosensitive material.
Well-known emulsification dispersion methods include dissolving oil using an oil such as dibutyl phthalate, tricresyl phosphate, glyceryl triacetate or diethyl phthalate, or an auxiliary solvent such as ethyl acetate or cyclohexanone, and mechanically emulsifying the dispersion. The method of producing is mentioned.
[0221]
Further, as the solid fine particle dispersion method, a reducing agent powder is dispersed in an appropriate solvent such as water by a ball mill, a colloid mill, a vibrating ball mill, a sand mill, a jet mill, a roller mill, or an ultrasonic wave to create a solid dispersion. A method is mentioned. In this case, a protective colloid (for example, polyvinyl alcohol) or a surfactant (for example, an anionic surfactant such as sodium triisopropylnaphthalenesulfonate (a mixture of three isopropyl groups having different substitution positions)) may be used. Good.
In the mills, beads such as zirconia are usually used as a dispersion medium, and Zr and the like eluted from these beads may be mixed in the dispersion medium. The amount of Zr mixed into the dispersion medium is in the range of 1 ppm to 1000 ppm depending on the dispersion conditions. If the amount of Zr mixed in the heat-sensitive recording material is 0.5 mg or less per 1 g of silver, there is no practical problem.
The aqueous dispersion preferably contains a preservative (for example, benzoisothiazolinone sodium salt).
[0222]
(Description of organic silver salt)
1) Composition
Organic silver salts that can be used in the present invention are relatively stable to light, but when heated to 80 ° C. or higher in the presence of exposed photosensitive silver halide and reducing agent. It is a silver salt that functions as a silver ion supplier and forms a silver image. The organic silver salt may be any organic substance that can supply silver ions that can be reduced by a reducing agent. Regarding such non-photosensitive organic silver salt, paragraph numbers 0048 to 0049 of JP-A No. 10-62899, page 18 line 24 to page 19 line 37 of European Patent Publication No. 080864A1, European Patent Publication No. 0962812A1, JP-A-11-349591, JP-A-2000-7683, JP-A-2000-72711, and the like. Silver salts of organic acids, particularly silver salts of long-chain aliphatic carboxylic acids (having 10 to 30, preferably 15 to 28 carbon atoms) are preferred. Preferable examples of the fatty acid silver salt include silver lignocerate, silver behenate, silver arachidate, silver stearate, silver oleate, silver laurate, silver caproate, silver myristate, silver palmitate, silver erucate and the like. Including a mixture of In the present invention, among these fatty acid silvers, the silver behenate content is preferably 50 mol% to 100 mol%, more preferably 85 mol% to 100 mol%, still more preferably 95 mol% to 100 mol%. The following fatty acid silver is preferably used. Furthermore, it is preferable to use fatty acid silver having a silver erucate content of 2 mol% or less, more preferably 1 mol% or less, and still more preferably 0.1 mol% or less.
[0223]
Moreover, it is preferable that silver stearate content rate is 1 mol% or less. By setting the stearic acid content to 1 mol% or less, a silver salt of an organic acid having a low Dmin, high sensitivity and excellent image storage stability can be obtained. As said stearic acid content rate, 0.5 mol% or less is preferable and it is especially preferable not to contain substantially.
[0224]
Furthermore, when silver arachidate is included as the silver salt of the organic acid, the silver arachidate content is 6 mol% or less to obtain a low Dmin and an organic acid silver salt excellent in image storability. It is preferable at a point and it is still more preferable that it is 3 mol% or less.
[0225]
2) Shape and size
The shape of the organic silver salt that can be used in the present invention is not particularly limited, and may be any of a needle shape, a rod shape, a flat plate shape, and a flake shape.
In the present invention, scaly organic silver salts are preferred. Also, short needle-shaped, rectangular parallelepiped, cubic or potato-shaped amorphous particles having a major axis / uniaxial length ratio of 5 or less are preferably used. These organic silver particles have a feature that there is less fog at the time of thermal development than long needle-like particles having a ratio of the major axis to the uniaxial length of 5 or more. In particular, particles having a major axis / uniaxial ratio of 3 or less are preferable because the mechanical stability of the coating film is improved. In the present specification, the scaly organic silver salt is defined as follows. The organic acid silver salt was observed with an electron microscope, the shape of the organic acid silver salt particle was approximated to a rectangular parallelepiped, and the sides of the rectangular parallelepiped were designated a, b, and c from the shortest side (c was the same as b). Then, the shorter numerical values a and b are calculated, and x is obtained as follows.
x = b / a
[0226]
In this way, x is obtained for about 200 particles, and when the average value x (average) is obtained, particles satisfying the relationship of x (average) ≧ 1.5 are defined as flakes. Preferably, 30 ≧ x (average) ≧ 1.5, more preferably 15 ≧ x (average) ≧ 1.5. Incidentally, the needle shape is 1 ≦ x (average) <1.5.
[0227]
In the flake shaped particle, a can be regarded as a thickness of a tabular particle having a main plane with b and c as sides. The average of a is preferably 0.01 μm or more and 0.3 μm or less, and more preferably 0.1 μm or more and 0.23 μm or less. The average c / b is preferably 1 or more and 9 or less, more preferably 1 or more and 6 or less, still more preferably 1 or more and 4 or less, and most preferably 1 or more and 3 or less.
[0228]
By setting the equivalent sphere diameter to 0.05 μm or more and 1 μm or less, aggregation is hardly caused in the photosensitive material, and image storability is improved. The sphere equivalent diameter is preferably 0.1 μm or more and 1 μm or less. In the present invention, the method for measuring the equivalent sphere diameter is obtained by directly photographing a sample using an electron microscope and then image-processing the negative.
In the flake shaped particles, the spherical equivalent diameter / a of the particles is defined as the aspect ratio. The aspect ratio of the flake shaped particles is preferably 1.1 or more and 30 or less, more preferably 1.1 or more and 15 or less, from the viewpoint of preventing aggregation in the photosensitive material and improving the image storage stability. .
[0229]
The particle size distribution of the organic silver salt is preferably monodispersed. Monodispersion is preferably 100% or less, more preferably 80% or less, and even more preferably 50% of the value obtained by dividing the standard deviation of the lengths of the short and long axes by the short and long axes, respectively. It is as follows. The method for measuring the shape of the organic silver salt can be determined from a transmission electron microscope image of the organic silver salt dispersion. As another method for measuring monodispersity, there is a method of obtaining the standard deviation of the volume weighted average diameter of the organic silver salt, and the percentage (variation coefficient) of the value divided by the volume weighted average diameter is preferably 100% or less, more Preferably it is 80% or less, more preferably 50% or less. A commercially available laser light scattering particle size measuring device can be used for the measurement.
[0230]
3) Preparation method
Known methods and the like can be applied to the production and dispersion method of the organic acid silver used in the present invention. For example, the above-mentioned JP-A-10-62899, European Patent Publication No. 0803633A1, European Patent Publication No. 0962812A1, JP-A-11-349591, JP-A-2000-7683, JP-A-2000-72711, JP-A-2001-163889, 2001-163890, 2001-163827, 2001-33907, 2001-188313, 2001-83652, 2002-6442, 2002-49117, 2002-31870, 2002-107868 You can refer to the issue.
[0231]
In order to prepare the non-photosensitive organic silver salt so that the average sphere equivalent diameter is 0.05 μm or more and 1.0 μm or less and the variation coefficient of the volume weighted average of the sphere equivalent diameter is 30% or less, It is preferable to prepare by reacting at the reaction temperature shown and the mixing method. Further, a preparation method using a substantially transparent solution in which an alkali metal salt solution of an organic acid is dissolved in an organic solvent is preferable.
(Reaction temperature)
The organic silver salt particles in the present invention are preferably prepared at a reaction temperature of 60 ° C. or less from the viewpoint of preparing particles having a low Dmin. The chemical added, for example, the organic acid alkali metal aqueous solution may have a temperature higher than 60 ° C., but the temperature of the reaction bath to which the reaction solution is added is preferably 50 ° C. or lower. Furthermore, it is more preferable that it is 40 degrees C or less.
[0232]
(Mixing method)
The organic silver salt particles in the present invention are prepared by reacting a solution containing silver ions such as silver nitrate with an organic acid alkali metal salt solution or suspension, but the addition of 50% or more of the total added silver amount Is preferably performed simultaneously with the addition of the organic acid alkali metal salt solution or suspension. Examples of the addition method include a method of adding to the liquid surface of the reaction bath, a method of adding to the solution, and a method of adding to the closed mixing means described later, and any method may be used.
[0233]
(Example of reactor)
An example of a method of adding and preparing in a closed mixing means is shown below, but the present invention is not limited to this. FIG. 1 is an embodiment of a production apparatus for a non-photosensitive organic silver salt used in the present invention. In FIGS. 11 and 12, a silver ion-containing solution (for example, a silver nitrate aqueous solution) and an organic alkali metal salt solution are stored at a predetermined temperature. Reference numerals 13 and 14 are flow meters for measuring the flow rate when these solutions are added to the mixing device 18 which is sealed and filled with liquid via the pumps 15 and 16. In this embodiment, a pump 17 is provided which again supplies the prepared organic silver salt dispersion to the mixing device 18 as the third component. The liquid that has finished the reaction in the mixing device 18 is introduced into the heat exchanger 19 and quickly cooled.
(Water-soluble silver salt solution)
The pH of the silver ion-containing solution (for example, silver nitrate aqueous solution) used in the present invention is preferably pH 1 or more and 6 or less, more preferably pH 1.5 or more and 4 or less. Furthermore, acids and alkalis can be added for pH adjustment. The type of acid and alkali is not particularly limited.
The silver ion concentration of the silver ion-containing solution (for example, silver nitrate aqueous solution) used in the present invention is arbitrarily determined, but the molar concentration is preferably 0.03 mol / L or more and 6.5 mol / L or less, more preferably 0. It is 1 mol / L or more and 5 mol / L or less.
[0234]
(Aging)
The organic silver salt in the present invention may be ripened by raising the reaction temperature after the addition of the silver ion-containing solution (for example, silver nitrate aqueous solution) / or the organic acid alkali metal salt solution is completed. The aging in the present invention is considered to be different from the reaction temperature described above. During ripening, no addition of silver nitrate and organic acid alkali metal salt solution or suspension is performed. Aging is preferably performed at a reaction temperature of + 1 ° C. or higher and + 20 ° C. or lower, and more preferably + 1 ° C. or higher and + 10 ° C. or lower. The aging time is preferably determined by trial and error.
[0235]
(Split addition)
In the preparation of the organic salt salt in the present invention, the addition of the organic acid alkali metal salt solution may be divided into two or more and six or less times. By adding in a divided manner here, various functions can be imparted to the particles, such as addition for improving photographic performance and addition for changing the hydrophilicity of the surface. The number of divided additions is preferably 2 or more and 4 or less. Here, since the organic acid salt is solidified at a high temperature, it is necessary to take into account, for example, having a plurality of addition lines for dividing, or devising a circulation method, when dividing and adding.
[0236]
In the preparation of the organic silver salt in the present invention, 0.5 mol% or more and 30 mol% or less of the total number of added moles of the organic acid alkali metal salt solution may be added alone after the addition of the silver ion-containing solution is completed. preferable. Preferably, 3 mol% or more and 20 mol% or more are preferably added alone. This addition is preferably applied as a single divided addition. This addition may be added either in the closed mixing means or in the reaction vessel, but is preferably added to the reaction vessel. By carrying out this addition, it is possible to increase the hydrophilicity of the surface of the particles. As a result, the film forming property of the light-sensitive material is improved, and film peeling is improved.
[0237]
(Alkali metal solution of organic acid)
In the practice of the present invention, in order to form organic acid particles, at least one of a silver ion-containing solution, an organic acid alkali metal salt solution or suspension, and a solution prepared in advance in the reaction field, It is preferable that the alkali metal salt contains an organic solvent in an amount capable of forming a substantially transparent solution, not a string-like aggregate or micelle. The solution may be an organic solvent alone, but is preferably a mixed solution with water. The organic solvent used in the present invention is not particularly limited as long as it is water-soluble and has the above-mentioned properties. However, those that impede photographic performance are not preferred, preferably alcohol that can be mixed with water, acetone, A tertiary alcohol having 4 to 6 carbon atoms is preferred.
[0238]
Specifically, the alkali metal of the alkali metal salt of the organic acid used in the present invention is preferably Na or K. The alkali metal salt of the organic acid is prepared by adding NaOH or KOH to the organic acid. At this time, it is preferable that the amount of alkali is set to be equal to or less than the equivalent amount of the organic acid to leave the unreacted organic acid. In this case, the amount of residual organic acid is 3 mol% or more and 50 mol% or less, preferably 3 mol% or more and 30 mol% or less with respect to the total organic acid. Moreover, after adding an alkali more than desired amount, you may prepare by adding acids, such as nitric acid and a sulfuric acid, and neutralizing an excess alkali content.
Furthermore, the silver ion-containing solution and the organic acid alkali metal salt solution used in the present invention, or the liquid in the closed mixing vessel to which both liquids are added, are represented by, for example, general formula (1) in JP-A-62-65035. A water-soluble group-containing N heterocyclic compound as described in JP-A No. 62-150240, and an inorganic peroxide as described in JP-A No. 50-101019. A sulfur compound as described in JP-A-51-78319, a disulfide compound as described in JP-A-57-643, hydrogen peroxide, and the like can be added.
[0239]
In the organic acid alkali metal salt solution used in the present invention, the amount of the organic solvent is preferably 3% or more and 70% or less, more preferably 5% or more and 50% or less as the solvent volume with respect to the water volume. At this time, since the optimum solvent volume varies depending on the reaction temperature, the optimum amount can be determined by trial and error.
The concentration of the alkali metal salt of the organic acid used in the present invention is 5 to 50% by mass, preferably 7 to 45% by mass, more preferably 10 to 40% by mass. is there.
[0240]
The temperature of the third alcohol aqueous solution of the organic acid alkali metal salt added in the closed mixing means or in the reaction vessel is 50 for the purpose of maintaining the temperature necessary to avoid the crystallization and solidification of the organic acid alkali metal salt. The temperature is preferably from 90 ° C to 90 ° C, more preferably from 60 ° C to 85 ° C, most preferably from 65 ° C to 85 ° C. Further, in order to control the temperature of the reaction to be constant, it is preferably controlled to be constant at a certain temperature selected from the above range.
[0241]
As a result, the rate at which the third alcohol aqueous solution of the high-temperature organic acid alkali metal salt is rapidly cooled in the closed mixing means to precipitate in the form of fine crystals and the rate at which the organic silver salt is chlorinated by the reaction with the silver ion-containing solution are preferably controlled. The crystal form, crystal size, and crystal size distribution of the organic silver salt can be preferably controlled. At the same time, the performance can be further improved as a heat-developable material, particularly as a heat-developable photosensitive material.
[0242]
(Reaction vessel liquid)
The reaction vessel may contain a solvent in advance, and water is preferably used as the solvent put in advance, but a mixed solvent with the third alcohol is also preferably used.
[0243]
(Dispersing aid)
A dispersion aid that is soluble in an aqueous medium can be added to a tertiary alcohol aqueous solution of an organic acid alkali metal salt, a silver ion-containing solution, or a reaction solution. Any dispersing aid may be used as long as it can disperse the formed organic silver salt. A specific example is based on the description of the organic silver salt dispersion aid described below.
[0244]
(Desalination, dehydration)
In the method for preparing an organic silver salt, it is preferable to perform a desalting / dehydration step after the formation of the silver salt. The method is not particularly limited, and well-known and conventional means can be used. For example, known filtration methods such as centrifugal filtration, suction filtration, ultrafiltration, and flock-forming water washing by a coagulation method, and supernatant removal by centrifugal sedimentation are preferably used. Desalting / dehydration may be performed once or a plurality of times. Water may be added and removed continuously or separately. The desalting / dehydration is performed so that the conductivity of the finally dehydrated water is preferably 300 μS / cm or less, more preferably 100 μS / cm or less, and most preferably 60 μS / cm or less. The lower limit of conductivity in this case is not particularly limited, but is usually about 5 μS / cm.
[0245]
As the ultrafiltration method, for example, a method used for desalting / concentration of a silver halide emulsion can be applied. Reference can be made to Research Disclosure No. 10 208 (1972), No. 13 122 (1975), No. 16 351 (1977), and the like. The pressure difference and flow rate that are important as operating conditions can be selected by referring to the characteristic curve described in Haruhiko Oya's “Membrane Utilization Technology Handbook”, Koshobo Publishing (1978), p275. In order to suppress the aggregation and fogging of particles, it is necessary to find the optimum conditions. There are two methods for replenishing the solvent that is lost due to membrane permeation: a constant volume method in which the solvent is continuously added and a batch method in which the solvent is intermittently added, but the desalting time is relatively short. The formula is preferred.
[0246]
As the solvent to be replenished, pure water obtained by ion exchange or distillation is used. In order to maintain the pH at a target value, a pH adjusting agent or the like may be mixed in pure water, or organic You may add directly to a silver salt dispersion.
[0247]
As for ultrafiltration membranes, flat plate type, spiral type, cylindrical type, hollow fiber type, hollow fiber type, etc., which are already incorporated as modules, include Asahi Kasei Co., Ltd., Daicel Chemical Co., Ltd., Toray Co., Ltd., and Nitto Co., Ltd. Although it is commercially available from Denko etc., a spiral type or a hollow fiber type is preferred from the viewpoint of the total membrane area and detergency.
Moreover, it is preferable that the fraction molecular weight used as the threshold value parameter | index of the component which can permeate | transmit a film | membrane is 1/5 or less of the molecular weight of the polymer dispersing agent to be used.
[0248]
In the desalting by ultrafiltration in the present invention, prior to the treatment, it is preferable to disperse the liquid in advance until the particle size is about twice the average weight of the final particle size. The dispersing means may be any method such as a high-pressure homogenizer or a microfluidizer described later.
[0249]
It is preferable to keep the liquid temperature low after the grain formation until the desalting operation proceeds. This is because when the organic solvent used for dissolving the alkali metal salt of the organic acid penetrates into the generated organic silver salt particles, the shearing field when passing through the liquid feeding operation or the ultrafiltration membrane, This is because silver nuclei are easily generated by the pressure field. For this reason, in this invention, ultrafiltration operation is performed, keeping the temperature of organic silver salt particle dispersion at 1-30 degreeC, Preferably it is 5-25 degreeC.
[0250]
(Redistribution)
Further, in order to improve the coated surface state of the photothermographic material, particularly the photothermographic material, it is preferable to add and disperse the desalted and dehydrated organic silver salt to form a fine dispersion.
[0251]
Known methods and the like can be applied to the production and dispersion method of the organic silver salt used in the present invention. For example, the above-mentioned JP-A-8-234358, JP-A-10-62899, European Patent Publication No. 0803763A1, European Patent Publication No. 0968212A1, JP-A-11-349591, JP-A-2000-7683, 2000-72711, 2000-53682, 2000-75437, 2000-86669, 2000-143578, 2000-178278, 2000-256254, Japanese Patent Application Nos. 11-348228-30, 11-203413 No. 11-115457, No. 11-180369, No. 11-297964, No. 11-157638, No. 11-202081, Japanese Patent Application Nos. 2000-90093, No. 2000-195621, No. 2000-191226. 2000-213813, No. 2000-214155, the same 2000-191226 Patent or the like can be used as a reference.
[0252]
The method for finely dispersing the organic silver salt is known in the presence of a dispersing aid, such as known finer means (eg, high speed mixer, homogenizer, high speed impact mill, Banbury mixer, homomixer, kneader, ball mill, vibrating ball mill, planetary ball mill). , Attritor, sand mill, bead mill, colloid mill, jet mill, roller mill, tron mill, and high-speed stone mill).
[0253]
In order to obtain a uniform fatty silver salt solid dispersion having a high S / N, a small particle size, and no agglomeration, a large force is used as long as the organic silver salt particles as an image forming medium are not damaged or heated. It is preferable to give uniformly. For this purpose, a dispersion method is preferred in which a dispersion comprising an organic silver salt and a dispersant solution is converted into a high-speed flow and then the pressure is dropped. The dispersion medium in this case may be any solvent as long as the dispersion aid functions, but is preferably only water, and may contain an organic solvent as long as it is 20% by mass or less. Further, when a photosensitive silver salt is allowed to coexist at the time of dispersion, fogging is increased and sensitivity is remarkably lowered. Therefore, it is more preferable that the photosensitive silver salt is not substantially contained at the time of dispersion. In the present invention, the amount of the photosensitive silver salt in the dispersion to be dispersed is 0.1 mol% or less with respect to 1 mol of the organic silver salt in the liquid, and it is preferable not to add the photosensitive silver salt.
[0254]
For example, “dispersion system rheology and dispersion technology” (Toshio Kajiuchi, Hiroki Arai, 1991, Shinyamasha Publishing Co., Ltd.) Pp. 357-403), "Progress of Chemical Engineering, Vol. 24" (Chemical Engineering Society, Tokai Branch, 1990, Tsuji Shoten, p. 184-185), JP 59-49832, US Pat. No. 4,533,254, JP As described in detail in Japanese Patent Laid-Open Nos. 8-137044, 8-238848, 2-261525, and 1-94933, the redispersion method of the present invention uses a high-pressure pump to disperse a dispersion containing at least an organic silver salt. This is a method in which fine dispersion is performed by passing through a narrow slit provided in the pipe after the pressure is applied in the pipe, and then causing a sudden pressure drop in the dispersion. The
[0255]
For high-pressure homogenizers, in general, (a) “shearing force” generated when the dispersoid passes through a narrow gap (about 75 μm to 350 μm) at high pressure and high speed, (b) liquid-liquid collision in a narrow space of high pressure, Alternatively, it is considered that the impact force generated when colliding with the wall surface is not changed, and the cavitation force due to the subsequent pressure drop is further increased, and uniform and efficient dispersion is performed. In the old days, this type of dispersing device includes a gorin homogenizer. In this device, the liquid to be dispersed sent at a high pressure is converted into a high-speed flow in a narrow gap on the cylindrical surface, and this force is applied to the surrounding wall surface. Colliding and emulsifying / dispersing by the impact force. Examples of the liquid-liquid collision include a Y-type chamber of a microfluidizer, a spherical chamber using a spherical check valve as described in JP-A-8-103642, which will be described later, and the like. Includes a Z-type chamber of a microfluidizer. The working pressure is generally 100 to 600 kg / cm²(1-6 MPa), the flow rate is in the range of several m to 30 m / sec, and in order to increase the dispersion efficiency, a high-speed flow part is sawtoothed to increase the number of collisions has been devised. . Typical examples of such devices include a Gorin homogenizer, a microfluidizer manufactured by Microfluidics International Corporation, a microfluidizer manufactured by Mizuho Industry Co., Ltd., and a nanomizer manufactured by Special Machine Industries Co., Ltd. . Also described in JP-A-8-238848, JP-A-8-103642 and USP4533254.
[0256]
The organic silver salt can be dispersed in a desired particle size by adjusting the flow rate, the differential pressure at the time of pressure drop and the number of treatments, but from the viewpoint of photographic characteristics and particle size, the flow rate is 200 to 600 m / second, the pressure The differential pressure when descending is 900-3000kg / cm²The range of (9-30 MPa) is preferable, the flow rate is 300-600 m / sec, and the differential pressure during pressure drop is 1500-3000 kg / cm.²More preferably, it is in the range of (15-30 MPa). The number of distributed processes can be selected as necessary. Usually, a range of 1 to 10 times is selected, but about 1 to 3 times is selected from the viewpoint of productivity. It is not preferable from the viewpoint of dispersibility and photographic properties to increase the temperature of such a dispersion under high pressure. At high temperatures exceeding 90 ° C, the particle size tends to increase and fog tends to increase. . Therefore, a cooling device is included in the process before the conversion to the high-pressure and high-speed flow, the process after the pressure drop, or both of these processes. It is preferable to be kept at a temperature of 5 to 80 ° C., particularly 5 to 65 ° C. In particular, 1500 to 3000 kg / cm²It is effective to install the cooling device when dispersing at a high pressure in the range of (15 to 30 MPa). Depending on the required heat exchange amount, a cooling device using a static mixer in a double tube or triple tube, a multi-tube heat exchanger, a serpentine heat exchanger, or the like can be appropriately selected. In addition, in order to increase the efficiency of heat exchange, a suitable tube thickness, wall thickness, material, or the like may be selected in consideration of the operating pressure. The refrigerant used for the cooler is a heat exchanger such as 20 ° C. well water, 5-10 ° C. cold water treated with a refrigerator, or -30 ° C. ethylene glycol / water refrigerant, etc. can do.
[0257]
When organic silver salt is made into solid fine particles using a dispersant, for example, polyacrylic acid, acrylic acid copolymer, maleic acid copolymer, maleic acid monoester copolymer, acryloylmethylpropane sulfonic acid Synthetic anionic polymers such as copolymers, semi-synthetic anionic polymers such as carboxymethyl starch and carboxymethylcellulose, anionic polymers such as alginic acid and pectic acid, anions described in JP-A-52-92716, WO88 / 04794, etc. Surfactants, compounds described in Japanese Patent Application No. 7-350753, or known anionic, nonionic, cationic surfactants, other polyvinyl alcohol, polyvinyl pyrrolidone, carboxymethylcellulose, hydroxypropylcellulose, hydroxypropylmethy Known polymers such as cellulose, or a polymer compound existing in nature such as gelatin can be suitably selected and used. When a solvent is used as the dispersion medium, polyvinyl butyral, butyl ethyl cellulose, methacrylate copolymer, maleic anhydride ester copolymer, polystyrene and butadiene-styrene copolymer are preferably used.
[0258]
Dispersing aid is generally mixed with organic silver salt powder or wet cake organic silver salt before dispersion, and sent to the disperser as a slurry. The organic silver salt powder or wet cake may be obtained by heat treatment or treatment with a solvent. The pH may be controlled with an appropriate pH adjusting agent before or during dispersion.
[0259]
In addition to mechanical dispersion, it may be coarsely dispersed in a solvent by controlling the pH, and then finely divided by changing the pH in the presence of a dispersion aid. At this time, you may use a fatty acid solvent as a solvent used for rough dispersion.
[0260]
In addition, when the photosensitive silver salt is allowed to coexist at the time of dispersion of the organic silver salt, the fog is increased and the sensitivity is remarkably lowered. Therefore, it is more preferable that the photosensitive silver salt is not substantially contained at the time of dispersion. In the present invention, the amount of the photosensitive silver salt in the aqueous dispersion to be dispersed is 0.1 mol% or less with respect to 1 mol of the organic silver salt in the liquid, and no positive addition of the photosensitive silver salt is performed. Is.
[0261]
5) Amount added
The organic silver salt of the present invention can be used in a desired amount, but the total coating silver amount including silver halide is 0.1 to 5 g / m.²Is preferred, more preferably 03-3.0 g / m²More preferably, 0.5 to 2.0 g / m²It is. In particular, in order to improve image storage stability, the total amount of silver applied is 0.5 to 1.8 g / m.²Is preferable, preferably 0.5 to 1.6 g / m²It is.
[0262]
(Photosensitive silver halide)
1) Halogen composition
The photosensitive silver halide used in the present invention is not limited in the halogen composition, but preferably has a high silver iodide content of 5 mol% to 100 mol%. More preferably, they are 40 mol% or more and 100 mol% or less, More preferably, they are 90 mol% or more and 100 mol% or less. The rest is not particularly limited and can be selected from silver chloride, silver bromide, or organic silver salts such as silver thiocyanate and silver phosphate. Silver bromide and silver chloride are particularly preferred. By using such a silver halide having a high silver iodide content, it is possible to design a preferable photothermographic material in which image storage stability after development processing, in particular, an increase in fog due to light irradiation is remarkably small.
[0263]
The distribution of the halogen composition in the grains may be uniform, the halogen composition may be changed stepwise, or may be continuously changed. Further, silver halide grains having a core / shell structure can be preferably used. A preferable structure is a 2- to 5-fold structure, and more preferably 2- to 4-fold core / shell particles can be used. A technique for localizing silver bromide or silver iodide on the surface of silver chloride, silver bromide or silver chlorobromide grains can also be preferably used.
[0264]
2) Particle size
The average grain size of the high silver iodide used in the present invention is preferably 5 nm or more and 90 nm or less. If the size of the silver halide is large, it is generally not preferable because the amount of silver halide applied to achieve the required maximum density increases and the transparency of the film decreases.
In particular, the silver halide composition having a high silver iodide content according to the present invention has a specific action that the development is suppressed and the sensitivity is lowered and the density stability with respect to the development time is deteriorated when the coating amount is large. I found. For this reason, the maximum density cannot be obtained within a predetermined development time when the particle size exceeds a certain level. On the other hand, it has been found that if the amount added is limited to a certain amount or less, silver iodide has sufficient developability.
