JPH0623843B2 - Photosensitive material for heat development - Google Patents

Description

Description: FIELD OF THE INVENTION The present invention relates to a photothermographic material having a photosensitive layer containing a silver halide, a reducing agent and a polymerizable compound on a support.

BACKGROUND OF THE INVENTION A light-sensitive material having a photosensitive layer containing a silver halide, a reducing agent and a polymerizable compound on a support is suitable for an image forming method in which a latent image of silver halide is formed and the polymerizable compound is polymerized. Can be used.

As an example of the image forming method, Japanese Patent Publication No. 45-11149.
No. 47-20741, No. 49-10697, JP-A Nos. 57-138632 and 58-169143. In these methods, when the exposed silver halide is developed using a developer, a coexisting polymerizable compound (eg, vinyl compound) initiates polymerization to form an image-like polymer compound. Therefore, the above method requires a development process using a liquid, and the process requires a relatively long time.

As an improvement of the above method, JP-A-61-69062 discloses a method capable of forming a polymer compound by a dry treatment. This method consists of a photosensitive silver salt (silver halide), a reducing agent, and a crosslinkable compound (polymerizable compound).
A latent image of a photosensitive silver salt is formed by subjecting a recording material (photosensitive material) having a photosensitive layer composed of a binder and a binder carried on a support to imagewise exposure to form a latent image and then heat development. A polymer compound is formed on the exposed portion.

The above image forming method is a method of polymerizing the polymerizable compound in the portion where the latent image of silver halide is formed. The present inventors have invented a method capable of polymerizing a polymerizable compound in a portion where a latent image of silver halide is not formed, and this invention has been applied for a patent (Japanese Patent Application No. 60-2106).
57). In this method, in heat development, a reducing agent acts on the portion where the latent image of silver halide is formed to suppress the polymerization of the polymerizable compound, and at the same time, promotes the polymerization of other portions.

The polymerization reaction in the developing process of the above image forming method proceeds smoothly under alkaline conditions. For this reason,
A base or base precursor may be included in the photosensitive layer of the photosensitive material. The bases that can be contained in the photosensitive layer of the photosensitive material are described in JP-A-61-73145. However, when a base or a base precursor is added to the light-sensitive layer (particularly when a base is added), the sensitivity of the light-sensitive material tends to decrease during the storage period after production and before use. Further, the above-mentioned JP-A-61-1
None of the base precursors described in Japanese Patent No. 73145 satisfies the two requirements of stability during storage and rapid decomposition (base formation) during development.

[Summary of the Invention] The present inventor has conducted extensive studies for the purpose of providing an excellent photosensitive material that can be used in an image forming method.

An object of the present invention is to provide a light-sensitive material having excellent storage stability and capable of obtaining a clear image during development processing.

The present invention is a photothermographic material having a photosensitive layer containing a silver halide, a reducing agent and a polymerizable compound on a support, wherein the photosensitive layer is a base precursor represented by the following formula:
And a heat-meltable compound having a melting point of 30 to 200 ° C. and a polar group-containing heat-melting compound.

In _{{R (SO 2 CH 2 CO} 2 H) x} z · B y [ the above formulas, R represents an alkyl group, an alkylene group, an alkylene group -Q- alkylene group, an aryl group, an arylene group -Q- arylene group, and It is a monovalent or divalent group selected from the group consisting of heterocyclic residues (each group may have one or more substituents), and Q is -O-, -S-, -SO-. , And a —SO ₂ — group, a divalent group selected from the group consisting of —SO ₂ —, B is a monoacid base or a diacid base having a pKa of 9 or more and a total number of carbon atoms of 12 or less, and x is R Is 1 if R is divalent, 2 if R is divalent, y is equal to x if B is monoacidic, 1 if B is diacidic, and z Is 2 when R is a monovalent group and B is a diacid group,
Otherwise it is 1.]