[0265]
In this way, when using high silver iodide, the size of the silver halide grains is sufficiently larger than that of conventional silver bromide and silver iodide containing low iodine to achieve a sufficient maximum optical density. It is necessary to be small and to keep the addition amount of silver iodide low. The preferred silver halide grain size is 5 nm or more and 70 nm or less, and more preferably 5 nm or more and 55 nm or less. Especially preferably, it is 10 nm or more and 40 nm or less. The term “particle size” as used herein refers to the average diameter when converted to a circle having the same area as the projected area observed with an electron microscope.
[0266]
3) Particle shape
Examples of the shape of the silver halide grains in the present invention include cubes, octahedrons, dodecahedrons, tetrahedrons, tabular grains, spherical grains, rod-shaped grains, and potato-shaped grains. The shape of a plane body or a tetrahedron is preferable. The dodecahedron referred to here is a particle having {001}, {1 (−1) 0}, {101} faces. A tetrahedron is a particle having {110}, {101}, {100} faces. Both the dodecahedron and the dodecahedron particles can have an arbitrary β phase and γ phase content, but preferably have at least a γ phase. More preferably, the average γ phase ratio is 5 mol% or more and 90 mol% or less, more preferably 10 mol% or more and 70 mol% or less, and further preferably 25 mol% or more and 50 mol% or less.
The above γ phase refers to a high silver iodide structure having a hexagonal wurtzite structure, and the β phase refers to a high silver iodide structure having a cubic zinc blend structure.
The average γ phase ratio mentioned here is determined using the method proposed by C.R.Berry. This method is determined based on the peak ratio of the silver iodide β phases (100), (101), (002) and the γ phase (111) by the powder X-ray diffraction method. Details are described in, for example, Physical Review, Volume 161, No. 3, p.848-851 (1967).
[0267]
4) Particle formation method
Methods for forming photosensitive silver halide are well known in the art, for example, the methods described in Research Disclosure June 1978, No. 17029, and US Pat. No. 3,700,458 can be used, Specifically, a method is used in which a photosensitive silver halide is prepared by adding a silver supply compound and a halogen supply compound to gelatin or another polymer solution, and then mixed with an organic silver salt. In addition, the method described in paragraph Nos. 0217 to 0224 of JP-A-11-119374, the method described in JP-A-11-352627, and Japanese Patent Application No. 2000-42336 are also preferable.
[0268]
For example, a so-called hydration method in which a part of the organic silver salt is halogenated with an organic or inorganic halide is also preferably used. The organic halide used here may be any compound that reacts with an organic silver salt to produce silver halide, but N-halogenoimide (N-bromosuccinimide, etc.), halogenated quaternary nitrogen compound (odor) And tetrabutylammonium bromide), and aggregates of halogenated quaternary nitrogen salts and halogen molecules (pyridinium perbromide). Any inorganic halogen compound may be used as long as it is a compound that reacts with an organic silver salt to produce silver halide, but alkali metal halide or ammonium (sodium chloride, lithium bromide, potassium iodide, ammonium bromide, etc.) ), Alkaline earth metal halides (calcium bromide, magnesium chloride, etc.), transition metal halides (ferric chloride, cupric bromide, etc.), metal complexes having a halogen ligand (sodium iridate bromide) , Ammonium rhodate, etc.) and halogen molecules (bromine, chlorine, iodine). Moreover, you may use desired organic inorganic halide together. The amount of halide added at the time of hydrating is preferably 1 to 500 mmol, more preferably 10 to 250 mmol as a halogen atom per mol of the organic silver salt.
[0269]
The photosensitive silver halide grains can be desalted by washing with water known in the art, such as a noodle method or a flocculation method, but in the present invention, it may or may not be desalted.
[0270]
In the present invention, a particularly preferable method for forming photosensitive silver halide grains is a method for forming grains in the absence of an organic silver salt. The photosensitive silver halide grains in the present invention are mixed with a non-photosensitive organic silver salt after being subjected to processing for high sensitivity and stabilization such as control of appropriate shape and chemical sensitization after grain formation. Is preferred.
[0271]
5) Heavy metal
The photosensitive silver halide grains preferably contain at least one metal complex selected from rhodium, rhenium, ruthenium, osnium, iridium, cobalt, mercury or iron. One kind of these metal complexes may be used, or two or more kinds of complexes of the same metal and different metals may be used in combination. The preferred content is in the range of 1 nanomolar (nmol) to 10 millimolar (mmol), and more preferably in the range of 10 nanomolar (nmol) to 100 micromolar (μmol) per mole of silver. As a specific metal complex structure, a metal complex having a structure described in JP-A-7-225449 can be used. For cobalt and iron compounds, hexacyano metal complexes can be preferably used. Specific examples include ferricyanate ion, ferrocyanate ion, hexacyanocobaltate ion and the like, but are not limited thereto. The phase containing the metal complex in the silver halide may be uniform, may be contained in the core part at a high concentration, or may be contained in the shell part at a high concentration, and is not particularly limited.
[0272]
6) Gelatin
Various gelatins can be used as the gelatin contained in the photosensitive silver halide emulsion used in the present invention. In order to maintain a good dispersion state of the photosensitive silver halide emulsion in the organic silver salt-containing coating solution, it is preferable to use a low molecular weight gelatin having a molecular weight of 500 to 60,000. These low molecular weight gelatins may be used at the time of particle formation or dispersion after desalting, but are preferably used at the time of dispersion after desalting.
[0273]
7) Chemical sensitization
The photosensitive silver halide grains are preferably chemically sensitized. As a preferable chemical sensitization method, a sulfur sensitization method, a selenium sensitization method and a tellurium sensitization method can be used as is well known in the art. Further, noble metal sensitization methods such as gold compounds, platinum, palladium, iridium compounds and reduction sensitization methods can be used. As the compound preferably used in the sulfur sensitization method, selenium sensitization method and tellurium sensitization method, known compounds can be used, but compounds described in JP-A-7-128768 can be used.
[0274]
8) Sensitizing dye
As a sensitizing dye applicable to the present invention, it can spectrally sensitize silver halide grains in a desired wavelength region when adsorbed on silver halide grains, and has a spectral sensitivity suitable for the spectral characteristics of the exposure light source. The dye can be advantageously selected. The photothermographic material of the invention is preferably spectrally sensitized so as to have a spectral sensitivity peak particularly in the range of 300 nm to 500 nm. As for the sensitizing dye and the addition method, paragraphs 0103 to 0109 of JP-A-11-65021, compounds represented by general formula (II) of JP-A-10-186572, and general formulas (I) of JP-A-11-119374 ) And a dye described in Paragraph No. 0106, U.S. Pat.Nos. 5,510,236 and 3,871,887, Example 5, a dye disclosed in JP-A-2-96131 and JP-A-59-48753, European Patent Publication No. 074364A1 page 19 line 38 to page 20 line 35, Japanese Patent Application No. 2000-86865, Japanese Patent Application No. 2000-102560, Japanese Patent Application No. 2000-205399, etc. Specific examples shown in Japanese Patent Application No. 2002-102319 are represented by general formulas Da to Dd. 1 to No. The dyes listed in 53 are also preferably used in the present invention. These sensitizing dyes may be used alone or in combination of two or more. In the present invention, the time when the sensitizing dye is added to the silver halide emulsion is preferably the time from the desalting step to the coating, more preferably from the desalting to the end of chemical ripening.
[0275]
The addition amount of the sensitizing dye in the present invention can be set to a desired amount in accordance with the sensitivity and fogging performance, but is 10 per mol of silver halide in the image forming layer.^-6~ 1 mol is preferred, more preferably 10^-Four~Ten^-1Is a mole.
[0276]
In the present invention, a supersensitizer can be used to improve spectral sensitization efficiency. Examples of supersensitizers used in the present invention include European Patent Publication No. 587,338, U.S. Pat.Nos. 3,877,943, 4,873,184, JP-A Nos. 5-341432, 11-109547, and 10-111543. And the compounds described.
[0277]
9) Combined use of silver halide
The photosensitive silver halide emulsion in the photothermographic material used in the present invention may be one kind or two or more kinds (for example, those having different average grain sizes, those having different halogen compositions, those having different crystal habits, Those having different chemical sensitization conditions) may be used in combination. The gradation can be adjusted by using a plurality of types of photosensitive silver halides having different sensitivities. As technologies related to these, JP-A-57-119341, 53-106125, 47-3929, 48-55730, 46-5187, 50-73627, 57-150841, etc. Can be mentioned. As the sensitivity difference, it is preferable that each emulsion has a difference of 0.2 logE or more.
[0278]
10) Mixing silver halide into coating solution
The preferred addition time of the silver halide of the present invention to the image-forming layer coating solution is from 180 minutes before coating to immediately before, preferably from 60 minutes to 10 seconds before coating. There is no particular limitation as long as the effect is sufficiently exhibited. Specific mixing methods include mixing in a tank in which the average residence time calculated from the addition flow rate and the amount of liquid delivered to the coater is the desired time, and by N. Harnby, MFEdwards, AWNienow, Takahashi There is a method of using a static mixer described in Chapter 8 of "Liquid Mixing Technology" (published by Nikkan Kogyo Shimbun, 1989).
[0279]
11) Application amount
The coating amount of the silver halide grains in the present invention is 0.5 mol% or more and 15 mol% or less, preferably 0.5 mol% or more and 12 mol% or less with respect to 1 mol of the silver of the non-photosensitive organic silver salt. It is. It is particularly preferably 0.5 mol% or more and 7 mol% or less, more preferably 0.5 mol% or more and 5 mol% or less.
[0280]
12) A compound in which a one-electron oxidant produced by one-electron oxidation can emit one electron or more.
In the photothermographic material of the invention, it is preferable that the one-electron oxidant produced by one-electron oxidation contains a compound capable of emitting one electron or more. The compound can be used alone or in combination with the above-described various chemical sensitizers to increase the sensitivity of silver halide.
[0281]
The one-electron oxidant produced by one-electron oxidation contained in the photothermographic material of the present invention is a compound selected from the following types 1 to 5 that can emit one or more electrons.
[0282]
(Type 1)
A compound in which a one-electron oxidant produced by one-electron oxidation can further emit two or more electrons with a subsequent bond cleavage reaction.
(Type 2)
The one-electron oxidant produced by one-electron oxidation is a compound capable of releasing another electron with subsequent bond cleavage reaction, and has two or more adsorptive groups to silver halide in the same molecule. Compound.
(Type 3)
A compound capable of emitting one or more electrons after a one-electron oxidant produced by one-electron oxidation undergoes a subsequent bond formation process.
(Type 4)
A compound capable of emitting one or more electrons after a one-electron oxidant produced by one-electron oxidation undergoes a subsequent intramolecular ring-cleaving reaction.
(Type 5)
In the compound represented by XY, X represents a reducing group, Y represents a leaving group, and a one-electron oxidant formed by one-electron oxidation of the reducing group represented by X is followed by XY A compound capable of releasing Y by releasing Y with a bond cleavage reaction and releasing another electron therefrom.
[0283]
Preferred among the compounds of types 1 and 3 to 5 are “compounds having an adsorbing group for silver halide in the molecule” or “partial structure of spectral sensitizing dye in the molecule”. Compound ". More preferred is a “compound having an adsorptive group to silver halide in the molecule”. The compounds of types 1 to 4 are more preferably “compounds having a nitrogen-containing heterocyclic group substituted with two or more mercapto groups as an adsorptive group”.
[0284]
The compounds of types 1 to 5 will be described in detail.
In the type 1 compound, “bond cleavage reaction” specifically means cleavage of bonds between carbon-carbon, carbon-silicon, carbon-hydrogen, carbon-boron, carbon-tin, and carbon-germanium elements, These may be further accompanied by carbon-hydrogen bond cleavage. A type 1 compound is a compound capable of emitting two or more (preferably three or more) electrons for the first time after a one-electron oxidation to form a one-electron oxidant with a bond cleavage reaction.
[0285]
Among the compounds of type 1, preferred compounds are represented by general formula (A), general formula (B), general formula (1), general formula (2) or general formula (3).
[0286]
Formula (A)
Embedded image
[0287]
General formula (B)
Embedded image
[0288]
In general formula (A), RED₁₁Represents a reducing group which can be oxidized by one electron, and L₁₁Represents a leaving group. R₁₁₂Represents a hydrogen atom or a substituent. R₁₁₁Is carbon atom (C) and RED₁₁And a nonmetallic atomic group capable of forming a cyclic structure corresponding to a tetrahydro form, hexahydro form, or octahydro form of a 5-membered or 6-membered aromatic ring (including an aromatic heterocycle).
[0289]
In the general formula (B), RED₁₂Represents a reducing group which can be oxidized by one electron, and L₁₂Represents a leaving group. R₁₂₁And R₁₂₂Each represents a hydrogen atom or a substituent. ED₁₂Represents an electron donating group. R in the general formula (B)₁₂₁And RED₁₂, R₁₂₁And R₁₂₂Or ED₁₂And RED₁₂And may be bonded to each other to form a cyclic structure.
[0290]
These compounds represented by general formula (A) or general formula (B) are represented by RED.₁₁Or RED₁₂After the reducing group represented by₁₁Or L₁₂Is a compound that can release two or more electrons, preferably three or more electrons, by releasing them by bond cleavage reaction.
[0291]
General formula (1), general formula (2), general formula (3)
Embedded image
[0292]
In general formula (1), Z₁Represents an atomic group capable of forming a 6-membered ring with a nitrogen atom and two carbon atoms of a benzene ring, and R₁, R₂, R_N1Each represents a hydrogen atom or a substituent, and X₁Represents a substitutable substituent on the benzene ring, m₁Represents an integer of 0 to 3, L₁Represents a leaving group. ED in general formula (2)_{twenty one}Represents an electron donating group, R₁₁, R₁₂, R_N21, R₁₃, R₁₄Each represents a hydrogen atom or a substituent, and X_{twenty one}Represents a substitutable substituent on the benzene ring, m_{twenty one}Represents an integer of 0 to 3, L_{twenty one}Represents a leaving group. R_N21, R₁₃, R₁₄, X_{twenty one}And ED_{twenty one}May be bonded to each other to form a cyclic structure. In the general formula (3), R₃₂, R₃₃, R₃₁, R_N31, R_a, R_bEach represents a hydrogen atom or a substituent, and L₃₁Represents a leaving group. However, R_N31When represents a group other than an aryl group, R_aAnd R_bCombine with each other to form an aromatic ring.
[0293]
After these compounds are oxidized by one electron,₁, L_{twenty one}Or L₃₁Is a compound that can release two or more electrons, preferably three or more electrons, by releasing them by bond cleavage reaction.
[0294]
Hereinafter, the compound represented by formula (A) will be described in detail below.
In general formula (A), RED₁₁A reducing group that can be oxidized by one electron is represented by R described later.₁₁₁And a divalent group obtained by removing one hydrogen atom at a suitable site for ring formation from the following monovalent group. For example, alkylamino group, arylamino group (anilino group, naphthylamino group etc.), heterocyclic amino group (benzthiazolylamino group, pyrrolylamino group etc.), alkylthio group, arylthio group (phenylthio group etc.), heterocyclic thiol Group, alkoxy group, aryloxy group (phenoxy group etc.), heterocyclic oxy group, aryl group (phenyl group, naphthyl group, anthranyl group etc.), aromatic or non-aromatic heterocyclic group (5-membered to 7-membered) A monocyclic or condensed heterocyclic ring containing at least one heteroatom among nitrogen atom, sulfur atom, oxygen atom and selenium atom. Specific examples thereof include, for example, a tetrahydroquinoline ring, a tetrahydroisoquinoline ring, and a tetrahydroquinoxaline ring. , Tetrahydroquinazoline ring, indoline ring, indole ring, indazole ring, carbazo Ring, phenoxazine ring, phenothiazine ring, benzothiazoline ring, pyrrole ring, imidazole ring, thiazoline ring, piperidine ring, pyrrolidine ring, morpholine ring, benzimidazole ring, benzoimidazoline ring, benzoxazoline ring, methylenedioxyphenyl ring, etc. (Hereinafter referred to as RED for convenience)₁₁Is described as a monovalent radical name). RED₁₁May have a substituent.
[0295]
In the present invention, the substituent means a substituent selected from the following groups unless otherwise specified. Halogen atom, alkyl group (including aralkyl group, cycloalkyl group, active methine group, etc.), alkenyl group, alkynyl group, aryl group, heterocyclic group (regardless of the position of substitution), quaternized nitrogen atom A heterocyclic group (e.g., pyridinio group, imidazolio group, quinolinio group, isoquinolinio group), acyl group, alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl group, carboxy group or salt thereof, sulfonylcarbamoyl group, acylcarbamoyl group, sulfa Moylcarbamoyl group, carbazoyl group, oxalyl group, oxamoyl group, cyano group, carboximidoyl group, thiocarbamoyl group, hydroxy group, alkoxy group (including groups containing ethyleneoxy group or propyleneoxy group unit repeatedly), aryloxy group Heterocycle o Si group, acyloxy group, (alkoxy or aryloxy) carbonyloxy group, carbamoyloxy group, sulfonyloxy group, amino group, (alkyl, aryl, or heterocyclic) amino group, acylamino group, sulfonamide group, ureido group, thioureido Group, imide group, (alkoxy or aryloxy) carbonylamino group, sulfamoylamino group, semicarbazide group, thiosemicarbazide group, hydrazino group, ammonio group, oxamoylamino group, (alkyl or aryl) sulfonylureido group, acylureido group , Acylsulfamoylamino group, nitro group, mercapto group, (alkyl, aryl, or heterocyclic) thio group, (alkyl or aryl) sulfonyl group, (alkyl or aryl) sulfinyl group, sulfo group or Salts, sulfamoyl group, sulfonylsulfamoyl group or a salt thereof, phosphoric acid amide or a group containing a phosphoric acid ester structure and so forth. These substituents may be further substituted with these substituents.
[0296]
RED₁₁Are preferably an alkylamino group, an arylamino group, a heterocyclic amino group, an aryl group, an aromatic or non-aromatic heterocyclic group, more preferably an arylamino group (particularly an anilino group), an aryl group (particularly a phenyl group). Group). When these have a substituent, the substituent is preferably a halogen atom, an alkyl group, an alkoxy group, a carbamoyl group, a sulfamoyl group, an acylamino group, or a sulfonamide group.
However, RED₁₁When represents an aryl group, the aryl group preferably has at least one “electron-donating group”. Here, the “electron donating group” means a hydroxy group, an alkoxy group, a mercapto group, a sulfonamide group, an acylamino group, an alkylamino group, an arylamino group, a heterocyclic amino group, an active methine group, and a nitrogen atom in the ring. 5-membered, monocyclic or condensed, electron-rich aromatic heterocyclic group (for example, indolyl group, pyrrolyl group, imidazolyl group, benzimidazolyl group, thiazolyl group, benzthiazolyl group, indazolyl group, etc.), nitrogen A non-aromatic nitrogen-containing heterocyclic group (a group that can also be called a cyclic amino group such as a pyrrolidinyl group, an indolinyl group, a piperidinyl group, a piperazinyl group, or a morpholino group) substituted with an atom. Here, the active methine group means a methine group substituted by two “electron-withdrawing groups”, and the “electron-withdrawing group” means an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, It means a carbamoyl group, an alkylsulfonyl group, an arylsulfonyl group, a sulfamoyl group, a trifluoromethyl group, a cyano group, a nitro group, or a carbonimidoyl group. Here, the two electron-attracting groups may be bonded to each other to form a cyclic structure.
[0297]
In general formula (A), L₁₁Is specifically a carboxy group or a salt thereof, a silyl group, a hydrogen atom, a triarylboron anion, a trialkylstannyl group, a trialkylgermyl group, or -CR_C1R_C2R_C3Represents a group. Here, the silyl group specifically represents a trialkylsilyl group, an aryldialkylsilyl group, a triarylsilyl group, or the like, and may have an arbitrary substituent.
[0298]
L₁₁When represents a salt of a carboxy group, examples of counter ions that form salts include alkali metal ions, alkaline earth metal ions, heavy metal ions, ammonium ions, phosphonium ions, and the like, preferably alkali metal ions or ammonium ions. Alkali metal ions (especially Li⁺, Na⁺, K⁺Ion) is most preferred.
[0299]
L₁₁-CR_C1R_C2R_C3When representing a group, here R_C1, R_C2, R_C3Each independently represents a hydrogen atom, an alkyl group, an aryl group, a heterocyclic group, an alkylthio group, an arylthio group, an alkylamino group, an arylamino group, a heterocyclic amino group, an alkoxy group, an aryloxy group, or a hydroxy group. May be bonded to each other to form a cyclic structure, and may further have an arbitrary substituent. However, R_C1, R_C2, R_C3When one of them represents a hydrogen atom or an alkyl group, the remaining two do not represent a hydrogen atom or an alkyl group. R_C1, R_C2, R_C3Preferably, each independently represents an alkyl group, an aryl group (particularly a phenyl group), an alkylthio group, an arylthio group, an alkylamino group, an arylamino group, a heterocyclic group, an alkoxy group, or a hydroxy group. For example, phenyl group, p-dimethylaminophenyl group, p-methoxyphenyl group, 2,4-dimethoxyphenyl group, p-hydroxyphenyl group, methylthio group, phenylthio group, phenoxy group, methoxy group, ethoxy group, dimethylamino Group, N-methylanilino group, diphenylamino group, morpholino group, thiomorpholino group, hydroxy group and the like. Examples of the case where they are bonded to each other to form a cyclic structure include 1,3-dithiolan-2-yl group, 1,3-dithian-2-yl group, N-methyl-1,3-thiazolidine-2 -Yl group, N-benzyl-benzothiazolidin-2-yl group and the like.
-CR_C1R_C2R_C3The group is R_C1, R_C2, R_C3As a result of each selected within the above-mentioned range, the general formula (A) to L₁₁It is also preferred if it represents the same group as the residue excluding.
[0300]
In general formula (A), L₁₁Is preferably a carboxy group or a salt thereof, and a hydrogen atom. More preferably, it is a carboxy group or a salt thereof.
[0301]
L₁₁When represents a hydrogen atom, the compound represented by the general formula (A) preferably has a base moiety inherent in the molecule. After the compound represented by the general formula (A) is oxidized by the action of this base moiety,₁₁Is deprotonated, and further electrons are emitted therefrom.
[0302]
Here, the base is specifically a conjugate base of an acid having a pKa of about 1 to about 10. For example, nitrogen-containing heterocycles (pyridines, imidazoles, benzimidazoles, thiazoles, etc.), anilines, trialkylamines, amino groups, carbon acids (active methylene anions, etc.), thioacetic acid anions, carboxylates (- COO^-), Sulfate (-SO_Three ^-), Or amine oxide (> N⁺(O^-)-) And the like. Preferably, it is a conjugate base of an acid exhibiting a pKa of about 1 to about 8, more preferably carboxylate, sulfate or amine oxide, particularly preferably carboxylate. When these bases have anions, they may have counter cations, examples of which include alkali metal ions, alkaline earth metal ions, heavy metal ions, ammonium ions, phosphonium ions and the like. These bases are linked to the compound represented by the general formula (A) at an arbitrary position. The position at which these base sites bind is the RED of general formula (A)₁₁, R₁₁₁, R₁₁₂Any of these may be sufficient, and you may connect with the substituent of these groups.
[0303]
R in the general formula (A)₁₁₂Represents a substituent substitutable on a hydrogen atom or a carbon atom. However, R₁₁₂Is L₁₁And does not represent the same group.
R₁₁₂Is preferably a hydrogen atom, an alkyl group, an aryl group (such as a phenyl group), an alkoxy group (such as a methoxy group, an ethoxy group, and a benzyloxy group), a hydroxy group, an alkylthio group (such as a methylthio group and a butylthio group), an amino group, and an alkyl group An amino group, an arylamino group and a heterocyclic amino group, more preferably a hydrogen atom, an alkyl group, an alkoxy group, a hydroxy group, a phenyl group and an alkylamino group.
[0304]
R in the general formula (A)₁₁₁Is a ring structure corresponding to a tetrahydro, hexahydro or octahydro form of a 5-membered or 6-membered aromatic ring (including aromatic heterocycle), where the hydro form is an aromatic A ring structure in which a carbon-carbon double bond (or carbon-nitrogen double bond) in a ring (including an aromatic heterocycle) is partially hydrogenated means a tetrahydro form, and two hexahydro forms The three and octahydro forms mean a structure in which four carbon-carbon double bonds (or carbon-nitrogen double bonds) are hydrogenated. By being hydrogenated, the aromatic ring becomes a partially hydrogenated non-aromatic ring structure.
Specifically, pyrrolidine ring, imidazolidine ring, thiazolidine ring, pyrazolidine ring and oxazolidine ring, piperidine ring, tetrahydropyridine ring, tetrahydropyrimidine ring, piperazine ring, tetralin ring, tetrahydroquinoline ring, tetrahydroisoquinoline ring, tetrahydroquinazoline ring, And tetrahydroquinoxaline ring, tetrahydrocarbazole ring, octahydrophenanthridine ring and the like. These ring structures may have an arbitrary substituent.
[0305]
R₁₁₁More preferably, the cyclic structure formed by pyrrolidine ring, imidazolidine ring, piperidine ring, tetrahydropyridine ring, tetrahydropyrimidine ring, piperazine ring, tetrahydroquinoline ring, tetrahydroisoquinoline ring, tetrahydroquinazoline ring, tetrahydroquinoxaline ring, tetrahydrocarbazole ring Particularly preferred are pyrrolidine ring, piperidine ring, piperazine ring, tetrahydropyridine ring, tetrahydroquinoline ring, tetrahydroisoquinoline ring, tetrahydroquinazoline ring, tetrahydroquinoxaline ring, most preferably pyrrolidine ring, piperidine ring, tetrahydropyridine ring. , Tetrahydroquinoline ring and tetrahydroisoquinoline ring.
[0306]
In general formula (B), RED₁₂, L₁₂Are respectively RED of the general formula (A)₁₁, L₁₁The preferred range is also the same. However, RED₁₂Is a monovalent group except when it forms the following cyclic structure, specifically RED.₁₁And monovalent group names described in the above. R₁₂₁And R₁₂₂Is R in the general formula (A)₁₁₂The preferred range is also the same. ED₁₂Represents an electron donating group. R₁₂₁And RED₁₂, R₁₂₁And R₁₂₂Or ED₁₂And RED₁₂And may be bonded to each other to form a cyclic structure.
[0307]
ED in general formula (B)₁₂The electron donating group represented by RED₁₁Is the same as the electron-donating group described as the substituent for when A represents an aryl group. ED₁₂Preferably a hydroxy group, an alkoxy group, a mercapto group, a sulfonamide group, an alkylamino group, an arylamino group, an active methine group, a 5-membered monocyclic or condensed ring electron containing at least one nitrogen atom in the ring An excess aromatic heterocyclic group, a non-aromatic nitrogen-containing heterocyclic group substituted with a nitrogen atom, and a phenyl group substituted with these electron donating groups, and further a hydroxy group, a mercapto group, a sulfonamide group, an alkylamino group Groups, arylamino groups, active methine groups, non-aromatic nitrogen-containing heterocyclic groups substituted with nitrogen atoms, and phenyl groups substituted with these electron-donating groups (for example, p-hydroxyphenyl groups, p-dialkylaminophenyl groups) , O, p-dialkoxyphenyl group, etc.) are more preferable.
[0308]
R in the general formula (B)₁₂₁And RED₁₂, R₁₂₂And R₁₂₁Or ED₁₂And RED₁₂And may be bonded to each other to form a cyclic structure. The cyclic structure formed here is a non-aromatic carbocyclic or heterocyclic ring, which is a 5-membered to 7-membered monocyclic or condensed ring, and is a substituted or unsubstituted cyclic structure. R₁₂₁And RED₁₂When and form a ring structure, specific examples thereof include R in general formula (A).₁₁₁In addition to those listed as examples of the cyclic structure formed by pyrroline ring, imidazoline ring, thiazoline ring, pyrazoline ring, oxazoline ring, indane ring, morpholine ring, indoline ring, tetrahydro-1,4-oxazine ring, 2, 3-dihydrobenzo-1,4-oxazine ring, tetrahydro-1,4-thiazine ring, 2,3-dihydrobenzo-1,4-thiazine ring, 2,3-dihydrobenzofuran ring, 2,3-dihydrobenzothiophene A ring etc. are mentioned. ED₁₂And RED₁₂And form a ring structure, ED₁₂Preferably represents an amino group, an alkylamino group, or an arylamino group, and specific examples of the ring structure formed include a tetrahydropyrazine ring, a piperazine ring, a tetrahydroquinoxaline ring, and a tetrahydroisoquinoline ring. R₁₂₂And R₁₂₁When and form a ring structure, specific examples thereof include a cyclohexane ring and a cyclopentane ring.
[0309]
Next, general formulas (1) to (3) will be described.
In the general formulas (1) to (3), R₁, R₂, R₁₁, R₁₂, R₃₁Is R in the general formula (A)₁₁₂The preferred range is also the same. L₁, L_{twenty one}, L₃₁Is L in the general formula (A)₁₁Represents the same leaving group as the specific examples given in the description, and preferred ranges thereof are also the same. X₁, X_{twenty one}As the substituent represented by the formula (A),₁₁Is the same as the example of the substituent when has a substituent, and the preferred range is also the same. m₁, M_{twenty one}Is preferably an integer of 0 to 2, more preferably 0 or 1.
[0310]
R_N1, R_N21, R_N31When represents a substituent, the substituent is preferably an alkyl group, an aryl group, or a heterocyclic group, and these may further have an arbitrary substituent. R_N1, R_N21, R_N31Is preferably a hydrogen atom, an alkyl group or an aryl group, more preferably a hydrogen atom or an alkyl group.
[0311]
R₁₃, R₁₄, R₃₃, R_a, R_bWhen represents a substituent, the substituent is preferably an alkyl group, aryl group, acyl group, alkoxycarbonyl group, carbamoyl group, cyano group, alkoxy group, acylamino group, sulfonamido group, ureido group, thioureido group, alkylthio group. An arylthio group, an alkylsulfonyl group, an arylsulfonyl group, a sulfamoyl group, and the like.
[0312]
In general formula (1), Z₁The 6-membered ring formed by is a non-aromatic heterocycle condensed with the benzene ring of the general formula (1). Specifically, a tetrahydroquinoline ring, a tetrahydroquinoxaline ring as a ring structure including the condensed benzene ring, A tetrahydroquinazoline ring, preferably a tetrahydroquinoline ring or a tetrahydroquinoxaline ring. These may have a substituent.
[0313]
ED in general formula (2)_{twenty one}Is the ED of the general formula (B)₁₂The preferred range is also the same.
[0314]
In the general formula (2), R_N21, R₁₃, R₁₄, X_{twenty one}And ED_{twenty one}Any two of these may combine with each other to form a cyclic structure. Where R_N21And X_{twenty one}The cyclic structure formed by bonding is preferably a 5- to 7-membered non-aromatic carbocyclic or heterocyclic ring condensed with a benzene ring. Specific examples thereof include a tetrahydroquinoline ring and a tetrahydroquinoxaline. A ring, an indoline ring, a 2,3-dihydro-5,6-benzo-1,4-thiazine ring, and the like. Preferred are a tetrahydroquinoline ring, a tetrahydroquinoxaline ring and an indoline ring.
[0315]
In the general formula (3), R_N31When represents a group other than an aryl group, R_aAnd R_bCombine with each other to form an aromatic ring. Here, the aromatic ring is an aryl group (for example, a phenyl group or a naphthyl group) and an aromatic heterocyclic group (for example, a pyridine ring group, a pyrrole ring group, a quinoline ring group, or an indole ring group), and an aryl group is preferable. The aromatic ring group may have an arbitrary substituent.
In the general formula (3), R_aAnd R_bAre preferably bonded to each other to form an aromatic ring (particularly a phenyl group).
[0316]
In the general formula (3), R₃₂Is preferably a hydrogen atom, an alkyl group, an aryl group, a hydroxy group, an alkoxy group, a mercapto group, an amino group, etc., where R₃₂When R represents a hydroxy group,₃₃The case where represents an “electron-withdrawing group” is also a preferred example. Here, the “electron withdrawing group” is the same as described above, and an acyl group, an alkoxycarbonyl group, a carbamoyl group, and a cyano group are preferable.
[0317]
Next, the type 2 compound will be described.
In the type 2 compound, “bond cleavage reaction” means carbon-carbon, carbon-silicon, carbon-hydrogen, carbon-boron, carbon-tin, carbon-germanium bond cleavage, and carbon-hydrogen. This may be accompanied by cleavage of the bond.
[0318]
The type 2 compound is a compound having two or more (preferably 2 to 6, more preferably 2 to 4) adsorptive groups to silver halide in the molecule. More preferred is a compound having a nitrogen-containing heterocyclic group substituted with two or more mercapto groups as an adsorptive group. The number of adsorptive groups is preferably 2-6, more preferably 2-4. The adsorptive group will be described later.
[0319]
A preferable compound among the compounds of type 2 is represented by the general formula (C).
[0320]
General formula (C)
Embedded image
[0321]
The compound represented by the general formula (C) is RED₂After the reducing group represented by₂It is a compound that can release one more electron with this by leaving the group by bond cleavage reaction.
[0322]
In general formula (C), RED₂Is RED of general formula (B)₁₂Represents the same group, and the preferred range is also the same. L₂Is L in the general formula (A)₁₁Represents the same group as described above, and its preferred range is also the same. L₂When represents a silyl group, the compound is a compound having, as an adsorptive group, a nitrogen-containing heterocyclic group substituted with two or more mercapto groups in the molecule. R_{twenty one}, R_{twenty two}Represents a hydrogen atom or a substituent, and these are R in the general formula (A)₁₁₂The preferred range is also the same. RED₂And R_{twenty one}And may be bonded to each other to form a ring structure.
[0323]
The ring structure formed here is a 5-membered to 7-membered monocyclic or condensed, non-aromatic carbocycle or heterocycle, which may have a substituent. However, the ring structure is not a ring structure corresponding to a tetrahydro, hexahydro or octahydro form of an aromatic ring or an aromatic heterocycle. The ring structure is preferably a ring structure corresponding to a dihydro form of an aromatic ring or an aromatic heterocycle, and specific examples thereof include, for example, a 2-pyrroline ring, a 2-imidazoline ring, a 2-thiazoline ring, 1,2- Dihydropyridine ring, 1,4-dihydropyridine ring, indoline ring, benzimidazoline ring, benzothiazoline ring, benzoxazoline ring, 2,3-dihydrobenzothiophene ring, 2,3-dihydrobenzofuran ring, benzo-α-pyran ring, 1 , 2-dihydroquinoline ring, 1,2-dihydroquinazoline ring, 1,2-dihydroquinoxaline ring and the like, preferably 2-imidazoline ring, 2-thiazoline ring, indoline ring, benzoimidazoline ring, benzothiazoline ring, Benzoxazoline ring, 1,2-dihydropyridine ring, 1,2-dihydroquino Down ring, 1,2-dihydro-quinazoline ring, and the like 1,2-dihydro-quinoxaline ring, indoline ring, benzimidazoline ring, a benzothiazoline ring, 1,2-dihydroquinoline ring is more preferable, indoline ring is particularly preferred.
[0324]
Next, the compound of type 3 will be described.
In the type 3 compound, “bond formation process” means formation of an interatomic bond such as carbon-carbon, carbon-nitrogen, carbon-sulfur, carbon-oxygen and the like.
[0325]
The compound of type 3 is preferably a reactive group site (carbon-carbon double bond site, carbon-carbon triple bond site, fragrance) in which a one-electron oxidant formed by one-electron oxidation coexists in the molecule. And a non-aromatic heterocyclic group part of a benzo-condensed ring) to form a bond and then emit one electron or more electrons.
[0326]
More specifically, a type 3 compound has a one-electron oxidant formed by one-electron oxidation (a cation radical species or a neutral radical species produced by elimination of a proton therefrom) in the same molecule. It reacts with the coexisting reactive group, forms a bond, and generates a radical species having a new ring structure in the molecule. This radical species has a feature that electrons of the second electron are emitted directly or with elimination of protons.
And in some Type 3 compounds, the two-electron oxidant so produced is then subjected to a hydrolysis reaction in some cases, and in some cases tautomerization with direct proton transfer. There is a case in which one or more electrons, usually two or more electrons are emitted from the oxidization reaction. Alternatively, those having the ability to emit one or more electrons, usually two or more electrons, directly from a two-electron oxidant without going through such a tautomerization reaction are also included.
[0327]
The compound of type 3 is preferably represented by the general formula (D).
[0328]
Formula (D)
Embedded image
[0329]
In general formula (D), RED_ThreeRepresents a reducing group which can be oxidized by one electron, Y_ThreeIs RED_ThreeRepresents a reactive group site that reacts after one-electron oxidation, specifically a carbon-carbon double bond site, a carbon-carbon triple bond site, an aromatic group site, or a non-aromatic heterocycle of a benzo-fused ring An organic group containing a ring group site is represented. L_ThreeIs RED_ThreeAnd Y_ThreeRepresents a linking group for linking.
[0330]
RED_ThreeIs RED of general formula (B)₁₂And is preferably an arylamino group, a heterocyclic amino group, an aryloxy group, an arylthio group, an aryl group, an aromatic or non-aromatic heterocyclic group (particularly a nitrogen-containing heterocyclic group is preferred). And more preferably an arylamino group, a heterocyclic amino group, an aryl group, an aromatic or non-aromatic heterocyclic group, and among these heterocyclic groups, a tetrahydroquinoline ring group, a tetrahydroquinoxaline ring group, a tetrahydroquinazoline ring Group, indoline ring group, indole ring group, carbazole ring group, phenoxazine ring group, phenothiazine ring group, benzothiazoline ring group, pyrrole ring group, imidazole ring group, thiazole ring group, benzimidazole ring group, benzimidazoline ring group, Benzothiazoline ring group, 3,4-methylenedioxyphenyl-1-yl group Etc. are preferable.
RED_ThreeParticularly preferred are an arylamino group (particularly anilino group), an aryl group (particularly a phenyl group), and an aromatic or non-aromatic heterocyclic group.
[0331]
Where RED_ThreeWhen represents an aryl group, the aryl group preferably has at least one “electron-donating group”. The “electron donating group” is the same as described above.
[0332]
RED_ThreeWhen represents an aryl group, the substituent of the aryl group is more preferably an alkylamino group, a hydroxy group, an alkoxy group, a mercapto group, a sulfonamide group, an active methine group, a non-aromatic nitrogen-containing heterocycle substituted with a nitrogen atom More preferably an alkylamino group, a hydroxy group, an active methine group, and a non-aromatic nitrogen-containing heterocyclic group substituted with a nitrogen atom, and most preferably an alkylamino group and a non-aromatic group substituted with a nitrogen atom. Nitrogen heterocyclic group.
[0333]
Y_ThreeWhen the organic group containing a carbon-carbon double bond site represented by (for example, vinyl group) has a substituent, the substituent is preferably an alkyl group, a phenyl group, an acyl group, a cyano group, an alkoxycarbonyl group, A carbamoyl group, an electron donating group, and the like. The electron donating group is preferably an alkoxy group, a hydroxy group (which may be protected with a silyl group, such as a trimethylsilyloxy group, a t-butyldimethylsilyloxy group, Phenylsilyloxy group, triethylsilyloxy group, phenyldimethylsilyloxy group, etc.), amino group, alkylamino group, arylamino group, sulfonamide group, active methine group, mercapto group, alkylthio group, and these electron donors It is a phenyl group having a functional group as a substituent.
[0334]
Here, when the organic group containing a carbon-carbon double bond site has a hydroxy group as a substituent, Y_ThreeIs the partial structure on the right:> C₁= C₂(—OH) — is included, but this is tautomerized and the partial structure shown on the right:> C₁HC₂It may be (= O)-. In this case, the C₁It is also preferred that the substituent substituted for carbon is an electron withdrawing group, in which case Y_ThreeHas a partial structure of “active methylene group” or “active methine group”. The electron withdrawing group that can give such a partial structure of the active methylene group or active methine group is the same as that described in the description of the above-mentioned “active methine group”.
[0335]
Y_ThreeWhen the organic group containing a carbon-carbon triple bond site represented by (for example, ethynyl group) has a substituent, examples of the substituent include an alkyl group, a phenyl group, an alkoxycarbonyl group, a carbamoyl group, and an electron donating group. preferable.
[0336]
Y_ThreeRepresents an organic group containing an aromatic group, an aromatic group is preferably an aryl group having an electron donating group as a substituent (particularly a phenyl group is preferred) or an indole ring group, where the electron donating group is Preferred are a hydroxy group (which may be protected with a silyl group), an alkoxy group, an amino group, an alkylamino group, an active methine group, a sulfonamide group and a mercapto group.
[0337]
Y_ThreeRepresents an organic group containing a non-aromatic heterocyclic group portion of a benzo-fused ring, preferably a benzo-fused non-aromatic heterocyclic group that preferably has an aniline structure as a partial structure, for example, an indoline ring group, 1,2,3,4-tetrahydroquinoline ring group, 1,2,3,4-tetrahydroquinoxaline ring group, 4-quinolone ring group and the like can be mentioned.
[0338]
Y_ThreeMore preferred as the reactive group represented by is an organic group containing a carbon-carbon double bond site, an aromatic group site, or a benzo-fused non-aromatic heterocyclic group. More preferred are a carbon-carbon double bond site, a phenyl group having an electron donating group as a substituent, an indole ring group, and a benzo-fused non-aromatic heterocyclic group having an aniline structure as a partial structure. Here, the carbon-carbon double bond site preferably has at least one electron donating group as a substituent.
[0339]
Y_ThreeAs a result of the selection of the reactive group represented by_ThreeThe case where it has the same partial structure as the reducing group represented by general formula (D) is also a preferred example of the compound represented by general formula (D).
[0340]
L_ThreeRED_ThreeAnd Y_ThreeAnd specifically represents a single bond, an alkylene group, an arylene group, a heterocyclic group, -O-, -S-, -NR._N-, -C (= O)-, -SO₂The group which consists of individual group of-, -SO-, -P (= O)-, or a combination of these groups is represented. R here_NRepresents a hydrogen atom, an alkyl group, an aryl group, or a heterocyclic group. L_ThreeThe linking group represented by may have an arbitrary substituent. L_ThreeThe linking group represented by RED_ThreeAnd Y_ThreeIn any position of the group represented by the formula (1), each of the hydrogen atoms may be linked to replace any one hydrogen atom.
L_ThreePreferred examples of are: a single bond, an alkylene group (particularly a methylene group, an ethylene group, a propylene group), an arylene group (particularly a phenylene group), a —C (═O) — group, an —O— group, an —NH— group, -N (alkyl group)-group, and the bivalent coupling group which consists of a combination of these groups are mentioned.
[0341]
L_ThreeThe group represented by_ThreeCation radical species (X⁺.), Or a radical species (X.) generated from the proton withdrawn therefrom, and Y_ThreeWhen the reactive group represented by the above reacts to form a bond, the atomic group involved in this reaction is L_ThreeIt is preferable that a 3-7 membered cyclic structure including can be formed. For this purpose, radical species (X⁺-Or X-), the reactive group represented by Y, and L are preferably connected by 3 to 7 atomic groups.
[0342]
Next, the type 4 compound will be described.
A compound of type 4 is a compound having a ring structure substituted with a reducing group, and after the reducing group is oxidized by one electron, one or more electrons are emitted along with the ring structure cleavage reaction. Compound. The ring structure cleavage reaction referred to here means one having the following form.
[0343]
Embedded image
[0344]
In the formula, compound a represents a type 4 compound. In compound a, D represents a reducing group, and X and Y represent atoms forming a bond that is cleaved after one-electron oxidation in the ring structure. First, one-electron oxidation of the compound a generates a one-electron oxidant b. From this, the single bond of XX becomes a double bond, and at the same time, the bond of XY is cleaved to produce a ring-opened product c. Alternatively, a radical intermediate d may be generated from the one-electron oxidant b with proton desorption, and a ring opening e may be similarly generated therefrom. The compound of the present invention is characterized in that one or more electrons are subsequently released from the ring-opened product c or e thus produced.
[0345]
The ring structure possessed by the type 4 compound is a 3- to 7-membered carbocyclic or heterocyclic ring, and represents a monocyclic or condensed, saturated or unsaturated non-aromatic ring. A saturated ring structure is preferable, and a 3-membered ring or 4-membered ring is more preferable. Preferred examples of the ring structure include a cyclopropane ring, a cyclobutane ring, an oxirane ring, an oxetane ring, an aziridine ring, an azetidine ring, an episulfide ring, and a thietane ring. More preferred are cyclopropane ring, cyclobutane ring, oxirane ring, oxetane ring and azetidine ring, and particularly preferred are cyclopropane ring, cyclobutane ring and azetidine ring. The ring structure may have an arbitrary substituent.
[0346]
The compound of type 4 is preferably represented by the general formula (E) or (F).
[0347]
General formula (E)
Embedded image
[0348]
Formula (F)
Embedded image
[0349]
RED in general formula (E) and general formula (F)₄₁And RED₄₂Are respectively RED of the general formula (B)₁₂Represents a group having the same meaning, and the preferred range thereof is also the same. R₄₀~ R₄₄And R₄₅~ R₄₉Each represents a hydrogen atom or a substituent. In general formula (F), Z₄₂Is -CR₄₂₀R₄₂₁-, -NR₄₂₃-Represents-or -O-. R here₄₂₀, R₄₂₁Each represents a hydrogen atom or a substituent, and R₄₂₃Represents a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group.
[0350]
R in general formula (E) and general formula (F)₄₀And R₄₅Preferably represents a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group, more preferably a hydrogen atom, an alkyl group or an aryl group. R₄₁~ R₄₄And R₄₆~ R₄₉And preferably a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, a heterocyclic group, an arylthio group, an alkylthio group, an acylamino group, or a sulfonamide group, more preferably a hydrogen atom, an alkyl group, an aryl group, or a heterocyclic group. is there.
[0351]
R₄₁~ R₄₄In which at least one of these is a donor group, and R₄₁And R₄₂Or R₄₃And R₄₄Are preferably electron withdrawing groups. More preferably R₄₁~ R₄₄This is a case where at least one of the above is a donor group. More preferably R₄₁~ R₄₄At least one of them is a donor group and R₄₁~ R₄₄In this case, the group that is not a donor group is a hydrogen atom or an alkyl group.
[0352]
The donor group mentioned here is an “electron-donating group” or an aryl group substituted with at least one “electron-donating group”. The donor group is preferably an alkylamino group, an arylamino group, a heterocyclic amino group, a 5-membered monocyclic or condensed ring electron-rich aromatic heterocyclic group containing at least one nitrogen atom in the ring, nitrogen A non-aromatic nitrogen-containing heterocyclic group substituted with an atom or a phenyl group substituted with at least one electron-donating group is used. More preferably, an alkylamino group, an arylamino group, a 5-membered monocyclic or condensed ring-excessive aromatic heterocyclic group containing at least one nitrogen atom in the ring (an indole ring, a pyrrole ring, a carbazole ring, etc.) ), A phenyl group substituted with an electron donating group (such as a phenyl group substituted with three or more alkoxy groups, a phenyl group substituted with a hydroxy group, an alkylamino group, or an arylamino group). Particularly preferably, an arylamino group, a 5-membered monocyclic or condensed ring-containing electron-rich aromatic heterocyclic group (particularly a 3-indolyl group) or an electron-donating group containing at least one nitrogen atom in the ring is substituted. Used phenyl groups (particularly phenyl groups substituted with trialkoxyphenyl groups, alkylamino groups or arylamino groups).
[0353]
Z₄₂Preferably as -CR₄₂₀R₄₂₁-Or -NR₄₂₃-, More preferably -NR₄₂₃-. R₄₂₀, R₄₂₁Is preferably a hydrogen atom, an alkyl group, an aryl group, a heterocyclic group, an acylamino group or a sulfoneamino group, more preferably a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group. R₄₂₃Preferably represents a hydrogen atom, an alkyl group, an aryl group or an aromatic heterocyclic group, more preferably a hydrogen atom, an alkyl group or an aryl group.
[0354]
R₄₀~ R₄₉And R₄₂₀, R₄₂₁, R₄₂₃When each of these groups is a substituent, those having a total carbon number of 40 or less are preferable, more preferably a total carbon number of 30 or less, and particularly preferably a total carbon number of 15 or less. These substituents may be bonded to each other or other sites in the molecule (RED₄₁, RED₄₂Or Z₄₂) To form a ring.
[0355]
In the compounds of types 1 to 4 of the present invention, the adsorptive group to silver halide is a group that directly adsorbs to silver halide or a group that promotes adsorption to silver halide. Specifically, mercapto A heterocyclic group containing at least one atom selected from a group (or a salt thereof), a thione group (—C (═S) —), a nitrogen atom, a sulfur atom, a selenium atom and a tellurium atom, a sulfide group, a cationic group, Or an ethynyl group. However, the type 2 compound of the present invention does not contain a sulfide group as an adsorptive group.
[0356]
The mercapto group (or salt thereof) as the adsorptive group means the mercapto group (or salt thereof) itself, and more preferably a heterocyclic group or aryl group substituted with at least one mercapto group (or salt thereof). Or represents an alkyl group. Here, the heterocyclic group is a 5-membered to 7-membered monocyclic or condensed aromatic or non-aromatic heterocyclic group such as an imidazole ring group, a thiazole ring group, an oxazole ring group, or a benzimidazole ring group. , Benzthiazole ring group, benzoxazole ring group, triazole ring group, thiadiazole ring group, oxadiazole ring group, tetrazole ring group, purine ring group, pyridine ring group, quinoline ring group, isoquinoline ring group, pyrimidine ring group, triazine A cyclic group etc. are mentioned. Further, it may be a heterocyclic group containing a quaternized nitrogen atom. In this case, the substituted mercapto group may be dissociated into a meso ion. Examples of such a heterocyclic group include an imidazolium ring group, Examples include a pyrazolium ring group, a thiazolium ring group, a triazolium ring group, a tetrazolium ring group, a thiadiazolium ring group, a pyridinium ring group, a pyrimidinium ring group, and a triazinium ring group. Among them, a triazolium ring group (for example, 1,2,4- Triazolium-3-thiolate ring group) is preferable. Examples of the aryl group include a phenyl group and a naphthyl group. Examples of the alkyl group include linear, branched or cyclic alkyl groups having 1 to 30 carbon atoms. When the mercapto group forms a salt, the counter ion is a cation such as an alkali metal, alkaline earth metal, or heavy metal (Li⁺, Na⁺, K⁺, Mg²⁺, Ag⁺, Zn²⁺Etc.), ammonium ions, quaternized heterocyclic groups containing nitrogen atoms, phosphonium ions and the like.
[0357]
Further, the mercapto group as the adsorptive group may be tautomerized into a thione group, specifically, a thioamide group (here, —C (═S) —NH— group), and the thioamide group. A group having a partial structure of, ie, a chain or cyclic thioamide group, a thioureido group, a thiourethane group, or a dithiocarbamate group. Examples of cyclic groups include thiazolidine-2-thione group, oxazolidine-2-thione group, 2-thiohydantoin group, rhodanine group, isorhodanine group, thiobarbituric acid group, 2-thioxo-oxazolidine-4-one group Is mentioned.
[0358]
The thione group as an adsorptive group cannot be tautomerized to a mercapto group (including a hydrogen atom at the α-position of the thione group), including the case where the mercapto group described above is tautomerized into a thione group. A chain or cyclic thioamide group, thioureido group, thiourethane group, or dithiocarbamate group is also included.
[0359]
A heterocyclic group containing at least one atom selected from a nitrogen atom, a sulfur atom, a selenium atom and a tellurium atom as the adsorptive group is a -NH- group capable of forming imino silver (> NAg) and a partial structure of the heterocyclic ring A nitrogen-containing heterocyclic group, or a “—S—” group, a “—Se—” group, a “—Te—” group or a “═N—” group which can coordinate to a silver ion via a coordination bond. A heterocyclic group having a ring partial structure. Examples of the former include benzotriazole group, triazole group, indazole group, pyrazole group, tetrazole group, benzimidazole group, imidazole group, and purine group, and examples of the latter include thiophene. Group, thiazole group, oxazole group, benzothiazole group, benzoxazole group, thiadiazole group, oxadiazole group, triazine group, selenoazo Group, benzselenoazole group, tellurazole group, benztelluazole group and the like. The former is preferred.
[0360]
The sulfide group as the adsorptive group includes all groups having a partial structure of “—S—”, preferably alkyl (or alkylene) -S-alkyl (or alkylene), aryl (or arylene) -S—. A group having a partial structure of alkyl (or alkylene), aryl (or arylene) -S-aryl (or arylene). Furthermore, these sulfide groups may form a cyclic structure or may be an -S-S- group. Specific examples in the case of forming a cyclic structure include a thiolane ring, a 1,3-dithiolane ring or a 1,2-dithiolane ring, a thiane ring, a dithiane ring, a tetrahydro-1,4-thiazine ring (thiomorpholine ring) and the like. Groups. Particularly preferred as the sulfide group is a group having a partial structure of alkyl (or alkylene) -S-alkyl (or alkylene).
[0361]
The cationic group as the adsorptive group means a group containing a quaternized nitrogen atom, specifically, an ammonio group or a group containing a nitrogen-containing heterocyclic group containing a quaternized nitrogen atom. . However, the cationic group does not become a part of an atomic group forming a dye structure (for example, a cyanine chromophore). Here, the ammonio group is a trialkylammonio group, a dialkylarylammonio group, an alkyldiarylammonio group or the like, and examples thereof include a benzyldimethylammonio group, a trihexylammonio group, and a phenyldiethylammonio group. Examples of the nitrogen-containing heterocyclic group containing a quaternized nitrogen atom include a pyridinio group, a quinolinio group, an isoquinolinio group, an imidazolio group, and the like. A pyridinio group and an imidazolio group are preferable, and a pyridinio group is particularly preferable. These nitrogen-containing heterocyclic groups containing a quaternized nitrogen atom may have an arbitrary substituent, but in the case of a pyridinio group and an imidazolio group, the substituent is preferably an alkyl group, an aryl group, an acylamino group , A chloro atom, an alkoxycarbonyl group, a carbamoyl group and the like. In the case of a pyridinio group, a phenyl group is particularly preferred as a substituent.
[0362]
An ethynyl group as an adsorptive group means a —C≡CH group, and a hydrogen atom may be substituted.
The above adsorptive group may have an arbitrary substituent.
[0363]
Specific examples of the adsorptive group further include those described in pages 4 to 7 of JP-A No. 11-95355.
[0364]
Preferred as the adsorptive group in the present invention is a mercapto-substituted nitrogen-containing heterocyclic group (for example, 2-mercaptothiadiazole group, 3-mercapto-1,2,4-triazole group, 5-mercaptotetrazole group, 2-mercapto-1). , 3,4-oxadiazole group, 2-mercaptobenzoxazole group, 2-mercaptobenzthiazole group, 1,5-dimethyl-1,2,4-triazolium-3-thiolate group), or imino silver (> A nitrogen-containing heterocyclic group (for example, a benzotriazole group, a benzimidazole group, an indazole group, etc.) having a —NH— group that can form NAg) as a partial structure of the heterocyclic ring. Particularly preferred are 5-mercaptotetrazole group, 3-mercapto-1,2,4-triazole group, and benzotriazole group, most preferred are 3-mercapto-1,2,4-triazole group, and 5 -Mercaptotetrazole group.
[0365]
Of the compounds of the present invention, compounds having two or more mercapto groups as partial structures in the molecule are also particularly preferred compounds. Here, the mercapto group (—SH) may be a thione group if it can be tautomerized. Examples of such compounds include the above-described adsorptive groups having a mercapto group or thione group as a partial structure (for example, a ring-forming thioamide group, an alkyl mercapto group, an aryl mercapto group, a heterocyclic mercapto group, etc.) Or an adsorbing group having two or more mercapto groups or thione groups as a partial structure (for example, a dimercapto-substituted nitrogen-containing telocyclic group). You may have one or more.
[0366]
Examples of the adsorptive group having two or more mercapto groups as a partial structure (such as a dimercapto-substituted nitrogen-containing telocyclic group) include 2,4-dimercaptopyrimidine group, 2,4-dimercaptotriazine group, 3,5 -Dimercapto-1,2,4-triazole group, 2,5-dimercapto-1,3-thiazole group, 2,5-dimercapto-1,3-oxazole group, 2,7-dimercapto-5-methyl-s- Triazolo (1,5-A) -pyrimidine, 2,6,8-trimercaptopurine, 6,8-dimercaptopurine, 3,5,7-trimercapto-s-triazolotriazine, 4,6-dimercapto Examples include pyrazolopyrimidine, 2,5-dimercaptoimidazole, 2,4-dimercaptopyrimidine group, 2,4-dimercaptotriazine group, 3,5. Dimercapto-1,2,4-triazole group are particularly preferred.
[0367]
The adsorptive group may be substituted anywhere in the general formulas (A) to (F) and the general formulas (1) to (3), but in the general formulas (A) to (D), RED₁₁, RED₁₂, RED₂, RED_ThreeIn the general formulas (E) and (F), RED₄₁, R₄₁, RED₄₂, R₄₆~ R₄₈In the general formulas (1) to (3), R₁, R₂, R₁₁, R₁₂, R₃₁, L₁, L_{twenty one}, L₃₁It is preferably substituted at any position except for RED, and RED in all of the general formulas (A) to (F)₁₁~ RED₄₂More preferably, it is substituted.
[0368]
The partial structure of the spectral sensitizing dye is a group containing a chromophore of the spectral sensitizing dye, and is a residue obtained by removing any hydrogen atom or substituent from the spectral sensitizing dye compound. The partial structure of the spectral sensitizing dye may be substituted anywhere in the general formulas (A) to (F) and the general formulas (1) to (3), but in the general formulas (A) to (D), RED₁₁, RED₁₂, RED₂, RED_ThreeIn the general formulas (E) and (F), RED₄₁, R₄₁, RED₄₂, R₄₆~ R₄₈In the general formulas (1) to (3), R₁, R₂, R₁₁, R₁₂, R₃₁, L₁, L_{twenty one}, L₃₁It is preferably substituted at any position except for RED, and RED in all of the general formulas (A) to (F)₁₁~ RED₄₂More preferably, it is substituted. Preferred spectral sensitizing dyes are spectral sensitizing dyes typically used in color sensitization techniques such as cyanine dyes, complex cyanine dyes, merocyanine dyes, complex merocyanine dyes, homopolar cyanine dyes, Contains styryl dyes and hemicyanine dyes. Exemplary spectral sensitizing dyes are disclosed in Research Disclosure, Item 36544, September 1994. Those skilled in the art can synthesize these dyes by the procedures described in the Research Disclosure or F.M. Hamer's The Cyanine dyes and Related Compounds (Interscience Publishers, New yprk, 1964). Further, all the dyes described in JP-A-11-95355 (US Pat. No. 6,054,260), pages 7 to 14 are applied as they are.
[0369]
The compounds of types 1 to 4 of the present invention preferably have a total carbon number of 10 to 60. More preferably, it is 15-50, More preferably, it is 18-40, Most preferably, it is 18-30.
[0370]
The compounds of types 1 to 4 of the present invention are subjected to 1-electron oxidation triggered by exposure of the silver halide photographic light-sensitive material using the compound, and after the subsequent reaction, further 1 electron, or 2 electrons or more depending on the type. Electrons are emitted and oxidized, and the oxidation potential of the first electron is preferably about 1.4 V or less, and more preferably 1.0 V or less. This oxidation potential is preferably higher than 0V, more preferably higher than 0.3V. Accordingly, the oxidation potential is preferably in the range of about 0 to about 1.4V, more preferably about 0.3 to about 1.0V.
[0371]
Here, the oxidation potential can be measured by a cyclic voltammetry technique. Specifically, a sample is dissolved in a solution of acetonitrile: water (including 0.1 M lithium perchlorate) = 80%: 20% (volume%). After bubbling nitrogen gas for 10 minutes, a glassy carbon disk was used as the working electrode, a platinum wire was used as the counter electrode, and a calomel electrode (SCE) was used as the reference electrode at 25 ° C. and 0.1 V / Measured at a potential scanning speed of seconds. The oxidation potential versus SCE is taken at the peak potential of the cyclic voltammetry wave.
[0372]
In the case where the compounds of types 1 to 4 of the present invention are one-electron oxidized and further emit one electron after the subsequent reaction, the subsequent oxidation potential is preferably −0.5 V to −2 V. More preferably, it is -0.7V--2V, More preferably, it is -0.9V--1.6V.
[0373]
In the case where the compound of types 1 to 4 of the present invention is a compound that is oxidized by one electron and emits two or more electrons after the subsequent reaction and is oxidized, there is no particular limitation on the oxidation potential of this latter stage. Absent. This is because the oxidation potential of the second electron and the oxidation potential of the third and subsequent electrons cannot be clearly distinguished, and it is often difficult to accurately measure and distinguish these actually.
[0374]
Next, the compound of type 5 will be described.
A compound of type 5 is represented by XY, where X represents a reducing group, Y represents a leaving group, and a one-electron oxidant produced by one-electron oxidation of the reducing group represented by X is This is a compound capable of releasing X by further elimination of Y with subsequent XY bond cleavage reaction to generate an X radical, from which another electron is emitted. The reaction when such a type 5 compound is oxidized can be represented by the following formula.
[0375]
Embedded image
[0376]
The compound of type 5 preferably has an oxidation potential of 0 to 1.4V, more preferably 0.3V to 1.0V. The oxidation potential of the radical X · generated in the above reaction formula is preferably −0.7 V to −2.0 V, more preferably −0.9 V to −1.6 V.
[0377]
The compound of type 5 is preferably represented by the general formula (G).
[0378]
General formula (G)
Embedded image
[0379]
In general formula (G), RED₀Represents a reducing group, L₀Represents a leaving group, R₀And R₀₀Represents a hydrogen atom or a substituent. RED₀ And R₀And R₀And R₀₀And may be bonded to each other to form a ring structure. RED₀Is RED of general formula (C)₂Represents the same group, and the preferred range is also the same. R₀And R₀₀Is R in the general formula (C)_{twenty one}And R_{twenty two}The preferred range is also the same. However, R₀And R₀₀Except for the hydrogen atom, L₀Does not represent the same group. RED₀And R₀May be bonded to each other to form a ring structure, and examples of the ring structure include RED of the general formula (C).₂And R_{twenty one}Examples are the same as in the case of linking to form a ring structure, and the preferred range is also the same. R₀And R₀₀Examples of the ring structure formed by bonding to each other include a cyclopentane ring and a tetrahydrofuran ring. In general formula (G), L₀Is L in the general formula (C)₂The preferred range is also the same.
[0380]
The compound represented by the general formula (G) preferably has an adsorptive group to silver halide or a partial structure of spectral sensitizing dye in the molecule.₀When represents a group other than a silyl group, it does not have two or more adsorptive groups in the molecule at the same time. However, the sulfide group as the adsorptive group here is L₀You may have two or more regardless of this.
[0381]
Examples of the adsorptive group to the silver halide of the compound represented by the general formula (G) include the same adsorptive groups that the compounds of types 1 to 4 of the present invention may have. In addition, all those described as “silver halide adsorbing groups” on pages 4 to 7 of JP-A No. 11-95355 can be mentioned, and preferred ranges are also the same.
The partial structure of the spectral sensitizing dye that the compound represented by the general formula (G) may have is the partial structure of the spectral sensitizing dye that the compounds of types 1 to 4 of the present invention may have. However, at the same time, all those described as “light-absorbing groups” on pages 7 to 14 of JP-A-11-95355 can be mentioned, and the preferred ranges are also the same.
[0382]
Specific examples of the compounds of types 1 to 5 of the present invention are listed below, but the present invention is not limited thereto.
[0383]
Embedded image
[0384]
Embedded image
[0385]
Embedded image
[0386]
Embedded image
[0387]
The compounds of types 1 to 4 of the present invention are described in detail in Japanese Patent Application No. 2002-192373, Japanese Patent Application No. 2002-188537, Japanese Patent Application No. 2002-188536, Japanese Patent Application No. 2001-272137, and Japanese Patent Application No. 2002-192374, respectively. Same as described compound. Specific compound examples described in these patent application specifications can also be given as specific examples of the compounds of types 1 to 4 of the present invention. The synthesis examples of the compounds of types 1 to 4 of the present invention are also the same as those described in these patents.
[0388]
Specific examples of the compound of type 5 according to the present invention are further described in JP-A-9-211769 (compounds PMT-1 to S-37 described in Table E and Table F on pages 28 to 32), JP-A-9-211774. JP-A-11-95355 (compounds INV1-36), JP-T-2001-500996 (compounds 1-74, 80-87, 92-122), US Pat. No. 5,747,235, US Pat. No. 5,747, No. 236, European Patent No. 786692A1 (compounds INV1 to 35), European Patent No. 893732A1, US Pat. No. 6,054,260, US Pat. No. 5,994,051, etc. Examples of compounds referred to as “deprotonated electron donating sensitizers” are mentioned as they are.
[0389]
The compounds of types 1 to 5 of the present invention may be used at any time during the process of producing a photothermographic material when preparing a photosensitive silver halide emulsion. For example, at the time of photosensitive silver halide grain formation, desalting step, chemical sensitization, before coating. Moreover, it can also add in several steps in these processes. The addition position is preferably from the end of formation of the photosensitive silver halide grains to before the desalting step, at the time of chemical sensitization (immediately after the start of chemical sensitization to immediately after completion), and before application, more preferably from the time of chemical sensitization. Until before mixing with the non-photosensitive organic silver salt.
[0390]
The compounds of types 1 to 5 of the present invention are preferably added after being dissolved in water, a water-soluble solvent such as methanol or ethanol, or a mixed solvent thereof. When the compound is dissolved in water, the compound having higher solubility when the pH is increased or decreased may be dissolved at a higher or lower pH and added.
[0390]
The compounds of types 1 to 5 of the present invention are preferably used in emulsion layers containing a photosensitive silver halide and a non-photosensitive organic silver salt, but contain a photosensitive silver halide and a non-photosensitive organic silver salt. It may be added to the protective layer or intermediate layer together with the emulsion layer to be diffused during coating. The timing of addition of the compound of the present invention is preferably before or after the sensitizing dye, and preferably 1 × 10 5 per mole of silver halide.^-9~ 5x10^-1Mole, more preferably 1 × 10^-8~ 5x10^-2It is contained in the silver halide emulsion layer in a molar ratio.
[0392]
(Description of binder)
Any polymer may be used as the binder of the organic silver salt-containing layer of the present invention, and suitable binders are transparent or translucent and generally colorless, and include natural resins, polymers and copolymers, synthetic resins, polymers and copolymers, etc. Film-forming media such as gelatins, rubbers, poly (vinyl alcohol) s, hydroxyethyl celluloses, cellulose acetates, cellulose acetate butyrates, poly (vinyl pyrrolidone) s, casein, starch, poly (acrylic acid) ), Poly (methyl methacrylic acid), poly (vinyl chloride), poly (methacrylic acid), styrene-maleic anhydride copolymers, styrene-acrylonitrile copolymers, styrene-butadiene copolymers , Poly (vinyl acetal) s (eg, poly (vinyl Lumar) and poly (vinyl butyral)), poly (esters), poly (urethane) s, phenoxy resins, poly (vinylidene chloride) s, poly (epoxides), poly (carbonates), poly (vinyl acetate) s , Poly (olefin) s, cellulose esters, and poly (amides). The binder may be coated from water or an organic solvent or emulsion.
[0393]
In the present invention, the glass transition temperature of the binder that can be used in combination with the layer containing the organic silver salt is preferably 0 ° C. or higher and 80 ° C. or lower (hereinafter sometimes referred to as a high Tg binder), and preferably 10 ° C. to 70 ° C. Is more preferable, and it is still more preferable that it is 15 degreeC or more and 60 degrees C or less.
[0394]
In this specification, Tg was calculated by the following formula.
1 / Tg = Σ (Xi / Tgi)
Here, it is assumed that n monomer components from i = 1 to n are copolymerized in the polymer. Xi is the weight fraction of the i-th monomer (ΣXi = 1), and Tgi is the glass transition temperature (absolute temperature) of the homopolymer of the i-th monomer. However, Σ is the sum from i = 1 to n. The homopolymer glass transition temperature (Tgi) of each monomer was the value of Polymer Handbook (3rd Edition) (by J. Brandrup, E.H. Immergut (Wiley-Interscience, 1989)).
[0395]
Two or more binders may be used in combination as required. Further, a glass transition temperature of 20 ° C. or higher and a glass transition temperature of less than 20 ° C. may be used in combination. When two or more kinds of polymers having different Tg are blended, the weight average Tg is preferably within the above range.
[0396]
In the present invention, the organic silver salt-containing layer is preferably applied and dried using a coating solution in which 30% by mass or more of the solvent is water to form a film.
In the present invention, when the organic silver salt-containing layer is formed using a coating solution in which 30% by mass or more of the solvent is water and dried, the binder of the organic silver salt-containing layer is further an aqueous solvent ( When it is soluble or dispersible in an aqueous solvent), the performance is improved particularly when it is made of a latex of a polymer having an equilibrium water content of 2% by mass or less at 25 ° C. and 60% RH. The most preferable form is one prepared so that the ionic conductivity is 2.5 mS / cm or less, and as such a preparation method, there is a method of purifying using a separation functional membrane after polymer synthesis.
[0397]
The aqueous solvent in which the polymer is soluble or dispersible here is a mixture of water or water with 70% by mass or less of a water-miscible organic solvent. Examples of the water-miscible organic solvent include alcohols such as methyl alcohol, ethyl alcohol and propyl alcohol, cellosolvs such as methyl cellosolve, ethyl cellosolve and butyl cellosolve, ethyl acetate and dimethylformamide.
[0398]
In the case of a system in which the polymer is not dissolved thermodynamically and exists in a so-called dispersed state, the term aqueous solvent is used here.
[0399]
“Equilibrium moisture content at 25 ° C. and 60% RH” means the weight W1 of the polymer in the humidity-controlled equilibrium under the atmosphere of 25 ° C. and 60% RH and the weight W0 of the polymer in the absolutely dry state at 25 ° C. It can be expressed as
Equilibrium moisture content at 25 ℃ 60% RH = [(W1-W0) / W0] x 100 (mass%)
[0400]
For the definition and measurement method of the moisture content, for example, Polymer Engineering Course 14, Polymer Material Testing Method (Edited by Polymer Society, Jinshokan) can be referred to.
[0401]
The equilibrium moisture content of the binder polymer of the present invention at 25 ° C. and 60% RH is preferably 2% by mass or less, more preferably 0.01% by mass to 1.5% by mass, and still more preferably 0.02% by mass to 1% by mass. Is desirable.
[0402]
In the present invention, a polymer dispersible in an aqueous solvent is particularly preferred. Examples of the dispersion state may be latex in which fine particles of water-insoluble hydrophobic polymer are dispersed or polymer molecules in which the polymer molecule is dispersed in a molecular state or forming micelles. preferable. The average particle size of the dispersed particles is 1 to 50000 nm, preferably 5 to 1000 nm, more preferably 10 to 500 nm, and still more preferably 50 to 200 nm. The particle size distribution of the dispersed particles is not particularly limited, and may have a wide particle size distribution or a monodispersed particle size distribution. Mixing two or more types having a monodispersed particle size distribution is also a preferable method for controlling the physical properties of the coating solution.
[0403]
In the present invention, preferred embodiments of the polymer that can be dispersed in an aqueous solvent include acrylic polymers, poly (esters), rubbers (for example, SBR resin), poly (urethanes), poly (vinyl chloride) s, poly (acetic acid). Hydrophobic polymers such as vinyl), poly (vinylidene chloride) and poly (olefin) can be preferably used. These polymers may be linear polymers, branched polymers, crosslinked polymers, so-called homopolymers obtained by polymerizing a single monomer, or copolymers obtained by polymerizing two or more types of monomers. In the case of a copolymer, it may be a random copolymer or a block copolymer. The molecular weight of these polymers is 5,000 to 100,000, preferably 10,000 to 200,000 in number average molecular weight. When the molecular weight is too small, the mechanical strength of the emulsion layer is insufficient, and when the molecular weight is too large, the film formability is poor, which is not preferable. A crosslinkable polymer latex is particularly preferably used.
[0404]
(Specific examples of latex)
Specific examples of preferable polymer latex include the following. Below, it represents using a raw material monomer, the numerical value in a parenthesis is mass%, and molecular weight is a number average molecular weight. When a polyfunctional monomer was used, the concept of molecular weight was not applicable because a crosslinked structure was formed, so it was described as crosslinkability, and the description of molecular weight was omitted. Tg represents the glass transition temperature.
[0405]
Latex of P-1; -MMA (70) -EA (27) -MAA (3)-(molecular weight 37000, Tg61 ℃)
Latex of P-2; -MMA (70) -2EHA (20) -St (5) -AA (5)-(molecular weight 40000, Tg59 ° C)
Latex of P-3; -St (50) -Bu (47) -MAA (3)-(crosslinkability, Tg-17 ° C)
Latex of P-4; -St (68) -Bu (29) -AA (3)-(crosslinkability, Tg17 ° C)
Latex of P-5; -St (71) -Bu (26) -AA (3)-(crosslinkability, Tg24 ℃)
Latex of P-6; -St (70) -Bu (27) -IA (3)-(crosslinkability)
Latex of P-7; -St (75) -Bu (24) -AA (1)-(crosslinkability, Tg29 ° C)
Latex of P-8; -St (60) -Bu (35) -DVB (3) -MAA (2)-(crosslinkability)
P-9; -St (70) -Bu (25) -DVB (2) -AA (3)-latex (crosslinkable)
Latex of P-10; -VC (50) -MMA (20) -EA (20) -AN (5) -AA (5)-(molecular weight 80000)
P-11; -VDC (85) -MMA (5) -EA (5) -MAA (5)-latex (molecular weight 67000)
Latex of P-12; -Et (90) -MAA (10)-(molecular weight 12000)
P-13; -St (70) -2EHA (27) -AA (3) latex (molecular weight 130000, Tg43 ℃)
P-14; -MMA (63) -EA (35)-AA (2) latex (molecular weight 33000, Tg47 ℃)
Latex of P-15; -St (70.5) -Bu (26.5) -AA (3)-(crosslinkability, Tg23 ° C)
Latex of P-16; -St (69.5) -Bu (27.5) -AA (3)-(crosslinkability, Tg20.5 ℃)
[0406]
The abbreviations for the above structures represent the following monomers. MMA; methyl methacrylate, EA; ethyl acrylate, MAA; methacrylic acid, 2EHA; 2-ethylhexyl acrylate, St; styrene, Bu; butadiene, AA; acrylic acid, DVB; divinylbenzene, VC; vinyl chloride, AN; Vinylidene chloride, Et; ethylene, IA; itaconic acid.
[0407]
The polymer latex described above is also commercially available, and the following polymers can be used. Examples of acrylic polymers include Sebian A-4635, 4718, 4601 (manufactured by Daicel Chemical Industries, Ltd.), Nipol Lx811, 814, 821, 820, 857 (manufactured by Nippon Zeon Co., Ltd.), poly ( Examples of esters include polynet (urethanes) such as FINETEX ES650, 611, 675, 850 (Dainippon Ink Chemical Co., Ltd.), WD-size, WMS (Eastman Chemical). Are HYDRAN AP10, 20, 30, 40 (above Dainippon Ink Chemical Co., Ltd.) and examples of rubbers include LACSTAR 7310K, 3307B, 4700H, 7132C (above Dainippon Ink Chemical Co., Ltd.) , Nipol Lx416, 410, 438C, 2507 (made by Nippon Zeon Co., Ltd.) and other examples of poly (vinyl chloride) such as G351, G576 (made by Nippon Zeon Co., Ltd.), poly (vinylidene chloride) Examples of such as L502, L513 (manufactured by Asahi Kasei Kogyo Co., Ltd.) and other examples of poly (olefin), such as Chemipearl S120, SA100 (above Mitsui Petrochemical ( And the like).
[0408]
These polymer latexes may be used alone or in combination of two or more as required.
[0409]
(Preferred latex)
The polymer latex used in the present invention is particularly preferably a styrene-butadiene copolymer latex. The weight ratio of the styrene monomer unit to the butadiene monomer unit in the styrene-butadiene copolymer is preferably 40:60 to 95: 5. The proportion of the styrene monomer unit and the butadiene monomer unit in the copolymer is preferably 60 to 99% by mass. Moreover, it is preferable that the polymer latex of this invention contains 1-6 mass% of acrylic acid or methacrylic acid with respect to the sum of styrene and butadiene, More preferably, it contains 2-5 mass%. The polymer latex of the present invention preferably contains acrylic acid.
[0410]
Examples of the latex of styrene-butadiene acid copolymer preferably used in the present invention include P-3 to P-8,15 described above, LACSTAR-3307B, 7132C, and Nipol Lx416, which are commercially available products.
[0411]
If necessary, a hydrophilic polymer such as gelatin, polyvinyl alcohol, methylcellulose, hydroxypropylcellulose, carboxymethylcellulose may be added to the organic silver salt-containing layer of the light-sensitive material of the present invention. The amount of these hydrophilic polymers added is preferably 30% by mass or less, more preferably 20% by mass or less, based on the total binder of the organic silver salt-containing layer.
[0412]
The organic silver salt-containing layer (that is, the image forming layer) of the present invention is preferably formed using a polymer latex. The amount of binder in the organic silver salt-containing layer is such that the weight ratio of the total binder / organic silver salt is in the range of 1/110 to 10, more preferably in the range of 1/3 to 5/1, more preferably in the range of 1/1 to 3. The range is / 1.
[0413]
Further, such an organic silver salt-containing layer is usually a photosensitive layer (emulsion layer) containing a photosensitive silver halide which is a photosensitive silver salt. The weight ratio of silver is 400-5, more preferably 200-10.
[0414]
The total binder amount of the image forming layer of the present invention is preferably 0.2 to 30 g / m.², More preferably 1-15 g / m²More preferably 2-10 g / m²Range. The image forming layer of the present invention may contain a crosslinking agent for crosslinking, a surfactant for improving coating properties, and the like.
(Preferable solvent for coating solution)
[0415]
In the present invention, the solvent of the organic silver salt-containing layer coating solution of the photosensitive material (here, for simplicity, the solvent and the dispersion medium are collectively referred to as a solvent) is preferably an aqueous solvent containing 30% by mass or more of water. As a component other than water, any water-miscible organic solvent such as methyl alcohol, ethyl alcohol, isopropyl alcohol, methyl cellosolve, ethyl cellosolve, dimethylformamide, ethyl acetate may be used. The water content of the solvent of the coating solution is preferably 50% by mass or more, more preferably 70% by mass or more. Examples of preferred solvent compositions include water, water / methyl alcohol = 90/10, water / methyl alcohol = 70/30, water / methyl alcohol / dimethylformamide = 80/15/5, water / methyl alcohol / Ethyl cellosolve = 85/10/5, water / methyl alcohol / isopropyl alcohol = 85/10/5, etc. (numerical value is mass%).
[0416]
(Description of hydrogen bonding compound)
When the reducing agent in the present invention has an aromatic hydroxyl group (—OH) or an amino group, particularly in the case of the aforementioned bisphenols, non-reducing having a group capable of forming a hydrogen bond with these groups. It is preferable to use a sexual compound in combination. Examples of the group that forms a hydrogen bond with a hydroxyl group or an amino group include a phosphoryl group, a sulfoxide group, a sulfonyl group, a carbonyl group, an amide group, an ester group, a urethane group, a ureido group, a tertiary amino group, and a nitrogen-containing aromatic group. Can be mentioned. Among them, preferred are a phosphoryl group, a sulfoxide group, an amide group (however, it does not have a> N—H group and is blocked like> N—Ra (Ra is a substituent other than H)), a urethane group. (However, it has no> N—H group and is blocked like> N—Ra (Ra is a substituent other than H)), a ureido group (however, it has no> N—H group,> N-Ra (Ra is a substituent other than H).)
In the present invention, a particularly preferred hydrogen bonding compound is a compound represented by the following general formula (D).
Formula (D)
[0417]
Embedded image
[0418]
R in general formula (D)^{twenty one}Or R^{twenty three}Each independently represents an alkyl group, an aryl group, an alkoxy group, an aryloxy group, an amino group or a heterocyclic group, and these groups may be unsubstituted or may have a substituent. R^{twenty one}Or R^{twenty three}In the case where has a substituent, the substituent is a halogen atom, alkyl group, aryl group, alkoxy group, amino group, acyl group, acylamino group, alkylthio group, arylthio group, sulfonamido group, acyloxy group, oxycarbonyl group, carbamoyl Group, sulfamoyl group, sulfonyl group, phosphoryl group and the like. Preferred as substituents are alkyl groups or aryl groups such as methyl group, ethyl group, isopropyl group, t-butyl group, t-octyl group, phenyl group, 4-alkoxyphenyl group, 4-acyloxyphenyl group and the like can be mentioned.
[0419]
R^{twenty one}Or R^{twenty three}Specific examples of the alkyl group include methyl group, ethyl group, butyl group, octyl group, dodecyl group, isopropyl group, t-butyl group, t-amyl group, t-octyl group, cyclohexyl group, and 1-methylcyclohexyl group. Benzyl group, phenethyl group, 2-phenoxypropyl group, and the like. Examples of the aryl group include phenyl group, cresyl group, xylyl group, naphthyl group, 4-t-butylphenyl group, 4-t-octylphenyl group, 4-anisidyl group, and 3,5-dichlorophenyl group. Alkoxy groups include methoxy, ethoxy, butoxy, octyloxy, 2-ethylhexyloxy, 3,5,5-trimethylhexyloxy, dodecyloxy, cyclohexyloxy, 4-methylcyclohexyloxy, benzyl An oxy group etc. are mentioned. Examples of the aryloxy group include a phenoxy group, a cresyloxy group, an isopropylphenoxy group, a 4-t-butylphenoxy group, a naphthoxy group, and a biphenyloxy group. Examples of the amino group include a dimethylamino group, a diethylamino group, a dibutylamino group, a dioctylamino group, an N-methyl-N-hexylamino group, a dicyclohexylamino group, a diphenylamino group, and an N-methyl-N-phenylamino group. .
[0420]
R^{twenty one}Or R^{twenty three}Are preferably an alkyl group, an aryl group, an alkoxy group, or an aryloxy group. In terms of the effect of the present invention, R^{twenty one}Or R^{twenty three}Of these, at least one is preferably an alkyl group or an aryl group, and more preferably two or more are an alkyl group or an aryl group. In addition, R can be obtained at low cost.^{twenty one}Or R^{twenty three}Are preferably the same group.
Specific examples of the hydrogen bonding compound including the compound of the general formula (D) in the present invention are shown below, but the present invention is not limited thereto.
[0421]
Embedded image
[0422]
Specific examples of the hydrogen bonding compound include those described in European Patent No. 1096310, Japanese Patent Application Laid-Open No. 2002-156727, and Japanese Patent Application No. 2001-124796 in addition to the above.
The compound of the general formula (D) of the present invention can be used in a light-sensitive material by being incorporated in a coating solution in the form of a solution, an emulsified dispersion, or a solid dispersion fine particle dispersion in the same manner as the reducing agent. It is preferable to use it as a product. The compound of the present invention forms a hydrogen-bonding complex with a compound having a phenolic hydroxyl group or an amino group in a solution state, and depending on the combination of the reducing agent and the compound of the general formula (D) of the present invention, It can be isolated in the crystalline state. The use of the crystal powder isolated in this way as a solid dispersed fine particle dispersion is particularly preferable for obtaining stable performance. In addition, a method in which a reducing agent and the compound of the general formula (D) of the present invention are mixed in a powder and complexed at the time of dispersion with a sand grinder mill or the like using an appropriate dispersant can be preferably used.
The compound of the general formula (D) of the present invention is preferably used in the range of 1 to 200 mol%, more preferably in the range of 10 to 150 mol%, still more preferably 20 to 100 mol, based on the reducing agent. % Range.
[0423]
(Description of antifogging agent)
Antifoggants, stabilizers and stabilizer precursors which can be used in the present invention are disclosed in paragraph No. 0070 of JP-A-10-62899, page 20 line 57 to page 21 line 7 of EP 080364A1. And the compounds described in JP-A-9-281637 and 9-329864, US Pat. Nos. 6,083,681, 6,083,681, and EP 1048975. Antifoggants preferably used in the present invention are organic halides, and examples thereof include those disclosed in Japanese Patent Application Laid-Open No. 11-65021, paragraphs 0111 to 0112. In particular, an organic halogen compound represented by formula (P) in JP-A-2000-284399, an organic polyhalogen compound represented by formula (II) in JP-A-10-339934, JP-A-2001-31644 and JP The organic polyhalogen compounds described in 2001-33911 are preferred.
[0424]
1) Polyhalogen compounds
Hereinafter, the organic polyhalogen compound preferable in the present invention will be specifically described. A preferred polyhalogen compound of the present invention is a compound represented by the following general formula (H).
General formula (H)
Q- (Y) n-C (Z₁) (Z₂) X
In the general formula (H), Q represents an alkyl group, an aryl group or a heterocyclic group, Y represents a divalent linking group, n represents 0 or 1, Z₁And Z₂Represents a halogen atom, and X represents a hydrogen atom or an electron withdrawing group.
In general formula (H), Q is preferably an aryl group or a heterocyclic group.
In the general formula (H), when Q is a heterocyclic group, a nitrogen-containing heterocyclic group containing 1 to 2 nitrogen atoms is preferable, and a 2-pyridyl group and a 2-quinolyl group are particularly preferable.
[0425]
In the general formula (H), when Q is an aryl group, Q preferably represents a phenyl group substituted with an electron-withdrawing group having a positive Hammett's substituent constant σp. Regarding the Hammett's substituent constant, Journal of Medicinal Chemistry, 1973, Vol. 16, No. 11, 1207-1216, etc. can be referred to. Examples of such an electron withdrawing group include a halogen atom (fluorine atom (σp value: 0.06), chlorine atom (σp value: 0.23), bromine atom (σp value: 0.23), iodine atom. (Σp value: 0.18)), trihalomethyl group (tribromomethyl (σp value: 0.29), trichloromethyl (σp value: 0.33), trifluoromethyl (σp value: 0.54)), Cyano group (σp value: 0.66), nitro group (σp value: 0.78), aliphatic / aryl or heterocyclic sulfonyl group (for example, methanesulfonyl (σp value: 0.72)), aliphatic / aryl Or a heterocyclic acyl group (for example, acetyl (σp value: 0.50), benzoyl (σp value: 0.43)), alkynyl group (for example, C≡CH (σp value: 0.23)), aliphatic Aryl or heterocyclic oxycarbo Group (for example, methoxycarbonyl (σp value: 0.45), phenoxycarbonyl (σp value: 0.44)), carbamoyl group (σp value: 0.36), sulfamoyl group (σp value: 0.57), Examples thereof include a sulfoxide group, a heterocyclic group, and a phosphoryl group. The σp value is preferably in the range of 0.2 to 2.0, more preferably in the range of 0.4 to 1.0. Particularly preferred as the electron withdrawing group is a carbamoyl group, an alkoxycarbonyl group, an alkylsulfonyl group or an alkylphosphoryl group, and among them, a carbamoyl group is most preferred.
[0426]
X is preferably an electron-withdrawing group, more preferably a halogen atom, aliphatic / aryl or heterocyclic sulfonyl group, aliphatic / aryl or heterocyclic acyl group, aliphatic / aryl or heterocyclic oxycarbonyl group, A carbamoyl group and a sulfamoyl group, particularly preferably a halogen atom. Among the halogen atoms, a chlorine atom, a bromine atom and an iodine atom are preferable, a chlorine atom and a bromine atom are more preferable, and a bromine atom is particularly preferable.
Y is preferably -C (= O)-, -SO- or -SO.₂ -, More preferably -C (= O)-, -SO₂ -, Particularly preferably -SO₂ -.
n represents 0 or 1, and is preferably 1.
[0427]
Specific examples of the compound of the general formula (H) of the present invention are shown below.
[0428]
Embedded image
[0429]
Other preferred polyhalogen compounds of the invention include those described in JP-A Nos. 2001-31644, 2001-56526, and 2001-209145.
The compound represented by the general formula (H) of the present invention is 10 per mole of the non-photosensitive silver salt of the image forming layer.^-FourIt is preferably used in the range of ˜1 mol, more preferably 10^-3In the range of ~ 0.5 mol, more preferably 1 × 10^-2It is preferable to use in the range of ~ 0.2 mol.
In the present invention, the antifoggant is added to the light-sensitive material by the method described in the method for containing a reducing agent, and the organic polyhalogen compound is also preferably added as a solid fine particle dispersion.
[0430]
2) Other antifogging agents
Examples of other antifoggants include mercury (II) salts described in JP-A No. 11-65021, paragraph No. 0113, benzoic acids listed in paragraph No. 0114, salicylic acid derivatives of JP-A No. 2000-206642, and formulas of JP-A No. 2000-221634 A formalin scavenger compound represented by (S), a triazine compound according to claim 9 of JP-A-11-352624, a compound represented by formula (III) of JP-A-61-11791, 4-hydroxy-6- And methyl-1,3,3a, 7-tetrazaindene.
[0431]
The photothermographic material in the invention may contain an azolium salt for the purpose of fog prevention. Examples of the azolium salt include compounds represented by general formula (XI) described in JP-A-59-193447, compounds described in JP-B-55-12581, and general formula (II) described in JP-A-60-153039. And the compounds represented. The azolium salt may be added to any part of the photosensitive material, but the addition layer is preferably added to the layer having the photosensitive layer, and more preferably to the organic silver salt-containing layer. The azolium salt may be added in any step of preparing the coating solution. When added to the organic silver salt-containing layer, any step from the preparation of the organic silver salt to the preparation of the coating solution may be performed. To immediately before coating. The azolium salt may be added by any method such as powder, solution, fine particle dispersion. Moreover, you may add as a solution mixed with other additives, such as a sensitizing dye, a reducing agent, and a color toning agent. In the present invention, the addition amount of the azolium salt may be any amount, but is 1 × 10 10 per mole of silver.^-6Moles to 2 moles, preferably 1 × 10^-3More preferably, it is more than mol and less than 0.5 mol.
[0432]
(Other additives)
1) Mercapto, disulfide, and thiones
In the present invention, a mercapto compound, a disulfide compound, and a thione compound can be contained in order to suppress or promote development to control development, to improve spectral sensitization efficiency, and to improve storage stability before and after development. JP-A-10-62899, paragraphs 0067 to 0069, JP-A-10-186572, the compound represented by the general formula (I) and specific examples thereof, paragraphs 0033 to 0052, and EP 080364A1. 20 pages, lines 36-56. Of these, mercapto-substituted heteroaromatic compounds described in JP-A-9-297367, JP-A-9-304875, JP-A-2001-100358, Japanese Patent Application 2001-104213, Japanese Patent Application 2001-104214, and the like are preferable.
[0433]
2) Color preparation
In the photothermographic material of the present invention, it is preferable to add a color toning agent. For the color toning agent, paragraph numbers 0054 to 0055 of JP-A-10-62899, page 21 lines 23 to 48 of European Patent Publication No. 0803684A1, No. 2000-356317 and JP-A 2000-187298. In particular, phthalazinones (phthalazinone, phthalazinone derivatives or metal salts; for example, 4- (1-naphthyl) phthalazinone, 6-chlorophthalazinone, 5,7 -Dimethoxyphthalazinone and 2,3-dihydro-1,4-phthalazinedione); phthalazinones and phthalic acids (eg phthalic acid, 4-methylphthalic acid, 4-nitrophthalic acid, diammonium phthalate, sodium phthalate) , Potassium phthalate and tetrachlorophthalic anhydride); phthalazines (phthalazine, phthalazine derivatives or metal salts; eg 4- (1-naphthyl) phthalazine, 6-isopropyl (Thalazine, 6-t-butyl phthalazine, 6-chlorophthalazine, 5,7-dimethoxyphthalazine and 2,3-dihydrophthalazine); a combination of phthalazines and phthalic acids is preferred, especially phthalazines and phthalic acids The combination of is preferable. Of these, a particularly preferred combination is a combination of 6-isopropylphthalazine and phthalic acid or 4-methylphthalic acid.
[0434]
3) Plasticizer, lubricant
Regarding the plasticizer and lubricant that can be used in the photosensitive layer of the present invention, paragraph No. 0117 of JP-A No. 11-65021, the ultrahigh contrast agent for ultrahigh contrast image formation, and the addition method and amount thereof are the same. Paragraph No. 0118, Japanese Patent Application Laid-Open No. 11-223898, Paragraph Nos. 0136 to 0193, Japanese Patent Application Laid-Open No. 2000-284399, compounds of Formula (H), Formulas (1) to (3), Formulas (A) and (B), and Japanese Patent Application JP-A-11-65021, paragraph No. 0102, JP-A-11-65021, compounds of general formulas (III) to (V) described in JP-A-11-91652 (specific compounds: Chemical formulas 21 to 24), No. 223898, paragraph numbers 0194 to 0195.
[0435]
4) Ultra-high contrast agent
In order to form an ultrahigh contrast image suitable for printing plate making applications, it is preferable to add an ultrahigh contrast agent to the image forming layer. As for the ultra-high contrast agent and its addition method and addition amount, the formulas of JP-A No. 11-65021, paragraph No. 0118, JP-A No. 11-223898, paragraph Nos. 0136 to 0193, and Japanese Patent Application No. 11-87297 ( H), compounds of formulas (1) to (3), formulas (A) and (B), compounds of general formulas (III) to (V) described in Japanese Patent Application No. 11-91652 (specific compounds: 21 to 24), and the contrast accelerators are described in JP-A-11-65021, paragraph number 0102, and JP-A-11-223898, paragraph number 0194-0195.
[0436]
In order to use formic acid or formate as a strong fogging substance, it is preferably contained at 5 mmol or less, more preferably 1 mmol or less, per mol of silver on the side having the image forming layer containing photosensitive silver halide.
[0437]
When the ultrahigh contrast agent is used in the photothermographic material of the present invention, it is preferable to use an acid formed by hydrating diphosphorus pentoxide or a salt thereof in combination. Acids or salts thereof formed by hydration of diphosphorus pentoxide include metaphosphoric acid (salt), pyrophosphoric acid (salt), orthophosphoric acid (salt), triphosphoric acid (salt), tetraphosphoric acid (salt), hexametalin An acid (salt) etc. can be mentioned. Examples of the acid or salt thereof formed by hydrating diphosphorus pentoxide particularly preferably include orthophosphoric acid (salt) and hexametaphosphoric acid (salt). Specific examples of the salt include sodium orthophosphate, sodium dihydrogen orthophosphate, sodium hexametaphosphate, and ammonium hexametaphosphate.
Amount of acid or salt thereof formed by hydration of diphosphorus pentoxide (1m photosensitive material)²The coating amount per unit) may be a desired amount according to the performance such as sensitivity and fog, but 0.1 to 500 mg / m²Is preferred, 0.5-100 mg / m²Is more preferable.
The reducing agent, hydrogen bonding compound, development accelerator and polyhalogen compound of the present invention are preferably used as solid dispersions, and a preferred method for producing these solid dispersions is described in JP-A-2002-55405. .
[0438]
(Preparation and application of coating solution)
The preparation temperature of the image forming layer coating solution of the present invention is preferably from 30 ° C. to 65 ° C., more preferably from 35 ° C. to less than 60 ° C., and more preferably from 35 ° C. to 55 ° C. Further, it is preferable that the temperature of the image forming layer coating solution immediately after the addition of the polymer latex is maintained at 30 ° C. or more and 65 ° C. or less.
[0439]
(Layer structure and components)
The image forming layer of the present invention is composed of one or more layers on a support. In the case of a single layer, it consists of an organic silver salt, a photosensitive silver halide, a reducing agent and a binder, and optionally contains additional materials such as toning agents, coating aids and other auxiliary agents. In the case of two or more layers, the first image forming layer (usually the layer adjacent to the support) contains an organic silver salt and a light-sensitive silver halide, and some of the second image forming layer or both layers include Must contain other ingredients. The construction of a multicolor photosensitive photothermographic material may include a combination of these two layers for each color and includes all components in a single layer as described in US Pat. No. 4,708,928. Also good. In the case of a multi-dye multicolor photosensitive photothermographic material, each emulsion layer generally has a functional or non-functional barrier layer between each photosensitive layer as described in U.S. Pat.No. 4,460,681. By using, they are kept distinguished from each other.
The photothermographic material of the present invention can have a non-photosensitive layer in addition to the image forming layer. The non-photosensitive layer consists of (a) a surface protective layer provided on the image forming layer (on the side farther from the support), (b) between the plurality of image forming layers and between the image forming layer and the protective layer. An intermediate layer provided between them, (c) an undercoat layer provided between the image forming layer and the support, and (d) a back layer provided on the opposite side of the image forming layer.
[0440]
In addition, although a layer acting as an optical filter can be provided, it is provided as the layer (a) or (b). The antihalation layer is provided on the photosensitive material as the layer (c) or (d).
[0441]
1) Surface protective layer
In the photothermographic material of the invention, a surface protective layer can be provided for the purpose of preventing adhesion of the image forming layer. The surface protective layer may be a single layer or a plurality of layers.
The surface protective layer is described in JP-A No. 11-65021, paragraph numbers 0119 to 0120 and JP-A No. 2000-171936.
As the binder for the surface protective layer of the present invention, gelatin is preferable, but it is also preferable to use polyvinyl alcohol (PVA) or a combination thereof. As gelatin, inert gelatin (for example, Nitta gelatin 750), phthalated gelatin (for example, Nitta gelatin 801), and the like can be used. Examples of PVA include those described in JP-A No. 2000-171936, paragraphs 0009 to 0020, which are completely saponified PVA-105, partially saponified PVA-205, PVA-335, and modified polyvinyl alcohol MP-. Preferred is 203 (trade name, manufactured by Kuraray Co., Ltd.). Polyvinyl alcohol coating amount of protective layer (per layer) (support 1m²As per) 0.3-4.0g / m²Is preferably 0.3 to 2.0 g / m²Is more preferable.
[0442]
Total binder (including water-soluble polymer and latex polymer) coating amount of surface protective layer (per layer) (support 1m²As per) 0.3-5.0g / m²Is preferably 0.3 to 2.0 g / m²Is more preferable.
[0443]
2) Antihalation dye
The photothermographic material of the present invention preferably contains a dye having light absorption at the exposure wavelength in at least one of the photosensitive layer and the non-photosensitive layer for the purpose of preventing halation during exposure. Examples of the non-photosensitive layer include a non-photosensitive layer (an antihalation layer or an undercoat layer) on the support side of the photosensitive layer, and a non-photosensitive layer on the back surface on the opposite side of the support from the photosensitive layer.
The antihalation dye may be an infrared absorbing dye when the exposure wavelength is in the infrared region, and may be an ultraviolet absorbing dye when the exposure wavelength is in the ultraviolet region, both of which absorb in the visible region. Dyes that do not have or have low absorption in the visible range are preferred.
[0444]
When the exposure wavelength is in the visible range, it is preferable that the antihalation dye does not substantially retain the dye color after image formation, and it is preferable to use a means for decoloring by the heat of heat development. In particular, it is preferable to add a thermally decolorable dye and a base precursor to the non-photosensitive layer to function as a thermally decolorable antihalation layer. These techniques are described in JP-A-11-231457 and the like.
[0445]
The amount of antihalation dye added is determined by the use of the dye. In general, the optical density (absorbance) when measured at the target wavelength is preferably used in an amount exceeding 0.1, and more preferably 0.2 to 2. The amount of dye used to obtain such an optical density is generally 0.001 to 1 g / m.²Degree.
[0446]
When the exposure light source is laser light, the antihalation layer only needs to absorb light in a narrow wavelength region in accordance with the emission peak wavelength, so that the amount of dye applied can be reduced, and a photosensitive material is produced at low cost. be able to.
In addition, as the emission peak wavelength of laser light becomes shorter, higher-definition image recording becomes possible. For this reason, it is preferable that the light emission peak wavelength of a laser beam is 350-430 nm, and it is more preferable that it is 380-420 nm from a practical viewpoint.
[0447]
When laser light having an emission peak wavelength of 350 to 430 nm is used as an exposure light source, the antihalation dye preferably has an absorption maximum between 350 nm and 430 nm. Furthermore, when the emission peak wavelength of laser light is 380 to 420 nm, the dye preferably has an absorption maximum at 380 nm to 420 nm.
The layer containing a dye having an absorption maximum between 350 nm and 430 nm is preferably a photosensitive layer, a non-photosensitive layer on the support side of the photosensitive layer (which may be an antihalation layer), and opposite to the photosensitive layer with respect to the support This is a non-photosensitive layer on the back surface on the side.
[0448]
The type of the dye is not particularly limited as long as it has an absorption maximum between 350 nm and 430 nm. The absorption maximum observed between 350 nm and 430 nm may be main absorption or secondary absorption. Specific examples of dyes having an absorption maximum between 350 nm and 430 nm include azo dyes, azomethine dyes, quinone dyes (such as anthraquinone dyes and naphthoquinone dyes), quinoline dyes (such as quinophthalone dyes), and methine dyes (for example, Cyanine, merocyanine, oxonol, styryl, arylidene, aminobutadiene dyes, including polymethine dyes), carbonium dyes (eg, cationic dyes such as diphenylmethane dyes, triphenylmethane dyes, xanthene dyes, acridine dyes), azine dyes (eg. , Thiazine dyes, oxazine dyes, cation dyes such as phenazine dyes), aza [18] π electron dyes (for example, porphine dyes, tetraazaporphine dyes, phthalocyanine dyes, etc.), indigoid dyes (indigo, Indigo dyes), squarylium dyes, croconium dyes, pyromethene dyes, nitro / nitroso dyes, benzotriazole dyes, triazine dyes, etc., preferably azo dyes, azomethine dyes, quinone dyes, quinoline dyes, A methine dye, an aza [18] π electron dye, an indigoid dye, and a pyromethene dye, more preferably an azo dye, an azomethine dye, and a methine dye, with a methine dye being particularly preferred. These dyes may be in a solid fine particle dispersed state, an associated state (including a liquid crystal state), or two or more kinds of dyes may be used in combination.
[0449]
It is preferable to use an antihalation dye having a large absorption at the exposure wavelength because the amount of the dye applied can be reduced. Therefore, it is preferable that the antihalation dye is a dye exhibiting a sharp absorption spectrum peak with a narrow half width, or used in a state exhibiting such absorption. It is preferable to use the dye in a solid fine particle dispersed state or an associated state since the absorption can be increased and the absorption spectrum peak can be sharpened. In order to form the dye aggregate, it is preferable to use a dye having an ionic hydrophilic group. The full width at half maximum of dye absorption is preferably 100 nm or less, more preferably 75 nm or less, and even more preferably 50 nm or less.
[0450]
The antihalation dye may or may not be decolored after image formation. When the dye is not decolored (hereinafter referred to as “non-decoloring”), it is preferable that the dye is not noticeable, and it is preferable that the ratio obtained by slowing the absorption at the exposure wavelength by the absorption at 425 nm is larger. For example, when the photosensitive material is exposed and recorded with a semiconductor laser having a wavelength of 405 nm, the absorption ratio of 405 nm / 425 nm is preferably 5 or more, more preferably 10 or more, and particularly preferably 15 or more.
Examples of such dyes include aminobutadiene dyes, merocyanine dyes in which an acidic nucleus and a basic nucleus are directly connected, or polymethine dyes. In addition, a non-decolorable dye can be added as an aqueous solution if it is water-soluble.
[0451]
On the other hand, it is also preferable to decolorize the antihalation dye during the heat development process. As the dye decoloring method, the following are known, and any method can be used.
(1) A colorant (dye) comprising an electron-donating color developing organic compound and an acidic developer, as described in JP-A-9-34077 and JP-A-2001-51371, and a specific erasing agent. A method of decoloring by reacting with a colorant during heat development;
(2) Compounds that generate radicals by light irradiation or heating, such as those described in JP-A-9-133984, JP-A-2000-29168, 2000-284403, and 2000-347341. A method of erasing the decolorizable dye in combination with a chromatic dye.
(3) U.S. Pat. Nos. 5,135,842, 5,258,724, 5,314,795, 5,324,627, 5,384,237, JP-A-3-26765, 6-222504, A method of decolorizing the decolorizable dye by a combination of a compound capable of generating a base or a nucleophilic agent upon heating and a decolorizable dye described in JP-A-6-222505 and 7-36145.
(4) A method for decolorizing a dye by causing an intramolecular cyclization reaction by thermal decomposition of the dye itself, as described in US Pat. No. 4,894,358, JP-A-2-289856, and JP-A-59-182436 .
(5) Decolorizing properties described in JP-A-6-82948, JP-A-11-231457, JP-A-2000-112058, JP-A-2000-281923, JP-A-2000-169248 A method of decolorizing a dye by combining a very good intramolecular ring-closing decoloring dye and a base or a base precursor.
[0452]
Among the above, the combination of the decolorizer (including radical generator, base precursor, nucleophile generator) and decolorizable dye achieves both decolorization during heat development and storage stability when not developed. It is easy to make it preferable. In particular, a combination of an intramolecular ring-closing decoloring dye and a base precursor is more preferable because it can achieve both decoloring properties and stability at a high level.
[0453]
Among the intramolecular ring-closing decoloring dyes, preferred are dyes having a polymethine chromophore, more preferably nucleophilicity by the action of a base at a position capable of reacting with a polymethine moiety to form a 5- to 7-membered ring. A polymethine dye having a group capable of generating a site. Particularly preferred is a polymethine dye having a group capable of forming a nucleophilic group by dissociation at a position capable of forming a 5- to 7-membered ring, such as a dye represented by the following general formulas (1) and (2). is there.
In particular, it is preferable to use a dye represented by the following general formula (1) or (2).
[0454]
Embedded image
[0455]
In the general formulas (1) and (2), R¹Is a hydrogen atom, aliphatic group, aromatic group, -NR^{twenty one}R²⁶, -OR^{twenty one}Or -SR^{twenty one}Represents R^{twenty one}And R²⁶Each independently represents a hydrogen atom, an aliphatic group or an aromatic group, or R^{twenty one}And R²⁶And combine to form a nitrogen-containing heterocycle. R²Represents a hydrogen atom, an aliphatic group or an aromatic group, and R¹And R²And may combine with each other to form a 5- or 6-membered ring. L¹And L²Each independently represents a substituted or unsubstituted methine, and the substituents of methine may be bonded to each other to form an unsaturated aliphatic ring or an unsaturated heterocyclic ring. Z¹Is an atomic group necessary to complete a 5- or 6-membered nitrogen-containing heterocyclic ring, and the nitrogen-containing heterocyclic ring may be condensed with an aromatic ring, and the nitrogen-containing heterocyclic ring and the condensed ring are It may have a substituent. A represents an acidic nucleus, and B represents an aromatic group, an unsaturated heterocyclic group, or a group represented by the following general formula (3). n and m each represent an integer of 1 to 3. When n and m are each 2 or more, L is 2 or more¹And L²May be the same or different.
[0456]
Embedded image
[0457]
In general formula (3), L^ThreeRepresents substituted or unsubstituted methine, L²To form an unsaturated aliphatic ring or an unsaturated heterocyclic ring. R^ThreeRepresents an aliphatic group or an aromatic group. Z²Is an atomic group necessary for completing a 5- or 6-membered nitrogen-containing heterocyclic ring, and the nitrogen-containing heterocyclic ring may be condensed with an aromatic ring, and the nitrogen-containing heterocyclic ring and the condensed ring are substituted. It may have a group.
[0458]
Where R¹Is a hydrogen atom, aliphatic group, aromatic group, -NR^{twenty one}R²⁶, -OR^{twenty one}Or -SR^{twenty one}Represents R^{twenty one}And R²⁶Each independently represents a hydrogen atom, an aliphatic group or an aromatic group, or R^{twenty one}And R²⁶And combine to form a nitrogen-containing heterocycle. R¹Is -NR^{twenty one}R²⁶, -OR^{twenty one}Or -SR^{twenty one}It is preferable that R^{twenty one}Is preferably an aliphatic group or an aromatic group, more preferably an unsubstituted alkyl group, a substituted alkyl group, an unsubstituted aralkyl group, a substituted aralkyl group, an unsubstituted aryl group or a substituted aryl group. R²⁶Is preferably a hydrogen atom or an aliphatic group, more preferably a hydrogen atom, an unsubstituted alkyl group or a substituted alkyl group. R^{twenty one}And R²⁶The nitrogen-containing heterocyclic ring formed by combining with each other is preferably a 5-membered ring or a 6-membered ring. The nitrogen-containing heterocycle may have a hetero atom other than nitrogen (eg, oxygen atom, sulfur atom).
[0459]
In this specification, “aliphatic group” means an unsubstituted alkyl group, a substituted alkyl group, an unsubstituted alkenyl group, a substituted alkenyl group, an unsubstituted alkynyl group, a substituted alkynyl group, an unsubstituted aralkyl group or a substituted aralkyl group. To do. In the present invention, an unsubstituted alkyl group, a substituted alkyl group, an unsubstituted alkenyl group, a substituted alkenyl group, an unsubstituted aralkyl group or a substituted aralkyl group is preferred, and an unsubstituted alkyl group, a substituted alkyl group, an unsubstituted aralkyl group or a substituted aralkyl group Is more preferable. A chain aliphatic group is preferred to a cyclic aliphatic group. The chain aliphatic group may have a branch. The number of carbon atoms of the unsubstituted alkyl group is preferably 1-30, more preferably 1-15, still more preferably 1-10, and most preferably 1-8. The alkyl part of the substituted alkyl group is the same as the preferred range of the unsubstituted alkyl group.
[0460]
The number of carbon atoms of the unsubstituted alkenyl group and the unsubstituted alkynyl group is preferably 2 to 30, more preferably 2 to 15, further preferably 2 to 12, and 2 to 8. Is most preferred. The alkenyl part of the substituted alkenyl group and the alkynyl part of the substituted alkynyl group are the same as the preferred ranges of the unsubstituted alkenyl group and the unsubstituted alkynyl group, respectively. The number of carbon atoms in the unsubstituted aralkyl group is preferably 7 to 35, more preferably 7 to 20, still more preferably 7 to 15, and most preferably 7 to 10. The aralkyl part of the substituted aralkyl group is the same as the preferred range of the unsubstituted aralkyl group.
[0461]
Examples of substituents for aliphatic groups (substituted alkyl groups, substituted alkenyl groups, substituted alkynyl groups, substituted aralkyl groups) include halogen atoms (fluorine atoms, chlorine atoms, bromine atoms), hydroxyl groups, alkoxy groups, aryloxy groups Silyloxy group, heterocyclic oxy group, acyloxy group, carbamoyloxy group, alkoxycarbonyloxy group, aryloxycarbonyloxy group, nitro group, sulfo group, carboxyl group, acyl group, alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl group Alkylthiocarbonyl group, heterocyclic group, cyano group, amino group (including anilino group), acylamino group, aminocarbonylamino group, alkoxycarbonylamino group, aryloxycarbonylamino group, sulfamoylamino group, alkyl and Reelsulfonylamino group, mercapto group, alkylthio group, arylthio group, heterocyclic thio group, sulfamoyl group, alkyl and arylsulfinyl group, alkyl and arylsulfonyl group, alkoxycarbonyl group, imide group, phosphino group, phosphinyl group, phosphinyl group An oxy group, a phosphinylamino group, a phosphono group and a silyl group are included. The carboxyl group, sulfo group, and phosphono group may be in a salt state. The cation that forms a salt with the carboxyl group, phosphono group, or sulfo group is preferably ammonium or an alkali metal ion (eg, lithium ion, sodium ion, potassium ion).
[0462]
In the present specification, the “aromatic group” means an unsubstituted aryl group or a substituted aryl group. The number of carbon atoms of the unsubstituted aryl group is preferably 6-30, more preferably 6-20, still more preferably 6-15, and most preferably 6-12. The aryl part of the substituted aryl group is the same as the preferred range of the unsubstituted aryl group. Examples of the substituent of the aromatic group (substituted aryl group) include the aliphatic group and those exemplified in the examples of the substituent of the aliphatic group.
[0463]
In the general formulas (1) and (2), R²Represents a hydrogen atom, an aliphatic group or an aromatic group, and R¹And R²May combine to form a 5- or 6-membered ring. The definition of the aliphatic group and the aromatic group is as described above. R²Is preferably a hydrogen atom or an aliphatic group, more preferably a hydrogen atom or an alkyl group, further preferably a hydrogen atom or an alkyl group having 1 to 15 carbon atoms, and more preferably a hydrogen atom. Most preferred.
[0464]
In the general formulas (1), (2) and (3), L¹, L²And L^ThreeEach independently represents an optionally substituted methine. Methine substituents may be bonded to each other to form an unsaturated aliphatic ring or an unsaturated heterocyclic ring. Examples of the methine substituent include a halogen atom, an aliphatic group, and an aromatic group. The definition of the aliphatic group and the aromatic group is as described above. A methine substituent may be bonded to form an unsaturated aliphatic ring or an unsaturated heterocyclic ring. An unsaturated aliphatic ring is preferred over an unsaturated heterocyclic ring. The ring to be formed is preferably a 5-membered ring or a 6-membered ring, and more preferably a cyclopentene ring or a cyclohexene ring. It is particularly preferred that the methine is unsubstituted or substituted at the meso position with an alkyl group or an aryl group.
[0465]
In the general formula (1), n represents an integer of 1 to 3, and is preferably 1 or 2. When n is 2 or more, the repeated methine may be the same or different. In the general formula (2), m represents an integer of 1 to 3, and is preferably 1 or 2. When m is 2 or more, the repeated methine may be the same or different.
[0466]
In the general formulas (1) and (2), Z¹Is an atomic group necessary to complete a 5- or 6-membered nitrogen-containing heterocycle, and the nitrogen-containing heterocycle may be condensed with an aromatic ring, and the nitrogen-containing heterocycle and its condensed ring May have a substituent. Examples of the nitrogen-containing heterocycle include oxazole ring, thiazole ring, selenazole ring, pyrrole ring, pyrroline ring, imidazole ring and pyridine ring. A 5-membered ring is preferred over a 6-membered ring. The nitrogen-containing heterocycle may be condensed with an aromatic ring (benzene ring or naphthalene ring). The nitrogen-containing heterocycle and its condensed ring may have a substituent. Examples of the substituent include the substituents of the above-mentioned aromatic group, preferably a halogen atom (fluorine atom, chlorine atom, bromine atom), hydroxyl, nitro, carboxyl, sulfo, alkoxy, aryl group And an alkyl group. Carboxyl and sulfo may be in a salt state. The cation that forms a salt with carboxyl and sulfo is preferably ammonium or an alkali metal ion (eg, sodium ion, potassium ion).
[0467]
In the general formula (1), B represents an aromatic group, an unsaturated heterocyclic group, or the following general formula (3). The definition of the aromatic group is as described above. The aromatic group represented by B is preferably a substituted or unsubstituted phenyl group, and the substituent includes a halogen atom, an amino group, an acylamino group, an alkoxy group, an aryloxy group, an alkyl group, an alkylthio group, and an aryl group. Those having an amino group, acylamino group, alkoxy group or alkyl group at the 4-position are particularly preferred. The unsaturated heterocyclic group represented by B is preferably a 5- or 6-membered heterocyclic group composed of carbon, oxygen, nitrogen, or sulfur atoms. Of these, a 5-membered ring is particularly preferred. Preferred examples include substituted or unsubstituted pyrrole, indole, thiophene and furan.
[0468]
In the general formula (3), Z²Is an atomic group forming a 5- or 6-membered nitrogen-containing heterocycle, and Z¹May be the same or different. Examples of the nitrogen-containing heterocycle are the above Z¹The thing similar to what was illustrated in (5) is illustrated. In the general formula (3), R^ThreeRepresents an aliphatic group or an aromatic group, and is preferably an aliphatic group, particularly —CHR which is a substituent on the nitrogen atom of the general formula (1)²(COR¹) Is most preferable.
[0469]
In the general formula (2), A represents an acidic nucleus. The acidic nucleus is preferably a group obtained by removing one or more (usually two) hydrogen atoms from each of a cyclic ketomethylene compound or a compound having a methylene group sandwiched between electron-withdrawing groups. Examples of cyclic ketomethylene compounds include 2-pyrazolin-5-one, rhodanine, hydantoin, thiohydantoin, 2,4-oxazolidinedione, isoxazolone, barbituric acid, thiobarbituric acid, indandione, dioxopyrazolo Examples include pyridine, meldrum acid, hydroxypyridine, pyrazolidinedione, 2,5-dihydrofuran-2-one, and pyrrolin-2-one. These may have a substituent.
[0470]
The compound having a methylene group sandwiched between the electron withdrawing groups is Z^aCH₂Z^bIt can be expressed as. Z^aAnd Z^bAre each independently -CN, -SO₂R^a1, -COR^a1, -COOR^a2, -CONHR^a2, -SO₂NHR^a2, -C [= C (CN)₂] R^a1, -C [= C (CN)₂NHR^a1Represents R^a1Represents an alkyl group, an aryl group or a heterocyclic group, and R^a2Represents a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group, and R^a1And R^a2Each may have a substituent. Among these acidic nuclei, 2-pyrazolin-5-one, isoxazolone, barbituric acid, indandione, hydroxypyridine, pyrazolidinedione and dioxopyrazolopyridine are more preferable.
[0471]
The dye represented by the general formula (1) preferably forms a salt with an anion. When the dye represented by formula (1) has an anionic group such as a carboxyl group or a sulfo group as a substituent, the dye can form an inner salt. In other cases, the dye preferably forms a salt with the extramolecular anion. The anion is preferably monovalent or divalent, and more preferably monovalent. Examples of anions include halogen ions (Cl^-, Br^-, I^-), P-toluenesulfonic acid ion, ethyl sulfate ion, 1,5-disulfonaphthalene dianion, PF₆ ^-, BF_Four ^-And ClO_Four ^-Is included.
[0472]
The dyes represented by the general formulas (1) and (2) may be used in a molecular dispersion state, but are preferably used in a solid fine particle dispersion state or an association state. In order for the dye to form an aggregate, the dye preferably has an ionic hydrophilic group. Examples of the ionic hydrophilic group include a sulfo group, a carboxyl group, a phosphono group, and a quaternary ammonium group. As the ionic hydrophilic group, a carboxyl group, a phosphono group, and a sulfo group are preferable, and a carboxyl group and a sulfo group are particularly preferable. The carboxyl group, phosphono group, and sulfo group may be in the form of a salt. Examples of counter ions that form a salt include ammonium ions, alkali metal ions (eg, lithium ions, sodium ions, potassium ions), and organic cations. (Eg, tetramethylammonium ion, tetramethylguanidinium ion, tetramethylphosphonium).
[0473]
Next, general formulas of aminobutadiene dyes and merocyanine dyes preferably used as non-decoloring dyes for preventing halation are shown below.
[0474]
General formula (4)
Embedded image
[0475]
Where R⁴¹, R⁴²Each independently represents a hydrogen atom, an aliphatic group, an aromatic group, or a group of nonmetallic atoms necessary to form a 5- or 6-membered ring by linking each other. Also, R⁴¹, R⁴²May be bonded to a methine group adjacent to the nitrogen atom to form a 5- or 6-membered ring. A⁴¹Represents an acidic nucleus.
[0476]
General formula (5)
Embedded image
[0477]
Where R⁵¹~ R⁵⁵Each independently represents a hydrogen atom, an aliphatic group or an aromatic group;⁵¹And R⁵⁴Together may form a double bond, R⁵¹And R⁵⁴Together form a double bond, R⁵²And R⁵³May be linked to form a benzene ring or a naphthalene ring. R⁵⁵Represents an aliphatic group or an aromatic group, E represents an oxygen atom, a sulfur atom, an ethylene group,> N—R⁵⁶Or> C (R⁵⁷) (R⁵⁸) And R⁵⁶Represents an aliphatic group or an aromatic group, R⁵⁷, R⁵⁸Each independently represents a hydrogen atom or an aliphatic group. A⁵¹Represents an acidic nucleus.
[0478]
General formula (6)
Embedded image
[0479]
Where R⁶¹Represents a hydrogen atom, an aliphatic group, or an aromatic group. R⁶²Represents a hydrogen atom, an aliphatic group, or an aromatic group. Z⁶¹Represents an atomic group necessary for forming a nitrogen-containing heterocycle. Z⁶²And Z^{62 '}Is (N-R⁶²) Represents a group of atoms necessary for forming a heterocyclic or acyclic acidic terminal group together with m). However, Z⁶¹, And Z⁶²And Z^{62 '}Each may have a condensed ring. m represents 0 or 1;
[0480]
Hereinafter, the dyes represented by the general formulas (4), (5) and (6) will be described in detail.
R in the general formulas (4), (5) and (6)⁴¹, R⁴², R⁵¹~ R⁵⁸, R⁶¹And R⁶²An aliphatic group and an aromatic group in R are R¹The same aliphatic groups and aromatic groups described in the above can be applied, and examples of substituents are also the same.
[0481]
A⁴¹, A⁵¹As the acidic nucleus represented by the formula (2), those similar to those exemplified in A can be applied, each of a cyclic ketomethylene compound or a compound having a methylene group sandwiched between electron withdrawing groups. A group in which one or more (usually two) hydrogen atoms have been removed is preferred. Examples of more preferred methylene compounds include Z^aCH₂Z^b(Synonymous with those described in the description of A in the general formula (2)), 2-pyrazolin-5-one, isoxazolone, barbituric acid, indandione, meldrum acid, hydroxypyridine, pyrazolidinedione and dioxo And pyrazolopyridine. These may have a substituent.
R⁴¹And R⁴²Preferred examples of the 5- or 6-membered ring formed by linking pyrrolidine ring, piperidine ring, morpholine ring and the like.
[0482]
In the general formula (6), Z⁶¹Is an atomic group necessary to complete a 5- or 6-membered nitrogen-containing heterocycle, and the nitrogen-containing heterocycle may be condensed with an aromatic ring, and the nitrogen-containing heterocycle and its condensed ring May have a substituent. Examples of the nitrogen-containing heterocycle include thiazoline nucleus, thiazole nucleus, benzothiazole nucleus, oxazoline nucleus, oxazole nucleus, benzoxazole nucleus, selenazoline nucleus, selenazole nucleus, benzoselenazole nucleus, tellurazoline nucleus, tellurazole nucleus, benzotelrazole Nucleus, 3,3-dialkylindolenine nucleus (eg 3,3-dimethylindolenine), imidazoline nucleus, imidazole nucleus, benzimidazole nucleus, 2-pyridine nucleus, 4-pyridine nucleus, 2-quinoline nucleus, 4-quinoline nucleus 1-isoquinoline nucleus, 3-isoquinoline nucleus, imidazo [4,5-b] quinoxaline nucleus, oxadiazole nucleus, thiadiazole nucleus, tetrazole nucleus, pyrimidine nucleus, etc., preferably thiazoline nucleus, thiazole nucleus Benzothiazole nucleus, oxa Phosphorus nucleus, oxazole nucleus, benzoxazole nucleus, 3,3-dialkylindolenine nucleus (for example, 3,3-dimethylindolenine), imidazoline nucleus, imidazole nucleus, benzimidazole nucleus, 2-pyridine nucleus, 4-pyridine nucleus, 2 -Quinoline nucleus, 4-quinoline nucleus, 1-isoquinoline nucleus, 3-isoquinoline nucleus, more preferably thiazoline nucleus, thiazole nucleus, benzothiazole nucleus, oxazoline nucleus, oxazole nucleus, benzoxazole nucleus, 3,3-dialkylindo A renin nucleus (for example, 3,3-dimethylindolenine), an imidazoline nucleus, an imidazole nucleus, a benzimidazole nucleus, particularly preferably a thiazoline nucleus, a thiazole nucleus, a benzothiazole nucleus, an oxazoline nucleus, an oxazole nucleus, a benzoxazole nucleus, Most preferred It is a thiazoline nucleus, an oxazoline nucleus, a benzoxazole nucleus. The nitrogen-containing heterocycle may be condensed with an aromatic ring (benzene ring or naphthalene ring). The nitrogen-containing heterocycle and its condensed ring may have a substituent. Examples of the substituent include the above-mentioned aromatic substituents, preferably a halogen atom (fluorine atom, chlorine atom, bromine atom), hydroxyl group, nitro group, carboxyl group, sulfo group, An alkoxy group, an aryl group and an alkyl group; The carboxyl group and the sulfo group may be in a salt state. The cation that forms a salt with the carboxyl group and the sulfo group is preferably ammonium or an alkali metal ion (for example, sodium ion or potassium ion).
[0483]
Z⁶²And Z^{62 '}And (N-R⁶²) M together represent a group of atoms necessary to form a heterocyclic or acyclic acidic end group. The heterocyclic ring (preferably a 5- or 6-membered heterocyclic ring) may be any, but an acidic nucleus is preferable.
Next, the acidic nucleus and the acyclic acidic end group will be described. The acidic nuclei and acyclic acidic end groups can take the form of the acidic nuclei and acyclic acidic end groups of any common merocyanine dye. Z in the preferred form⁶²Is a thiocarbonyl group, a carbonyl group, an ester group, an acyl group, a carbamoyl group, a cyano group or a sulfonyl group, more preferably a thiocarbonyl group or a carbonyl group. Z^{62 '}Represents the remaining atomic groups necessary to form an acidic nucleus and an acyclic acidic end group. In the case of forming an acyclic acidic terminal group, a thiocarbonyl group, a carbonyl group, an ester group, an acyl group, a carbamoyl group, a cyano group, a sulfonyl group and the like are preferable.
m is 0 or 1, but is preferably 1.
[0484]
The acidic nuclei and acyclic acidic end groups mentioned here are, for example, “The Theory of the Photographic Process”, 4th edition, edited by James, Macmillan Publishing Co., Ltd. 1977, 197-200 Mitsugu. Here, an acyclic acidic terminal group means an acidic or electron-accepting terminal group that does not form a ring.
Acid nuclei and acyclic acidic end groups are specifically described in U.S. Pat. Nos. 3,567,719, 3,575,869, 3,804,634, No. 3,837,862, No. 4,002,480, No. 4,925,777, JP-A-3-167546, U.S. Pat. No. 5,994,051, U.S. Pat. Examples thereof include those described in Japanese Patent No. 5,747,236.
[0485]
The acidic nucleus is a heterocyclic ring (preferably a 5- or 6-membered nitrogen-containing heterocyclic ring) composed of a carbon atom, a nitrogen atom, and / or a chalcogen atom (typically an oxygen atom, a sulfur atom, a selenium atom, and a tellurium atom). And more preferably a 5-membered or 6-membered nitrogen-containing heterocyclic ring consisting of a carbon atom, a nitrogen atom, and / or a chalcogen atom (typically an oxygen atom, a sulfur atom, a selenium atom, and a tellurium atom). . Specifically, 2-pyrazolin-5-one, pyrazolidine-3,5-dione, imidazolin-5-one, hydantoin, 2 or 4-thiohydantoin, 2-iminooxazolidine-4-one, 2-oxazoline-5 -One, 2-thiooxazolidine-2,5-dione, 2-thiooxazoline-2,4-dione, isoxazolin-5-one, 2-thiazoline-4-one, thiazolidine-4-one, thiazolidine-2, 4-dione, rhodanine, thiazolidine-2,4-dithione, isorhodanine, indan-1,3-dione, thiophen-3-one, thiophen-3-one-1,1-dioxide, indoline-2-one, indoline- 3-one, 2-oxoindazolinium, 3-oxoindazolinium, 5,7-dioxo-6,7-dihi Rothiazolo [3,2-a] pyrimidine, cyclohexane-1,3-dione, 3,4-dihydroisoquinolin-4-one, 1,3-dioxane-4,6-dione, barbituric acid, 2-thiobarbitur Acid, chroman-2,4-dione, indazolin-2-one, pyrido [1,2-a] pyrimidine-1,3-dione, pyrazolo [1,5-b] quinazolone, pyrazolo [1,5-a] Benzimidazole, pyrazolopyridone, 1,2,3,4-tetrahydroquinoline-2,4-dione, 3-oxo-2,3-dihydrobenzo [d] thiophene-1,1-dioxide, 3-dicyanomethine-2, 3-Dihydrobenzo [d] thiophene-1,1-dioxide nuclei, carbonyl groups or thiocarbonyl groups forming these nuclei are active in acidic nuclei Nuclei having an exomethylene structure substituted at the tylene position, and nuclei having an exomethylene structure substituted at the active methylene position of an active methylene compound having a structure such as ketomethylene or cyanomethylene as a raw material for an acyclic acidic end group , And nuclei in which this is repeated.
These acidic nuclei and acyclic acidic terminal groups may be substituted or condensed with the substituents or rings shown in the examples of the substituents of the aromatic group.
[0486]
Z⁶²And Z^{62 '}And (N-R⁶²) M is preferably hydantoin, 2 or 4-thiohydantoin, 2-oxazoline-5-one, 2-thiooxazoline-2,4-dione, thiazolidine-2,4-dione, rhodanine, thiazolidine-2,4- Dithione, barbituric acid, 2-thiobarbituric acid, more preferably hydantoin, 2 or 4-thiohydantoin, 2-oxazolin-5-one, rhodanine, barbituric acid, 2-thiobarbituric acid . Particularly preferred are 2 or 4-thiohydantoin, 2-oxazolin-5-one and rhodanine.
[0487]
When the dye represented by the general formulas (4) to (6) is water-soluble, it preferably has an ionic hydrophilic group. Examples and preferred examples of the ionic hydrophilic group are the same as those described in the general formulas (1) and (2).
[0488]
Specific examples of preferably used antihalation dyes are shown below, but the antihalation dyes are not limited to the following specific examples.
[0489]
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[0490]
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[0491]
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[0492]
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[0493]
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[0494]
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[0495]
[Chemical Formula 86]
[0496]
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[0497]
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[0498]
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[0499]
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[0500]
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[0501]
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[0502]
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[0503]
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[0504]
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[0505]
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[0506]
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[0507]
Regarding the synthesis of antihalation dye compounds, a general method is described in “The Cyanine Dyes and Related Compounds”, Frances Hamer, Interscience Publishers, 1964. It can be synthesized by a method in conformity with Japanese Unexamined Patent Publication Nos. 2000-112058, 2000-86927 and 2000-86928.
[0508]
When the antihalation dye is decolored in the process of heat development, it can be decolored by applying a decoloring agent under heating conditions. Particularly, in the dyes of the general formulas (1) and (2), the active methylene group in the dye is deprotonated by the action of the base, and the nucleophilic species generated thereby nucleophilically attacks the methylene chain in the molecule, Discolors by forming an intramolecular ring closure. Accordingly, any base that can be used for this reaction can deprotonate the active methylene group in the dye. The number of ring members newly formed by the intramolecular ring-closing reaction is not particularly limited, but is preferably a 5- to 7-membered ring, and more preferably a 5-membered ring or a 7-membered ring. The substantially colorless compound formed in this way is a stable compound and does not return to the original dye, and there is no problem such as coloring due to the once decolored dye returning to its original state.
[0509]
The heating temperature in the decoloring reaction of the dye is preferably 40 to 200 ° C, more preferably 80 to 150 ° C, still more preferably 100 to 130 ° C, and 115 to 125 ° C. Is most preferred. The heating time is preferably 5 to 120 seconds, more preferably 10 to 60 seconds, further preferably 12 to 30 seconds, and most preferably 14 to 25 seconds. In the photothermographic material, heating for heat development can be used. As will be described later, it is preferable to use a heat-responsive base precursor (details will be described later) that generates a base by supplying heat. In such a case, the actual heating temperature and heating time are determined in consideration of the temperature and time required for thermal development or the temperature and time required for thermal decomposition.
[0510]
The decoloring agent necessary for the decoloring reaction is preferably a radical, a nucleophile, a base or a precursor thereof. When using the dye represented by the general formula (1) or (2), it is preferable to decolorize using a base or a base precursor. The base necessary for the decoloring reaction is a broad base, and includes a nucleophile (Lewis base) in addition to a narrow base. When the base coexists with the dye, the decoloring reaction may proceed slightly even at room temperature. Accordingly, it is preferable that the base is physically or chemically isolated from the dye, and when the color is to be erased, the isolated state is released by heating, for example, and the base and the dye are brought into contact (reaction). As a means for physically separating both, at least one of the dye and the base is encapsulated in a microcapsule; at least one of the dye and the base is encapsulated in a fine particle of a hot-melt material; or Bases are included in different layers; there is a means. The microcapsules include those that burst by pressure and those that burst by heating. Since the decoloring reaction proceeds easily under heating conditions, it is convenient to use microcapsules that burst (thermally responsive) upon heating. For sequestration, at least one of base and dye is encapsulated in microcapsules. Both can be encapsulated in separate microcapsules. When the outer shell of the microcapsule is opaque, it is preferable that the dye is contained outside the microcapsule and the base is encapsulated in the microcapsule. The thermo-responsive microcapsules are described in Hiroyuki Moriga, Introductory / Special Paper Chemistry (Showa 50), and JP-A-1-150575.
[0511]
Wax or the like can be used as the hot-melt material used for separating the dye from the base. One of a base and a dye (preferably a base) can be added to the fine particles of the heat-meltable substance for isolation. The melting point of the hot-melt material is preferably between room temperature and the heating temperature when the decoloring reaction proceeds. When the layer containing the dye and the layer containing the base are separated and separated from each other, it is preferable to provide a barrier layer containing a hot-melt material between these layers.
[0512]
It is preferable to chemically separate the dye and the base because they are easy to implement. As a means for chemically isolating both, it is preferable to use a precursor that can generate (including release) a base by heating. As the base precursor, a thermal decomposition type base precursor is representative, and in particular, a thermal decomposition type (decarboxylation type) base precursor composed of a salt of a carboxylic acid and a base is representative. When the decarboxylated base precursor is heated, the carboxyl group of the carboxylic acid undergoes a decarboxylation reaction, and the organic base is released. As the carboxylic acid constituting the thermal decomposition method base precursor, sulfonylacetic acid or propiolic acid which is easily decarboxylated can be used. The sulfonylacetic acid and propiolic acid preferably have, as a substituent, a group having an aromaticity that promotes decarboxylation (an aryl group or an unsaturated heterocyclic group). The base precursor of sulfonyl acetate is described in JP-A-59-168441, and the base precursor of propiolate is described in JP-A-59-180537. The base component of the decarboxylation type base precursor is preferably an organic base, more preferably amidine, guanidine or a derivative thereof. The organic base is preferably a diacid base, a triacid base or a tetraacid base, more preferably a diacid base, and most preferably a diacid base of an amidine derivative or a guanidine derivative.
[0513]
The diacid base, triacid base or tetraacid base precursor of the amidine derivative is described in JP-B-7-59545. The diacid base, triacid base or tetraacid base precursor of the guanidine derivative is described in JP-B-8-10321. The diacid base of the amidine derivative or guanidine derivative comprises (A) two amidine or guanidine moieties, (B) a substituent of the amidine or guanidine moiety and (C) a divalent linking two amidine or guanidine moieties. Consists of a linking group. Examples of the substituent of (B) include an alkyl group (including a cycloalkyl group), an alkenyl group, an alkynyl group, an aralkyl group, and a heterocyclic residue. Two or more substituents may combine to form a nitrogen-containing heterocycle. The linking group (C) is preferably an alkylene group or a phenylene group. As an example of a diacid base precursor of an amidine derivative or a guanidine derivative, a base precursor described in Chemical formula 55 to Chemical formula 95 of JP-A No. 11-231457 can be preferably used in the present invention.
[0514]
When the dye is decolored, the optical density after heat development can be reduced to 0.1 or less. Two or more decoloring dyes may be used in combination in the photothermographic material. Similarly, two or more kinds of base precursors may be used in combination. In thermal decoloration using such decoloring dyes and base precursors, substances that lower the melting point by 3 ° C. or more when mixed with a base precursor as described in JP-A-11-352626 (for example, diphenylsulfone, 4- Use of chlorophenyl (phenyl) sulfone), 2-naphthyl benzoate, or the like is preferable from the viewpoint of thermal decoloring property and the like.
[0515]
The layer containing the antihalation dye preferably contains a binder together with the dye. As the binder, a hydrophilic polymer (eg, polyvinyl alcohol, gelatin) is preferably used. In general, in the photothermographic material, the addition amount of the antihalation dye is preferably used in such an amount that the optical density (absorbance) exceeds 0.1 when measured at a target wavelength. More preferably, it is 2 to 2.0. The amount of the dye used to obtain such an optical density can be reduced by using an aggregate, and is generally 0.001 to 0.2 g / m.²Degree. Preferably, 0.001 to 0.1 g / m²More preferably, 0.001 to 0.05 g / m²It is. In the mode of decolorizing the antihalation dye, the optical density can be lowered to 0.1 or less by decoloring the dye. Two or more dyes may be used in combination. Similarly, two or more kinds of base precursors may be used in combination. The use amount (mol) of the base precursor is preferably 1 to 100 times, more preferably 3 to 30 times the use amount (mol) of the dye. The base precursor is preferably dispersed and contained in any layer of the photothermographic material in the form of solid fine particles.
[0516]
As a method for adding the antihalation dye to the non-photosensitive layer, a method of adding a solid fine particle dispersion or an aggregate dispersion to the coating solution for the non-photosensitive layer can be employed. This addition method is the same as the method of adding a dye to an ordinary photothermographic material.
[0517]
3) Back layer
The back layer applicable to the present invention is described in paragraph numbers 0128 to 0130 of JP-A No. 11-65021.
[0518]
In the present invention, a colorant having an absorption maximum at 300 to 450 nm can be added for the purpose of improving silver tone and aging of the image. Such colorants are disclosed in JP-A Nos. 62-210458, 63-104046, 63-103235, 63-208846, 63-306436, 63-314535, and JP-A-01-61745. No. 1, Japanese Patent Laid-Open No. 2001-100363, and the like. Such colorants are usually 0.1 mg / m²~ 1g / m²The back layer provided on the opposite side of the photosensitive layer is preferable as the layer to be added in the range of.
In order to adjust the base color tone, it is preferable to use a dye having an absorption peak at 580 to 680 nm. As the dye for this purpose, an azomethine oil-soluble dye described in JP-A-4-359967 and JP-A-4-359968 having a small absorption intensity on the short wavelength side, and a phthalocyanine water-soluble dye described in Japanese Patent Application No. 2002-96797 are preferable. The dye for this purpose may be added to any layer, but is more preferably added to the non-photosensitive layer on the emulsion surface side or the back surface side.
[0519]
The photothermographic material of the present invention is a so-called single-sided photosensitive material having a photosensitive layer containing at least one silver halide emulsion on one side of the support and a back layer on the other side. preferable.
[0520]
4) Matting agent
In the present invention, it is preferable to add a matting agent for improving transportability, and the matting agent is described in paragraph Nos. 0126 to 0127 of JP-A No. 11-65021. Matting agent is photosensitive material 1m²When expressed in terms of coating amount per unit, preferably 1 to 400 mg / m², More preferably 5 to 300 mg / m²It is.
In the present invention, the shape of the matting agent may be either a regular shape or an irregular shape, but is preferably a regular shape, and a spherical shape is preferably used. The average particle size is preferably 0.5 to 10 μm, more preferably 1.0 to 8.0 μm, and still more preferably 2.0 to 6.0 μm. The variation coefficient of the size distribution is preferably 50% or less, more preferably 40% or less, and still more preferably 30% or less. Here, the coefficient of variation is a value represented by (standard deviation of particle size) / (average value of particle size) × 100. It is also preferable to use two types of matting agents having a small variation coefficient and having an average particle size ratio larger than 3.
The emulsion surface may have any matte degree as long as no stardust failure occurs, but the Beck smoothness is preferably 30 seconds or more and 2000 seconds or less, particularly preferably 40 seconds or more and 1500 seconds or less. The Beck smoothness can be easily obtained by Japanese Industrial Standard (JIS) P8119 “Smoothness test method using Beck tester for paper and paperboard” and TAPPI standard method T479.
[0521]
In the present invention, the matte degree of the back layer is preferably a Beck smoothness of 1200 seconds or less and 10 seconds or more, preferably 800 seconds or less and 20 seconds or more, and more preferably 500 seconds or less and 40 seconds or more.
[0522]
In the present invention, the matting agent is preferably contained in the outermost surface layer of the photosensitive material, the layer functioning as the outermost surface layer, or a layer close to the outer surface, and is contained in a layer acting as a so-called protective layer. It is preferable.
[0523]
5) Polymer latex
In particular, when the photothermographic material of the present invention is used for printing applications in which dimensional change is a problem, it is preferable to use a polymer latex for the surface protective layer or the back layer. For such polymer latex, “Synthetic resin emulsion (Hiraku Okuda, Hiroshi Inagaki, published by Kobunshi Publishing (1978))”, “Application of synthetic latex (Takaaki Sugimura, Ikuo Kataoka, Junichi Suzuki, Keiji Kasahara, Takashi "Molecular Publications (1993))" and "Synthetic Latex Chemistry (Souichi Muroi, published by High Polymers Publication (1970))", specifically, methyl methacrylate (33.5% by mass) / ethyl Latex of acrylate (50% by mass) / methacrylic acid (16.5% by mass) copolymer, latex of methyl methacrylate (47.5% by mass) / butadiene (47.5% by mass) / itaconic acid (5% by mass), ethyl acrylate / methacrylic acid Copolymer latex, methyl methacrylate (58.9% by mass) / 2-ethylhexyl acrylate (25.4% by mass) / styrene (8.6% by mass) / 2-hydro Latex of methyl methacrylate (5.1 mass%) / acrylic acid (2.0 mass%) copolymer, methyl methacrylate (64.0 mass%) / styrene (9.0 mass%) / butyl acrylate (20.0 mass%) / 2-hydroxyethyl methacrylate (5.0 Mass%) / acrylic acid (2.0 mass%) copolymer latex and the like. Further, as a binder for the surface protective layer, a combination of polymer latex described in Japanese Patent Application No. 11-6872 and the technique described in Paragraph Nos. 0021 to 0025 of Japanese Patent Application Laid-Open No. 2000-267226, Japanese Patent Application No. 11-6872 The technology described in paragraph numbers 0027 to 0028 of the specification and the technology described in paragraph numbers 0023 to 0041 of JP 2000-19678 may be applied. The ratio of the polymer latex in the surface protective layer is preferably 10% by mass or more and 90% by mass or less, and particularly preferably 20% by mass or more and 80% by mass or less of the total binder.
[0524]
6) Membrane pH
The photothermographic material of the present invention preferably has a film surface pH of 7.0 or less, more preferably 6.6 or less before heat development. The lower limit is not particularly limited, but is about 3. The most preferred pH range is in the range of 4 to 6.2. The film surface pH is preferably adjusted using an organic acid such as a phthalic acid derivative, a non-volatile acid such as sulfuric acid, or a volatile base such as ammonia from the viewpoint of reducing the film surface pH. In particular, ammonia is volatile and is preferable for achieving a low film surface pH because it can be removed before the coating process or heat development.
In addition, it is also preferable to use ammonia in combination with a nonvolatile base such as sodium hydroxide, potassium hydroxide, or lithium hydroxide. A method for measuring the film surface pH is described in paragraph No. 0123 of JP-A-2000-284399.
[0525]
7) Hardener
A hardener may be used for each layer such as the photosensitive layer, protective layer, and back layer of the present invention. Examples of hardeners are THJames' “THE THEORY OF THE PHOTOGRAPHIC PROCESS FOURTH EDITION” (Macmillan Publishing Co., Inc., published in 1977), each of the methods described on pages 77 to 87, Chrome Alum, 2 , 4-Dichloro-6-hydroxy-s-triazine sodium salt, N, N-ethylenebis (vinylsulfoneacetamide), N, N-propylenebis (vinylsulfoneacetamide) and polyvalent metals described on page 78 Ions, polyisocyanates such as US Pat. No. 4,281,060 and JP-A-6-208193, epoxy compounds such as US Pat. No. 4,791,042, and vinyl sulfone compounds such as JP-A 62-89048 are preferably used.
[0526]
The hardener is added as a solution, and the addition time of this solution into the protective layer coating solution is from 180 minutes before to immediately before application, preferably from 60 minutes to 10 seconds before application. As long as the effects of the present invention are sufficiently exhibited, there is no particular limitation. Specific mixing methods include mixing in a tank in which the average residence time calculated from the addition flow rate and the amount of liquid delivered to the coater is the desired time, and by N. Harnby, MFEdwards, AWNienow, Takahashi There is a method of using a static mixer or the like described in Chapter 8 of the translation of Koji “Liquid Mixing Technology” (published by Nikkan Kogyo Shimbun, 1989).
[0527]
8) Surfactant
JP-A-11-65021 paragraph number 0132 for surfactants applicable to the present invention, paragraph number 0133 for solvents, paragraph number 0134 for supports, paragraph number for antistatic or conductive layers The method for obtaining a color image is described in paragraph No. 0136 of the same publication, and the slip agent is described in paragraph Nos. 0061 to 0064 of JP-A No. 11-84573 and paragraph Nos. 0049 to 0062 of Japanese Patent Application No. 11-106881.
In the present invention, it is preferable to use a fluorosurfactant. Specific examples of the fluorosurfactant include compounds described in JP-A-10-197985, JP-A-2000-19680, JP-A-2000-214554, and the like. In addition, polymeric fluorine-based surfactants described in JP-A-9-281636 are also preferably used. In the photothermographic material of the present invention, it is preferable to use a fluorosurfactant described in JP-A No. 2002-82411, Japanese Patent Application Nos. 2001-242357 and 2001-264110. In particular, the fluorosurfactants described in Japanese Patent Application Nos. 2001-242357 and 2001-264110 are preferable in terms of charge adjustment ability, stability of the coated surface, and smoothness when coating and manufacturing with an aqueous coating solution. The fluorine-based surfactant described in Japanese Patent Application No. 2001-264110 is most preferable in that it has a high charge control capability and requires a small amount of use.
In the present invention, the fluorosurfactant can be used on either the emulsion surface or the back surface, and is preferably used on both surfaces. Further, it is particularly preferable to use in combination with a conductive layer containing the above-described metal oxide. In this case, sufficient performance can be obtained even if the amount of the fluorosurfactant used on the surface having the conductive layer is reduced or removed.
The preferred amount of fluorosurfactant used is 0.1 mg / m for each of the emulsion surface and back surface²~ 100mg / m²In the range, more preferably 0.3 mg / m²~ 30mg / m²Range, more preferably 1 mg / m²~ 10mg / m²Range. In particular, the fluorosurfactant described in Japanese Patent Application No. 2001-264110 has a large effect and is 0.01 to 10 mg / m.²Is preferably in the range of 0.1 to 5 mg / m²The range of is more preferable.
[0528]
9) Antistatic agent
In the present invention, it is preferable to have a conductive layer containing a metal oxide or a conductive polymer. The antistatic layer may serve as an undercoat layer, a back layer surface protective layer, or the like, or may be provided separately. As the conductive material for the antistatic layer, a metal oxide in which conductivity is improved by introducing oxygen defects or different metal atoms into the metal oxide is preferably used. Examples of metal oxides are ZnO, TiO₂, SnO₂And for ZnO, addition of Al and In, SnO₂For Sb, Nb, P, halogen elements, etc., TiO₂In contrast, addition of Nb, Ta or the like is preferable. Especially SnO with Sb added₂Is preferred. The amount of different atoms added is preferably in the range of 0.01 to 30 mol%, more preferably in the range of 0.1 to 10 mol%. The shape of the metal oxide may be spherical, needle-like, or plate-like, but needle-like particles having a long axis / uniaxial ratio of 2.0 or more, preferably 3.0 to 50 are preferable from the viewpoint of providing conductivity. The amount of metal oxide used is preferably 1 mg / m²~ 1000mg / m²In the range, more preferably 10 mg / m²~ 500mg / m²Range, more preferably 20 mg / m²~ 200mg / m²Range. The antistatic layer of the present invention may be disposed on either the emulsion surface side or the back surface side, but is preferably disposed between the support and the back layer. Specific examples of the antistatic layer of the present invention are disclosed in paragraph No. 0135 of JP-A-11-65021, JP-A-56-143430, JP-A-56-143431, JP-A-58-62646, JP-A-56-120519, JP-A-11- No. 84573, paragraph numbers 0040 to 0051, US Pat. No. 5,575,957, and JP-A No. 11-223898, paragraph numbers 0078 to 0084.
[0529]
10) Support
The transparent support is a polyester, particularly polyethylene, which has been heat-treated in a temperature range of 130 to 185 ° C. in order to relieve internal strain remaining in the film during biaxial stretching and to eliminate thermal shrinkage strain generated during heat development. Terephthalate is preferably used. In the case of a photothermographic material for medical use, the transparent support may be colored with a blue dye (for example, dye-1 described in Examples of JP-A-8-240877) or may be uncolored. Examples of the support include water-soluble polyesters disclosed in JP-A-11-84574, styrene-butadiene copolymers described in JP-A-10-186565, and vinylidene chloride described in JP-A-2000-39684 and JP-A-11-106881, paragraphs 0063 to 0080. It is preferable to apply an undercoating technique such as a copolymer. When the emulsion layer or the back layer is coated on the support, the water content of the support is preferably 0.5 wt% or less.
[0530]
11) Other additives
An antioxidant, a stabilizer, a plasticizer, an ultraviolet absorber, or a coating aid may be further added to the photothermographic material. Various additives are added to either the photosensitive layer or the non-photosensitive layer. For these, reference can be made to WO98 / 36322, EP803764A1, JP-A-10-186567, 10-18568 and the like.
[0531]
12) Application method
The photothermographic material in the invention may be applied by any method. Specifically, various coating operations are used, including extrusion coating, slide coating, curtain coating, dip coating, knife coating, flow coating, or extrusion coating using a hopper of the type described in U.S. Pat. Stephen F. Kistler and Petert M. Schweizer “LIQUID FILM COATING” (CHAPMAN & HALL, 1997) pages 399 to 536, preferably used for extrusion coating or slide coating, particularly preferably for slide coating It is done. An example of the shape of the slide coater used for slide coating is shown in Figure 11b.1 on page 427 of the same book. If desired, two or more layers can be coated simultaneously by the method described in pages 399 to 536 of the same document, the method described in US Pat. No. 2,761,791 and British Patent No. 837,095. Particularly preferred coating methods in the present invention are those described in JP-A Nos. 2001-194748, 2002-153808, 2002-153803, and 2002-182333.
[0532]
The organic silver salt-containing layer coating solution in the present invention is preferably a so-called thixotropic fluid. Regarding this technique, JP-A-11-52509 can be referred to. The organic silver salt-containing layer coating solution in the present invention has a shear rate of 0.1 S.^-1The viscosity in is preferably 400 mPa · s or more and 100,000 mPa · s or less, and more preferably 500 mPa · s or more and 20,000 mPa · s or less. Also, shear rate 1000S^-1Is preferably 1 mPa · s or more and 200 mPa · s or less, and more preferably 5 mPa · s or more and 80 mPa · s or less.
[0533]
In the case of preparing the coating liquid of the present invention, a known in-line mixer or implant mixer is preferably used when mixing two kinds of liquids. A preferred in-line mixer of the present invention is described in JP-A-2002-85948, and an implant mixer is described in JP-A-2002-90940.
The coating solution in the present invention is preferably subjected to defoaming treatment in order to keep the coated surface state good. A preferred defoaming treatment method of the present invention is the method described in JP-A-2002-66431.
When applying the coating solution of the present invention, it is preferable to perform static elimination in order to prevent adhesion of dust, dust, and the like due to electric resistance of the support. An example of a preferable static elimination method in the present invention is described in JP-A-2002-143747.
In the present invention, it is important to precisely control the drying air and the drying temperature in order to dry the non-setting image forming layer coating solution. The preferred drying method of the present invention is described in detail in JP-A Nos. 2001-194749 and 2002-139814.
The photothermographic material of the present invention is preferably subjected to a heat treatment immediately after coating and drying in order to improve film formability. The temperature of the heat treatment is preferably in the range of 60 ° C. to 100 ° C. as the film surface temperature, and the heating time is preferably in the range of 1 second to 60 seconds. A more preferable range is a film surface temperature of 70 to 90 ° C. and a heating time of 2 to 10 seconds. A preferred heat treatment method of the present invention is described in JP-A No. 2002-107872.
In order to stably and continuously produce the photothermographic material of the present invention, the production methods described in JP-A Nos. 2002-156728 and 2002-182333 are preferably used.
[0534]
The photothermographic material is preferably a mono-sheet type (a type capable of forming an image on the photothermographic material without using another sheet such as an image receiving material).
[0535]
13) Packaging materials
The light-sensitive material of the present invention is preferably packaged with a packaging material having a low oxygen permeability and / or moisture permeability in order to suppress fluctuations in photographic performance during raw storage or to improve curling, curling, etc. Oxygen permeability is 50ml / atm ・ m at 25 ℃²・ It is preferably less than day, more preferably 10 ml / atm · m²・ Day or less, more preferably 1.0ml / atm ・ m²・ It is less than day. Moisture permeability is 10g / atm · m²・ It is preferably less than day, more preferably 5g / atm · m²・ Day or less, more preferably 1g / atm ・ m²・ It is less than day.
Specific examples of the packaging material having a low oxygen permeability and / or moisture permeability are disclosed in, for example, JP-A-8-254793. This is a packaging material described in JP-A-2000-206653.
[0536]
14) Other available technologies
Techniques that can be used for the photothermographic material of the present invention include EP803764A1, EP883022A1, WO98 / 36322, JP 56-62648, 58-62644, JP 9-43766, and 9- 281637, 9-297367, 9-304869, 9-311405, 9-329865, 10-10669, 10-62899, 10-69023, 10-186568, 10-90823, 10-171063, 10-186565, 10-186567, 10-186569 to 10-186572, 10-197974, 10-197982, 10 -197983, 10-197985 to 10-197987, 10-207001, 10-207004, 10-221807, 10-282601, 10-288823, 10-288823, 10-288824 10-307365, 10-312038, 10-339934, 11-7100, 11-15105, 11-24200, 11-24201, 11-30832, 11-84574, 11-65021, 11-109547, 11-125880, 11-129629, 11-133536 to 11-133539, 11-133542, 11 -133543, 11-223898, 11-352627, 11-305377, 11-305378, 11-305384, 11-305380, 11-316435, 11-327076, 11-338096, 11-338098, 11-338099, 11- 343420, JP 2000-187298, 2000-10229, 2000-47345, 2000-206642, 2000-98530, 2000-98531, 2000-112059, 2000-112060 No., 2000-112104, 2000-112064, 2000-171936.
[0537]
In the case of a multicolor color photothermographic material, each emulsion layer generally uses a functional or non-functional barrier layer between each photosensitive layer, as described in US Pat. No. 4,460,681. Thus, they are kept distinguished from each other.
The construction in the case of a multicolor color photothermographic material may include a combination of these two layers for each color, and includes all components in a single layer as described in US Pat. No. 4,708,928. May be.
[0538]
(Image forming method)
1) Exposure
The light-sensitive material of the present invention may be exposed by any method, but scanning exposure with a laser beam is preferred. Laser light can be red to infrared light emitting He-Ne laser, red semiconductor laser, or blue to green light emitting Ar.⁺, He—Ne, He—Cd laser, and blue semiconductor laser can be used. Preferred is a red to infrared semiconductor laser, and the peak wavelength of the laser light is 600 nm to 900 nm, preferably 620 nm to 850 nm. On the other hand, in particular, in particular, a module in which an SHG (Second Harmonic Generator) element and a semiconductor laser are integrated and a blue semiconductor laser have been developed, and a laser output device in a short wavelength region has been closed up. The blue semiconductor laser is expected to increase in demand in the future because high-definition image recording is possible, the recording density is increased, and a stable output is obtained with a long lifetime.
The emission peak wavelength of the laser light is 300 nm to 500 nm, preferably 350 nm to 450 nm, more preferably 390 nm to 430 nm, red to near infrared 600 nm to 900 nm, preferably 620 nm to 870 nm, more preferably 640 nm to 830 nm.
[0539]
It is also preferable that the laser light is oscillated in a vertical multi by a method such as high frequency superposition.
[0540]
2) Thermal development
The photothermographic material of the present invention may be developed by any method, but is usually developed by raising the temperature of the photothermographic material exposed imagewise. A preferred development temperature is 80 to 250 ° C, preferably 100 to 140 ° C, more preferably 110 to 130 ° C. The development time is preferably 1 to 60 seconds, more preferably 3 to 30 seconds, still more preferably 5 to 25 seconds, and most preferably 7 to 15 seconds.
[0541]
Either a drum type heater or a plate type heater may be used as the thermal development method, but the plate type heater method is more preferable. The plate-type heater-based heat development method is preferably the method described in JP-A-11-133572, and a visible image is obtained by bringing the heat-developable photosensitive material on which the latent image has been formed into contact with the heating means in the heat developing section. In the heat development apparatus, the heating unit includes a plate heater, and a plurality of press rollers are disposed to face each other along one surface of the plate heater, and the press roller is disposed between the press roller and the plate heater. A heat development apparatus characterized in that heat development is performed by passing a photothermographic material. It is preferable to divide the plate heater into 2 to 6 stages and lower the temperature about 1 to 10 ° C. at the tip. For example, there are examples in which four sets of plate heaters that can be independently controlled are used and controlled so as to be 112 ° C., 119 ° C., 121 ° C., and 120 ° C.
[0542]
Such a method is also described in JP-A-54-30032, which can exclude moisture and organic solvents contained in the photothermographic material out of the system, and can be rapidly developed in the photothermographic material. It is also possible to suppress a change in the shape of the support of the photothermographic material due to the heating.
[0543]
As another heating method, a backside resistive heating layer as shown in U.S. Pat. Nos. 4,460,681 and 4,374,921 is provided for energization. It is possible to generate heat and heat it.
[0544]
3) System
As a medical laser imager provided with an exposure part and a heat development part, “Dry Imager-FM-DPL” of Fuji Film Medical Co., Ltd. can be mentioned. The system is Fuji Medical Review No. 8, pages 39 to 55, and these techniques can be used. In addition, “Dry Picks (7000) System” of Fuji Film Medical Co., Ltd. can be mentioned in recent years. Further, it can be applied as a photothermographic material for a laser imager in “AD network” proposed by Fuji Film Medical Co., Ltd. as a network system conforming to the DICOM standard.
[0545]
(Use of the present invention)
[0546]
The photothermographic material using the high silver iodide photographic emulsion of the present invention forms a black-and-white image with a silver image, and is a photothermographic material for medical diagnosis, a photothermographic material for industrial photography, and a photothermographic material for printing. It is preferably used as a photothermographic material for COM.
[0547]
[0548]
【Example】
EXAMPLES Hereinafter, the present invention will be specifically described with reference to examples, but the present invention is not limited to these examples.
Example 1
[0549]
1. Preparation of PET support and undercoating
1-1. Film formation
[0550]
Using terephthalic acid and ethylene glycol, PET having an intrinsic viscosity of IV = 0.66 (measured in phenol / tetrachloroethane = 6/4 (weight ratio) at 25 ° C.) was obtained according to a conventional method. This was pelletized and dried at 130 ° C. for 4 hours. Thereafter, the film was extruded from a T-die and quenched to prepare an unstretched film having a thickness such that the film thickness after heat setting was 175 μm.
[0551]
This was longitudinally stretched 3.3 times using rolls with different peripheral speeds, and then stretched 4.5 times with a tenter. The temperatures at this time were 110 ° C. and 130 ° C., respectively. Thereafter, after heat setting at 240 ° C. for 20 seconds, the film was relaxed by 4% in the lateral direction at the same temperature. After slitting the chuck part of the tenter, knurling is performed on both ends and 4 kg / cm.²And a roll having a thickness of 175 μm was obtained.
[0552]
1-2. Surface corona discharge treatment
Using a solid state corona discharge treatment machine 6KVA model manufactured by Pillar, both surfaces of the support were treated at room temperature at 20 m / min. From the current and voltage readings at this time, the support is 0.375 kV · A · min / m.²It was found that the process was done. The treatment frequency at this time was 9.6 kHz, and the gap clearance between the electrode and the dielectric roll was 1.6 mm.
[0553]
1-3. undercoat
1) Preparation of undercoat layer coating solution
Formulation (1) (for the undercoat layer on the photosensitive layer side)
59g pesresin A-520 (30% by mass solution) manufactured by Takamatsu Yushi Co., Ltd.
Polyethylene glycol monononyl phenyl ether 5.4g
(Average number of ethylene oxide = 8.5) 10% by mass solution
MP-1000 (polymer fine particles, average particle size 0.4μm) 0.91g by Soken Chemical Co., Ltd.
935ml distilled water
[0554]
Formulation (2) (for back layer 1st layer)
Styrene-butadiene copolymer latex 158g
(Solid content 40% by mass, styrene / butadiene weight ratio = 68/32)
2,4-Dichloro-6-hydroxy-S-triazine sodium salt
(8% by weight aqueous solution) 20g
10% 1% by weight aqueous solution of sodium laurylbenzenesulfonate
Distilled water 854ml
[0555]
Formula (3) (Back side 2nd layer)
SnO₂/ SbO (9/1 mass ratio, average particle size 0.038μm, 17 mass% dispersion) 84g
Gelatin (10 mass% aqueous solution) 89.2g
Metrows TC-5 (2% by weight aqueous solution) manufactured by Shin-Etsu Chemical Co., Ltd.8.6g
MP-1000 0.01g manufactured by Soken Chemical Co., Ltd.
10% 1% by weight aqueous solution of sodium dodecylbenzenesulfonate
NaOH (1% by mass) 6ml
Proxel (made by ICI) 1ml
805ml of distilled water
[0556]
2) Undercoat
After both surfaces of the biaxially stretched polyethylene terephthalate support having a thickness of 175 μm are subjected to the corona discharge treatment, the undercoat coating solution formulation {circle around (1)} is applied to one surface (photosensitive layer surface) with a wire bar. .6ml / m²(Per side) and dried at 180 ° C. for 5 minutes, and then the undercoat coating liquid formulation (2) is applied to the back side (back side) with a wire bar at a wet coating amount of 5.7 ml / m.²And then dried at 180 ° C. for 5 minutes. Further, the undercoat coating liquid formulation (3) is applied to the back surface (back surface) with a wire bar so that the wet coating amount is 7.7 ml / m.²And then dried at 180 ° C. for 6 minutes to prepare an undercoat support.
[0557]
2. Back layer
1) Preparation of back layer coating solution
(Preparation of antihalation layer coating solution)
Gelatin 60 g, polyacrylamide 24.5 g, 1 mol / L sodium hydroxide 2.2 g, monodisperse polymethyl methacrylate fine particles (average particle size 8 μm, particle size standard deviation 0.4) 2.4 g, benzoisothiazolinone 08 g, 0.3 g of sodium polyethylene sulfonate, 0.21 g of blue dye compound-1, 6.8 g of UV absorber-1, 8.3 g of acrylic acid / ethyl acrylate copolymer (copolymerization weight ratio 5/95) And the whole was made up to 818 ml with water to prepare an antihalation layer coating solution.
[0558]
(Preparation of back surface protective layer coating solution)
The container was kept at 40 ° C., gelatin 40 g, liquid paraffin emulsion as liquid paraffin 1.5 g, benzoisothiazolinone 30 mg, 1 mol / L sodium hydroxide 6.8 g, sodium t-octylphenoxyethoxyethane sulfonate 0 0.5 g, polystyrene sulfonate 0.27 g, fluorosurfactant (F-1) 2% by mass aqueous solution 5.4 ml, acrylic acid / ethyl acrylate copolymer (copolymerization weight ratio 5/95) 6.0 g , N, N-ethylenebis (vinylsulfone acetamide) 2.0 g was mixed and made up to 1000 ml with water to obtain a back surface protective layer coating solution.
[0559]
2) Application of back layer
The coating amount of the antihalation layer coating solution on the back surface side of the undercoat support is 1.70 g / m.²In addition, the coating amount of the back surface protective layer was 0.79 g / m for the gelatin coating amount.²Then, a simultaneous multilayer coating was applied and dried to form a back layer.
[0560]
3. Image forming layer and surface protective layer
3-1. Preparation of coating materials
[0561]
(Photosensitive silver halide emulsion)
1) Preparation of photosensitive silver halide emulsion 1
To 1420 ml of distilled water, 4.3 ml of a 1% by mass potassium iodide solution was added, and a solution obtained by adding 3.5 ml of 0.5 mol / L sulfuric acid and 88.3 g of phthalated gelatin was stirred in a stainless steel reaction vessel. While maintaining the liquid temperature at 42 ° C., the solution A in which distilled water was diluted to 22.56 g of silver nitrate and diluted to 195.6 ml and the solution B in which 21.8 g of potassium iodide was diluted to 218 ml with distilled water were added at a constant flow rate. The whole amount was added over 9 minutes. Thereafter, 10 ml of a 3.5% by mass aqueous hydrogen peroxide solution was added, and further 10.8 ml of a 10% by mass aqueous solution of benzimidazole was added.
[0562]
Further, Solution C diluted with 51.86 g of silver nitrate and diluted to 317.5 ml and Solution D obtained by diluting 60 g of potassium iodide to a volume of 600 ml with distilled water were added to Solution C over 120 minutes at a constant flow rate. Solution D was added by the controlled double jet method while maintaining pAg at 8.1. 1 x 10 per mole of silver^-FourThe total amount of iridium (III) hexachloride potassium salt was added in a molar amount 10 minutes after the start of addition of Solution C and Solution D. In addition, 5 seconds after the completion of the addition of the solution C, an aqueous solution of potassium iron (II) hexacyanide was added at 3 × 10 5^-FourThe whole molar amount was added. The pH was adjusted to 3.8 using 0.5 mol / L sulfuric acid, stirring was stopped, and precipitation, desalting, and washing steps were performed. The pH was adjusted to 5.9 with 1 mol / L sodium hydroxide to prepare a silver halide dispersion having a pAg of 8.0.
[0563]
The silver halide dispersion was maintained at 38 ° C. with stirring, 5 ml of a methanol solution of 0.34% by mass of 1,2-benzisothiazolin-3-one was added, and the temperature was raised to 47 ° C. 20 minutes after the temperature rise, sodium benzenethiosulfonate was 7.6 × 10 6 in 1 mol of silver with a methanol solution.^-Five5 minutes later, the following tellurium sensitizer C was added in a methanol solution to give 2.9 × 10 6 per mol of silver.^-FourMole was added and aged for 91 minutes. 1.3 ml of a 0.8% by weight methanol solution of N, N'-dihydroxy-N "-diethylmelamine was added, and after another 4 minutes, 5-methyl-2-mercaptobenzimidazole was added to the solution in methanol solution at 4.8 × 10 6 per mole of silver.^-3Mole and 1-Phenyl-2-heptyl-5-mercapto-1,3,4-triazole in methanol solution to 5.4 × 10 5 per mol of silver^-3A silver halide emulsion 1 was prepared by adding a molar amount.
[0564]
The grains in the prepared silver halide emulsion 1 were pure silver iodide grains having an average sphere equivalent diameter of 0.040 μm and a sphere equivalent diameter variation coefficient of 18%. The particle size and the like were determined from an average of 1000 particles using an electron microscope. Moreover, it is a tetrahedral particle | grain which has (001), {100}, {101} face, The ratio of the (gamma) phase was 30% when measured using the X-ray powder diffraction analysis.
[0565]
(Preparation of silver halide emulsion 2)
The temperature of the reaction solution was changed to 65 ° C., 5 ml of a 5% methanol solution of 2,2 ′-(ethylenedithio) diethanol was added after the addition of solutions A and B, and solution D while maintaining pAg at 10.5. Was added by a controlled double jet method, and 3 minutes after the addition of tellurium sensitizer during chemical sensitization, bromoauric acid was added at 5 × 10 5 per mole of silver.^-FourMoles and potassium thiocyanate 2 x 10 per mole of silver^-3A silver halide emulsion 2 was prepared in the same manner as Emulsion 1 except that mol was added.
[0566]
Grains in the prepared silver halide emulsion have an average equivalent circle diameter of projected area of 0.164 μm, a grain thickness of 0.032 μm, an average aspect ratio of 5, an average sphere equivalent diameter of 0.11 μm, and a coefficient of variation of the equivalent sphere diameter of 23. % Pure silver iodide tabular grains. When measured using X-ray powder diffraction analysis, the proportion of the γ phase was 80%.
[0567]
(Preparation of silver halide emulsion 3)
Silver halide emulsion 3 in exactly the same manner as silver halide emulsion 1 except that the temperature of the reaction solution was changed to 27 ° C. and solution D was added by the controlled double jet method while maintaining pAg at 10.2. It was created.
[0568]
Grains in the prepared silver halide emulsion were pure silver iodide grains having an average sphere equivalent diameter of 0.022 μm and a sphere equivalent diameter variation coefficient of 17%. Further, they were dodecahedron grains having (001), {1 (-1) 0}, and {101} planes, and were silver iodide substantially consisting of a β phase as measured by X-ray powder diffraction analysis.
[0569]
(Preparation of mixed emulsions A1 to A3 for coating solutions)
Silver halide emulsion 1, silver halide emulsion 2 and silver halide emulsion 3 are dissolved in a molar ratio of 5: 2: 3, and 1 mol of benzothiazolium iodide is added in a 1% by mass aqueous solution. 7 × 10 per^-3Mole was added. Further, water is added so that the content of silver halide per 1 kg of the mixed emulsion for coating solution is 38.2 g as silver, and 1- (3-methylureidophenyl)-is obtained so that the amount is 0.34 g per 1 kg of the mixed emulsion for coating solution. 5-mercaptotetrazole was added.
[0570]
Further, as “a compound in which a one-electron oxidant produced by one-electron oxidation can emit one electron or more”, compounds 2 and 20 and 26 are each 2 × 10 2 per mole of silver halide silver.^-3Molar amounts were added.
Furthermore, as shown in Table 14, the compound having an adsorbing group and a reducing group of the present invention was added.
Mixed emulsion A1: An emulsion to which no compound having an adsorbing group and a reducing group is added.
Mixed emulsion A2: Compound No. 1 as a compound having an adsorbing group and a reducing group. 19, 49, and 71 are each 8 × 10 4 per mole of silver applied^-3It is an emulsion with a molar addition.
Mixed emulsion A3: Compound No. 1 as a compound having an adsorbing group and a reducing group. 19 and 71 are each 8 × 10 4 per mole of silver applied^-3It is an emulsion with a molar addition.
[0571]
(Preparation of silver halide emulsion 4)
Similar to the preparation of silver halide emulsion 1, except that a mixed solution of potassium iodide and potassium bromide was used instead of potassium iodide, and 70 mol% of silver iodide and 30 mol% of silver bromide were uniformly formed. A silver halide emulsion 4 having a halogen composition was prepared.
The grain size of the obtained grains was equivalent to that of the silver halide emulsion 1 by adjusting the temperature during grain formation.
[0572]
(Preparation of silver halide emulsion 5)
Similar to the preparation of silver halide emulsion 2, except that a mixed solution of potassium iodide and potassium bromide was used instead of potassium iodide, and 70 mol% of silver iodide and 30 mol% of silver bromide were homogeneous. A silver halide emulsion 5 having a halogen composition was prepared.
The grain size of the obtained grains was equivalent to that of the silver halide emulsion 2 by adjusting the temperature at the grain formation.
[0573]
(Preparation of silver halide emulsion 6)
Similar to the preparation of silver halide emulsion 3, except that a mixed solution of potassium iodide and potassium bromide was used instead of potassium iodide, and 70 mol% of silver iodide and 30 mol% of silver bromide were uniformly formed. A silver halide emulsion 4 having a halogen composition was prepared.
The grain size of the obtained grains was equivalent to that of the silver halide emulsion 3 by adjusting the temperature during grain formation.
[0574]
(Preparation of mixed emulsions B1 to B3 for coating solution)
In the mixed emulsions A1 to A3 for coating solution, instead of the silver halide emulsion 1, the silver halide emulsion 2, and the silver halide emulsion 3, the silver halide emulsion 4, the silver halide emulsion 5, and the silver halide emulsion 6 are used. A mixed emulsion B for coating solution was prepared using a silver molar ratio of 5: 2: 3.
[0575]
(Preparation of silver halide emulsion 7)
Similar to the preparation of silver halide emulsion 1, except that a mixed solution of potassium iodide and potassium bromide was used instead of potassium iodide, and 3.5 mol% of silver iodide and 96.5 mol of silver bromide. A silver halide emulsion 7 having a uniform halogen composition of% was prepared.
The grain size of the obtained grains was equivalent to that of the silver halide emulsion 1 by adjusting the temperature during grain formation.
[0576]
(Preparation of silver halide emulsion 8)
Similar to the preparation of silver halide emulsion 2, except that a mixed solution of potassium iodide and potassium bromide was used instead of potassium iodide, and 3.5 mol% of silver iodide and 96.5 mol of silver bromide. A silver halide emulsion 8 having a uniform halogen composition of% was prepared.
The grain size of the obtained grains was equivalent to that of the silver halide emulsion 2 by adjusting the temperature at the grain formation.
[0577]
(Preparation of silver halide emulsion 9)
Similar to the preparation of silver halide emulsion 3, except that a mixed solution of potassium iodide and potassium bromide was used instead of potassium iodide, and 3.5 mol% silver iodide and 96.5 mol silver bromide. A silver halide emulsion 9 having a uniform halogen composition of% was prepared.
The grain size of the obtained grains was equivalent to that of the silver halide emulsion 3 by adjusting the temperature during grain formation.
[0578]
(Preparation of mixed emulsions C1 to C3 for coating solution)
In the mixed emulsions A1 to A3 for coating solution, instead of silver halide emulsion 1, silver halide emulsion 2, and silver halide emulsion 3, silver halide emulsion 7, silver halide emulsion 8, and silver halide emulsion 9 are used. A mixed emulsion C for coating solution was prepared using a silver molar ratio of 5: 2: 3.
[0579]
(Preparation of organic silver salt dispersion)
1) Preparation of organic silver salt dispersion
<Preparation of recrystallized behenic acid>
100 kg of behenic acid (product name Edenor C22-85R) manufactured by Henkel was mixed in 1200 kg of isopropyl alcohol, dissolved at 50 ° C., filtered through a 10 μm filter, cooled to 30 ° C., and recrystallized. The cooling speed during recrystallization was controlled at 2 ° C./hour. The obtained crystals were centrifugally filtered, washed with 200 kg of isopropyl alcohol, and then dried. When the obtained crystals were esterified and subjected to GC-FID measurement, the behenic acid content was 98 mol%, in addition, lignoceric acid 1.9 mol%, arachidic acid 0.1 mol%, and erucic acid 0.001 mol% It was.
[0580]
<Preparation of organic silver salt dispersion>
Recrystallized behenic acid 88 kg, distilled water 422 L, 5 mol / L NaOH aqueous solution 49.2 L and t-butyl alcohol 120 L were mixed and stirred at 75 ° C. for 1 hour to react to obtain sodium behenate solution B. Separately, 206.2 L (pH 4.0) of an aqueous solution containing 39.1 kg of silver nitrate was prepared and kept warm at 10 ° C. Keep the reaction vessel containing 635L distilled water and 30L t-butyl alcohol at 30 ° C, and with sufficient agitation, the total amount of the previous sodium behenate solution and the total amount of silver nitrate aqueous solution are 93 minutes and 15 seconds respectively at a constant flow rate. And added over 87 minutes and 6 seconds. At this time, only the silver nitrate aqueous solution is added for 11 minutes after the start of the addition of the aqueous silver nitrate solution, and then the addition of the sodium behenate solution is started. After the addition of the aqueous silver nitrate solution, only the sodium behenate solution is added for 17 minutes and 9 seconds. It was made to be. At this time, the temperature in the reaction vessel was 30 ° C., and the external temperature was controlled so that the liquid temperature was constant. The pipe of the addition system for the sodium behenate solution was kept warm by circulating hot water outside the double pipe so that the liquid temperature at the outlet at the tip of the addition nozzle was 75 ° C. Moreover, the piping of the addition system of the silver nitrate aqueous solution was kept warm by circulating cold water outside the double pipe. The addition position of the sodium behenate solution and the addition position of the aqueous silver nitrate solution were arranged symmetrically around the stirring axis, and were adjusted so as not to contact the reaction solution.
[0581]
After completion of the addition of the sodium behenate solution, the mixture was left stirring for 20 minutes at the same temperature, heated to 35 ° C. over 30 minutes, and then aged for 210 minutes. Immediately after completion of aging, the solid content was separated by centrifugal filtration, and the solid content was washed with water until the conductivity of filtered water reached 80 μS / cm. Thus, a fatty acid silver salt was obtained. The obtained solid content was stored as a wet cake without drying.
[0582]
When the morphology of the obtained silver behenate particles was evaluated by electron micrograph, the average sphere equivalent diameter was 0.40 μm, and the sphere equivalent diameter was a crystal having a volume weighted average variation coefficient of 11%.
[0583]
Add 19.7 kg of polyvinyl alcohol (trade name: PVA-217) and water to a wet cake equivalent to 269 kg dry solids, make the total amount 1000 kg, and then slurry with a dissolver blade. PM-10 type).
[0584]
Next, the pre-dispersed stock solution is subjected to a dispersion machine (trade name: Microfluidizer M-610, manufactured by Microfluidics International Corporation, using a Z-type interaction chamber) with a pressure of 900 kg / cm.²And was treated three times to obtain a silver behenate dispersion. The cooling operation was set at a dispersion temperature of 10 ° C. by installing a serpentine heat exchanger before and after the interaction chamber and adjusting the temperature of the refrigerant.
[0585]
(Preparation of reducing agent dispersion)
1) Preparation of reducing agent-1 dispersion
Reducing agent-1 (2,2'-methylenebis- (4-ethyl-6-tert-butylphenol)) 10 kg and denatured polyvinyl alcohol (Kuraray Co., Ltd., POVAL MP203) 10 mass% aqueous solution 16 kg, water 10 kg Add and mix well to make a slurry. This slurry was fed with a diaphragm pump and dispersed in a horizontal sand mill (UVM-2: manufactured by Imex Co., Ltd.) filled with zirconia beads having an average diameter of 0.5 mm for 3 hours, and then 0.2 g of benzoisothiazolinone sodium salt Water was added to prepare a reducing agent concentration of 25% by mass. This dispersion was heat-treated at 60 ° C. for 5 hours to obtain a reducing agent-1 dispersion. The reducing agent particles contained in the reducing agent dispersion thus obtained had a median diameter of 0.40 μm and a maximum particle diameter of 1.4 μm or less. The obtained reducing agent dispersion was filtered through a polypropylene filter having a pore size of 3.0 μm to remove foreign substances such as dust and stored.
[0586]
2) Preparation of reducing agent-2 dispersion
10 mass of reducing agent-2 (6,6'-di-t-butyl-4,4'-dimethyl-2,2'-butylidenediphenol) and modified polyvinyl alcohol (Kuraray Co., Ltd., Poval MP203) 10 kg of water was added to 16 kg of% aqueous solution and mixed well to form a slurry. This slurry was fed with a diaphragm pump and dispersed for 3 hours 30 minutes in a horizontal sand mill (UVM-2: manufactured by Imex Co., Ltd.) filled with zirconia beads having an average diameter of 0.5 mm, and then benzoisothiazolinone sodium salt 0.2 g and water were added to prepare a reducing agent concentration of 25% by mass. This dispersion was heated at 40 ° C. for 1 hour, and then further heated at 80 ° C. for 1 hour to obtain a reducing agent-2 dispersion. The reducing agent particles contained in the reducing agent dispersion thus obtained had a median diameter of 0.50 μm and a maximum particle diameter of 1.6 μm or less. The obtained reducing agent dispersion was filtered through a polypropylene filter having a pore size of 3.0 μm to remove foreign substances such as dust and stored.
[0587]
(Preparation of hydrogen bonding compound-1 dispersion)
Add 10 kg of water to 10 kg of 10% aqueous solution of hydrogen bonding compound-1 (tri (4-t-butylphenyl) phosphine oxide) and denatured polyvinyl alcohol (Kuraray Co., Ltd., Poval MP203). Mix to make a slurry. This slurry was fed with a diaphragm pump and dispersed in a horizontal sand mill (UVM-2: manufactured by Imex Co., Ltd.) filled with zirconia beads having an average diameter of 0.5 mm for 4 hours, and then 0.2 g of benzoisothiazolinone sodium salt Water was added to prepare a hydrogen bonding compound concentration of 25% by mass. This dispersion was heated at 40 ° C. for 1 hour and then further heated at 80 ° C. for 1 hour to obtain a hydrogen bonding compound-1 dispersion. The hydrogen bonding compound particles contained in the hydrogen bonding compound dispersion thus obtained had a median diameter of 0.45 μm and a maximum particle diameter of 1.3 μm or less. The obtained hydrogen bonding compound dispersion was filtered through a polypropylene filter having a pore size of 3.0 μm to remove foreign substances such as dust and stored.
[0588]
(Preparation of dispersion of development accelerator)
1) Dispersion of development accelerator 1-68)
Development accelerator No. 10 kg of 1-68 and 20 kg of a 10% by weight aqueous solution of modified polyvinyl alcohol (Kuraray Co., Ltd., Poval MP203) were added with 10 kg of water and mixed well to obtain a slurry. This slurry was fed with a diaphragm pump and dispersed for 3 hours 30 minutes in a horizontal sand mill (UVM-2: manufactured by Imex Co., Ltd.) filled with zirconia beads having an average diameter of 0.5 mm, and then benzoisothiazolinone sodium salt 0.2 g and water were added so that the concentration of the development accelerator was 20% by mass to obtain a development accelerator-1 dispersion. The development accelerator particles contained in the development accelerator dispersion thus obtained had a median diameter of 0.48 μm and a maximum particle diameter of 1.4 μm or less. The obtained development accelerator dispersion was filtered through a polypropylene filter having a pore size of 3.0 μm to remove foreign substances such as dust and stored.
[0589]
2) Development accelerator-6-41
The solid dispersion of Development Accelerator-6-41 was also dispersed by the same method as Development Accelerator-1-68 to obtain a 20 mass% dispersion.
[0590]
(Preparation of solid dispersion of color tone modifier-1)
The solid dispersion of the color tone modifier-1 was also dispersed by the same method as for the development accelerator-1-68 to obtain a 15% by mass dispersion.
[0591]
(Preparation of organic polyhalogen compound dispersion)
1) Preparation of organic polyhalogen compound dispersion-1
Add 10 kg of organic polyhalogen compound-1 and 10 kg of 20 wt% aqueous solution of modified polyvinyl alcohol MP203, 0.4 kg of 20 wt% aqueous solution of sodium triisopropylnaphthalenesulfonate and 14 kg of water, and mix well to form a slurry. . This slurry was fed with a diaphragm pump, dispersed in a horizontal sand mill UVM-2 filled with zirconia beads having an average diameter of 0.5 mm for 5 hours, and then 0.2 g of benzoisothiazolinone sodium salt and water were added to form an organic polyhalogen compound. The organic polyhalogen compound dispersion (a) was obtained so that the concentration of The organic polyhalogen compound particles contained in the polyhalogen compound dispersion thus obtained had a median diameter of 0.41 μm and a maximum particle diameter of 2.0 μm or less. The obtained organic polyhalogen compound dispersion was filtered through a polypropylene filter having a pore size of 10.0 μm to remove foreign substances such as dust and stored.
[0592]
2) Preparation of organic polyhalogen compound dispersion-2
Add 10 kg of organic polyhalogen compound-2, 20 kg of 10 wt% aqueous solution of modified polyvinyl alcohol MP203, 0.4 kg of 20 wt% aqueous solution of sodium triisopropylnaphthalenesulfonate, and 8 kg of water, and mix well to form a slurry. . This slurry was fed with a diaphragm pump, dispersed in a horizontal sand mill UVM-2 filled with zirconia beads having an average diameter of 0.5 mm for 5 hours, and then 0.2 g of benzoisothiazolinone sodium salt and water were added to form an organic polyhalogen compound. The concentration of was adjusted to 25% by mass. This dispersion was heated at 40 ° C. for 5 hours to obtain an organic polyhalogen compound-2 dispersion. The organic polyhalogen compound particles contained in the polyhalogen compound dispersion thus obtained had a median diameter of 0.36 μm and a maximum particle diameter of 1.5 μm or less. The obtained organic polyhalogen compound dispersion was filtered through a polypropylene filter having a pore size of 3.0 μm to remove foreign substances such as dust and stored.
[0593]
(Preparation of phthalazine compound solution)
8 kg of modified polyvinyl alcohol MP203 was dissolved in 174.57 kg of water, then 3.15 kg of a 20% by weight aqueous solution of sodium triisopropylnaphthalenesulfonate and 14.28 kg of a 70% by weight aqueous solution of 6-isopropylphthalazine were added, and phthalazine compound-1 A 5 wt% solution was prepared.
[0594]
(Preparation of mercapto compound)
1) Mercapto compound-1 aqueous solution
7 g of mercapto compound-1 (1- (3-sulfophenyl) -5-mercaptotetrazole sodium salt) was dissolved in 993 g of water to obtain a 0.7% by mass aqueous solution.
[0595]
2) Mercapto compound-2 aqueous solution
20 g of mercapto compound-2 (1- (3-methylureidophenyl) -5-mercaptotetrazole) was dissolved in 980 g of water to obtain a 2.0 mass% aqueous solution.
[0596]
(Preparation of pigment-1 dispersion)
C.I. Pigment Blue 60 (64 g) and Kao Co., Ltd. (Demol N) 6.4 g were mixed with 250 g of water and mixed well to form a slurry. Prepare 800 g of zirconia beads with an average diameter of 0.5 mm, put them in a vessel together with the slurry, disperse with a disperser (1 / 4G sand grinder mill: manufactured by IMEX Co., Ltd.) for 25 hours, add water to add pigment concentration Was prepared so as to be 5% by mass to obtain a pigment-1 dispersion. The pigment particles contained in the pigment dispersion thus obtained had an average particle size of 0.21 μm.
[0597]
(Preparation of SBR latex solution)
In a polymerization kettle of a gas monomer reactor (TAS-2J type manufactured by Pressure Glass Industrial Co., Ltd.), 287 g of distilled water and a surfactant (Pionin A-43-S (manufactured by Takemoto Yushi Co., Ltd.)): solid content 48.5 %) 7.73 g, 1 mol / liter NaOH 14.06 ml, ethylenediaminetetraacetic acid tetrasodium salt 0.15 g, styrene 255 g, acrylic acid 11.25 g, tert-dodecyl mercaptan 3.0 g, the reaction vessel was sealed and the stirring speed was 200 rpm. Stir with. After degassing with a vacuum pump and repeating nitrogen gas replacement several times, 108.75 g of 1,3-butadiene was injected to raise the internal temperature to 60 ° C. A solution obtained by dissolving 1.875 g of ammonium persulfate in 50 ml of water was added thereto, and the mixture was stirred as it was for 5 hours. The mixture was further heated to 90 ° C. and stirred for 3 hours. After the reaction was completed, the internal temperature was lowered to room temperature, and then 1 mol / liter NaOH and NH._FourNa with OH⁺Ion: NH_Four ⁺The addition treatment was performed so that the ion was 1: 5.3 (molar ratio), and the pH was adjusted to 8.4. Thereafter, the mixture was filtered through a polypropylene filter having a pore size of 1.0 μm to remove foreign substances such as dust and stored to obtain 774.7 g of SBR latex. When the halogen ions were measured by ion chromatography, the chloride ion concentration was 3 ppm. As a result of measuring the concentration of the chelating agent by high performance liquid chromatography, it was 145 ppm.
[0598]
The latex has an average particle size of 90 nm, Tg = 17 ° C., solid content concentration of 44% by mass, equilibrium water content of 0.6% by mass at 25 ° C. and 60% RH, and ionic conductivity of 4.80 mS / cm. Using a conductivity meter CM-30S manufactured by Kogyo Co., Ltd., measuring latex stock solution (44% by mass) at 25 ° C.), pH 8.4
[0599]
3-2. Preparation of coating solution
1) Preparation of image forming layer
(Preparation of image forming layer coating solutions 1 to 9)
To 1000 g of the organic silver salt dispersion obtained above and 276 ml of water, organic polyhalogen compound dispersion-1, organic polyhalogen compound dispersion-2, phthalazine solution, SBR latex (Tg: 17 ° C.) liquid, reducing agent-1 Add dispersion, reducing agent-2 dispersion, hydrogen bonding compound-1 dispersion wp, and add dispersion of development accelerator-1-68 and development accelerator-6-41 dispersion as shown in Table 14. In addition, after adding the color tone adjusting agent-1 dispersion, the mercapto compound-1 aqueous solution, and the mercapto compound-2 aqueous solution in sequence, the silver halide emulsion A for coating solution preparation is added immediately before coating, and mixed well and coated as it is. The solution was fed to the die and applied.
[0600]
(Preparation of image forming layer coating solutions 10 to 18)
Image forming layer coating solutions 10 to 18 were prepared in the same manner as the image forming layer coating solutions 1 to 9, except that silver halide emulsions B1 to B3 were used instead of silver halide emulsions A1 to A3.
[0601]
(Preparation of image forming layer coating solutions 19 to 27)
Image forming layer coating solutions 19 to 27 were prepared in the same manner as the image forming layer coating solutions 1 to 9 except that silver halide emulsions C1 to C3 were used instead of silver halide emulsions A1 to A3.
[0602]
2) Preparation of intermediate layer coating solution
Polyvinyl alcohol PVA-205 (manufactured by Kuraray Co., Ltd.) 1000 g, pigment 5 mass% dispersion 272 g, methyl methacrylate / styrene / butyl acrylate / hydroxyethyl methacrylate / acrylic acid copolymer (copolymer weight ratio 64/9/20 / 5/2) 27% 5% aqueous solution of aerosol OT (American Cyanamid Co., Ltd.) in 4200 ml of 19% latex solution, 135 ml of 20% aqueous solution of diammonium phthalate, total amount 10000g Add water and adjust with NaOH so that the pH is 7.5 to obtain an intermediate layer coating solution, 9.1 ml / m²Then, the solution was fed to the coating die.
The viscosity of the coating solution was 58 [mPa · s] when measured with a B-type viscometer at 40 ° C. (No. 1 rotor, 60 rpm).
[0603]
3) Preparation of surface protective layer first layer coating solution
64 g of inert gelatin dissolved in water, 112 g of 19.0% by weight latex of methyl methacrylate / styrene / butyl acrylate / hydroxyethyl methacrylate / acrylic acid copolymer (copolymerization weight ratio 64/9/20/5/2), phthalic acid 30 ml of 15 mass% methanol solution, 23 ml of 10 mass% aqueous solution of 4-methylphthalic acid, 28 ml of 0.5 mol / L sulfuric acid, 5 ml of 5 mass% aqueous solution of Aerosol OT (American Cyanamid), phenoxyethanol Add 0.5g and 0.1g of benzoisothiazolinone, add water to make a total amount of 750g to make a coating solution, and mix 18.6ml / m of 26% 4% chromium alum mixed with static mixer just before coating.²Then, the solution was fed to the coating die.
The viscosity of the coating solution was 20 [mPa · s] at a B-type viscometer of 40 ° C. (No. 1 rotor, 60 rpm).
[0604]
4) Preparation of surface protective layer second layer coating solution
Inert gelatin 80g dissolved in water, methyl methacrylate / styrene / butyl acrylate / hydroxyethyl methacrylate / acrylic acid copolymer (copolymerization mass ratio 64/9/20/5/2) latex 27.5 mass% liquid 102g, fluorine-based 3.2 ml of 5% by weight surfactant (F-1) solution, 32 ml of 2% by weight aqueous solution of fluorosurfactant (F-2), 23 ml of 5% by weight aerosol OT solution, polymethylmethacrylate microparticles (Average particle size 0.7μm) 4g, polymethyl methacrylate fine particles (average particle size 4.5μm) 21g, 4-methylphthalic acid 1.6g, phthalic acid 4.8g, 0.5mol / L sulfuric acid 44ml, benzoisothiazolinone 10mg Add water to make 650g, and mix 445ml of an aqueous solution containing 4% by weight of chromium alum and 0.67% by weight of phthalic acid with a static mixer just before coating to make the surface protective layer second layer coating solution, 8.3ml / m²Then, the solution was fed to the coating die.
The viscosity of the coating solution was 19 [mPa · s] at a B-type viscometer of 40 ° C. (No. 1 rotor, 60 rpm).
[0605]
3-3. Coating
Samples 1 to 1 of the photothermographic material were coated simultaneously on the surface opposite to the back surface by the slide bead coating method in the order of the image forming layer, intermediate layer, protective layer first layer and protective layer second layer from the undercoat surface. 36 was created. At this time, the image forming layer and the intermediate layer were adjusted to 31 ° C., the protective layer first layer was adjusted to 36 ° C., and the protective layer second layer was adjusted to 37 ° C.
Table 1 shows each sample No., types of organic silver salts used therein and silver halide.
Coating amount of each compound in the image forming layer (g / m²) Is as follows.
[0606]
Organic silver salt (as silver behenate coating amount) 5.27
Pigment (C.I.Pigment Blue 60) 0.036
Polyhalogen compound-1 0.09
Polyhalogen compound-2 0.14
Phthalazine Compound-1 0.18
SBR latex 9.43
Reducing agent-1 0.55
Reducing agent-2 0.22
Hydrogen bonding compound-1 0.28
Development accelerator 1-68 (shown in Table 14)
Development accelerator-6-41 (shown in Table 14)
Color tone adjusting agent-1 0.008
Mercapto Compound-1 0.002
Mercapto compound-2 0.006
Silver halide (as Ag) 0.046
[0607]
The coating and drying conditions are as follows.
The coating was performed at a speed of 160 m / min, the gap between the coating die tip and the support was set to 0.10 to 0.30 mm, and the pressure in the decompression chamber was set to 196 to 882 Pa lower than the atmospheric pressure. The support was neutralized with an ion wind before coating.
In the subsequent chilling zone, after cooling the coating liquid with wind at a dry bulb temperature of 10 to 20 ° C., it is transported in a non-contact type, and in a helical contactless dryer, the dry bulb temperature is 23 to 45 ° C., It dried with the dry wind of the wet bulb temperature 15-21 degreeC.
After drying, the humidity was adjusted at 25 ° C. and a humidity of 40-60% RH, and then the film surface was heated to 70-90 ° C. After heating, the film surface was cooled to 25 ° C.
[0608]
The photothermographic material thus prepared had a Beck smoothness of 550 seconds on the image forming layer surface side and 130 seconds on the back surface. Further, the pH of the film surface on the image forming layer surface side was measured and found to be 6.0.
[0609]
The structures of the compounds used in the examples of the present invention are shown below.
[0610]
Embedded image
[0611]
Embedded image
[0612]
Embedded image
[0613]
Embedded image
[0614]
Embedded image
[0615]
[Table 14]
[0616]
4). Performance evaluation
1) Preparation
The obtained sample was cut into half-cut sizes, packaged in the following packaging materials in an environment of 25 ° C. and 50% RH, and stored at room temperature for 2 weeks.
[0617]
(Packaging material)
PET 10 μm / PE 12 μm / Aluminum foil 9 μm / Ny 15 μm / Polyethylene 50 μm containing 3% by mass of carbon, oxygen permeability: 0.02 ml / atm · m²・ 25 ℃ ・ day, moisture permeability: 0.10g / atm ・ m²・ 25 ℃ ・ day.
[0618]
2) Exposure and development processing
Nichia Corporation (semiconductor laser NLHV3000E from 9) was mounted as a light source for Fuji Medical Dry Laser Imager FM-DPL, and the laser light intensity was 0 and 1 mW / mm²~ 1000mW / mm²The above samples were exposed with varying between. The oscillation peak wavelength of the laser was 405 nm. For thermal development, the four panel heaters of the above apparatus were set at 112 ° C., 118 ° C., 120 ° C., and 120 ° C., and the linear velocity was adjusted so that the development time was 14 seconds in total.
[0619]
3) Evaluation
(sensitivity)
The reciprocal of the exposure amount necessary to give the fog of Sample 1 + blackening density of 1.0 is shown as a relative value, where 100 is 100. The larger the value, the higher the sensitivity.
(Cover)
The density is shown in the unexposed area.
(Raw preservation)
Each sample sealed with the packaging material described above was stored under forced storage conditions at 45 ° C. for 7 days, and then subjected to exposure and heat development treatment, and changes in sensitivity were examined in comparison with samples stored frozen.
Raw storage stability (sensitivity change) = sensitivity of samples stored frozen-Sensitivity after storage under forced storage conditions at 45 ° C for 7 days
[0620]
(Printout resistance)
Each heat-developed sample was left in a room at 25 ° C. and 70% RH under 200 lux under a fluorescent lamp for 20 days. The increase in fogging before standing was measured.
[0621]
The results obtained are shown in Table 15. The photothermographic material according to the present invention has high sensitivity, low fog, strong raw storage and printout resistance, and exhibits excellent performance. In particular, when a compound having an adsorbing group and a reducing group and a development accelerator are used in combination, the result is an unexpected result in which the effect of increasing the sensitivity with a low fog is significantly greater than the individual effects. Further, this effect was more remarkable as the silver iodide content was higher.
[0622]
[Table 15]
[0623]
【The invention's effect】
According to the present invention, there is provided a photothermographic material having high sensitivity, excellent raw storability and excellent image storability.

Claims (9)

A photothermographic material having an image forming layer containing a photosensitive silver halide, a non-photosensitive organic silver salt, a reducing agent, and a binder on the same surface of a support , represented by the following general formula (I) At least one development accelerator selected from a compound having an adsorbing group and a reducing group for photosensitive silver halide or a precursor thereof, and compounds represented by the following general formulas (1), (2) and (3) A photothermographic material comprising:
(In General Formula (1), Q ¹ represents a 5- to 7-membered unsaturated ring bonded to NHNH—R ¹ at a carbon atom, and R ¹ represents a carbamoyl group. General Formulas (2) and (3) X ² and X ³ each independently represent a hydrogen atom or a substituent, and R ²¹ and R ^{31 to} R ³² each independently represent a hydrogen atom or a substituent, provided that in the general formula (2) The compound has a carbamoyl group at the 2-position with respect to the OH group, m and p each independently represents an integer of 0 to 4, and n represents an integer of 0 to 2) .
Formula (I)
A- (W) n-B
(In the formula, A represents an atomic group containing a group capable of adsorbing to silver halide, W represents a divalent linking group, n represents 0 or 1, and B represents a reducing group derived from phenidones. Represents.) 2. The photothermographic material according to claim 1 , wherein the adsorption group to the silver halide is a dimercapto-substituted heterocyclic group. In the general formula (1), R ¹ is a substituted carbamoyl group represented by —CO—NH—R ^{1 ′} , and R ^{1 ′} is an alkyl group having 1 to 10 carbon atoms or an aryl group, The photothermographic material according to claim 1 . Wherein the reducing agent is, heat-developable photosensitive material according to any one of claims 1 to 3, characterized by being represented by the following general formula (7).
(In General Formula (7), R ⁷¹ and R ^{71 ′} each independently represents an alkyl group having 1 to 20 carbon atoms. R ⁷² and R ^{72 ′} can each independently be substituted with a hydrogen atom or a benzene ring. X ⁷¹ and X ^{72 ′} each independently represents a hydrogen atom or a group that can be substituted on a benzene ring, L represents an —S— group or a —CHR ⁷³ — group, and R ⁷³ represents a hydrogen atom or an alkyl group. Represents a group.) The silver iodide content of the photosensitive silver halide is photothermographic material according to any one of claims 1 to 4, characterized in that at most 5 mol% to 100 mol%. The silver iodide content of the photosensitive silver halide is photothermographic material according to any one of claims 1 to 5, characterized in that 40 mol% to 100 mol%. The photothermographic material according to any one of claims 1 to 6, characterized in that is exposed by the laser light source. 8. The photothermographic material according to claim 7 , wherein the laser light source is a laser light source having a wavelength of 350 nm to 450 nm. The photothermographic material according to claim 7 or claim 8, wherein the laser light source is a blue semiconductor laser.