EFFECTS OF THE INVENTION The light-sensitive material of the present invention is characterized in that the light-sensitive layer contains, in addition to the base precursor represented by the above formula, a heat-melting compound having a melting point of 30 ° C. to 200 ° C. and a polar group. And

In the above-mentioned JP-A-61-73145, some of the base precursors represented by the above formula are applicable to a light-sensitive material having a photosensitive layer containing a silver halide, a reducing agent and a polymerizable compound on a support. As a basic base precursor. However, the base precursor represented by the above formula is stored in an extremely stable state in the above-mentioned photosensitive layer, but its decomposition rate during heat development is slow, and the demand for rapid generation of base was not sufficiently satisfied. .

According to the studies of the present inventors, the heat-meltable compound having a melting point of 30 ° C. to 200 ° C. and having a polar group serves as a solvent for the above-mentioned base precursor during heating, and therefore the base precursor is contained in the heat-meltable compound. It has been found that it dissolves, which significantly accelerates the decomposition reaction of the base precursor.

In the light-sensitive material of the present invention, the light-sensitive layer has a melting point of 30 ° C. to 200 ° C.
By containing a heat-fusible compound having a polar group and a temperature of ℃, the decomposition rate of the base precursor represented by the above formula at the time of heat development is increased, and a base is rapidly produced during heat development. It is a thing. Therefore, the light-sensitive material of the present invention has excellent storability, a base is rapidly generated in the heat development process, and the polymerization reaction of the polymerizable compound proceeds smoothly, so that a very clear image can be obtained. Further, the heating time in the heat development process can be shortened and the heat development process can be performed by heating at a low temperature.

The base precursor represented by the above formula is extremely stable during storage (normal temperature), and the heat-fusible compound is a solid during storage (normal temperature) and exhibits no decomposition promoting action. There is almost no fear that the excellent storage stability of the base precursor will deteriorate.

[Detailed Description of the Invention] The base precursor used in the light-sensitive material of the present invention is shown below. It should be noted that the following base precursors and examples of applying the following base precursors to silver salt photographic type photothermographic materials and heat-sensitive recording materials are described in JP-A-61-5.
It is described in Japanese Patent No. 1139.

In _{{R (SO 2 CH 2 CO} 2 H) x} z · B y above formulas, R represents an alkyl group (preferably 1 to 5 carbon atoms), an alkylene group (preferably 1 to 5 carbon atoms ), An alkylene group-Q-alkylene group (each alkylene group preferably has 1 to 5 carbon atoms),
Consists of an aryl group, an arylene group-Q-arylene group, and a heterocyclic residue (preferably a 5-membered or 6-membered ring, and preferably containing 1 to 4 nitrogen atoms, oxygen atoms or sulfur atoms as hetero atoms). It is a monovalent or divalent group selected from the group (each group may have one or more substituents).

In addition, Q is -O-, -S-, -SO-, and -S.
It is a divalent group selected from the group consisting of O ₂ —.

Examples of the substituent capable of substituting R are halogen atom (fluorine atom, chlorine atom, bromine atom, iodine atom), nitro group, cyano group, carbamoyl group (the nitrogen atom of the carbamoyl group is an alkyl group, A cycloalkyl group or an aryl group may be bound), a sulfamoyl group (an alkyl group, a cycloalkyl group or an aryl group may be bound to the nitrogen atom of the sulfamoyl group), an alkoxycarbonyl group, an alkoxy group, Examples thereof include an alkyl group, a trifluoromethyl group, a vinyl group, an acylamino group, a carboxylic acid group, and an alkylsulfinyl group.

Among R described above, an alkylene group, an aryl group,
A monovalent or divalent group selected from the group consisting of an arylene group and a heterocyclic residue is preferable (each group may have one or more substituents). Further, an aryl group or a heterocyclic residue substituted with an electron-attracting group having a Hammett sigma value of more than 0 (eg, halogen atom, cyano group, nitro group, carbamoyl group, sulfamoyl group) is particularly preferable.

Preferred specific examples of R include methylene group, ethylene group, phenyl group, p-chlorophenyl group, p-bromophenyl group, p-iodophenyl group, 3,4-dichlorophenyl group, 2,5-dichlorophenyl group, 2,4 dichlorophenyl group, 3-nitrophenyl group, 4-nitrophenyl group, 4-cyanophenyl group, 3-carbamoylphenyl group, 3-sulfamoylphenyl group, 2-methoxycarbonylphenyl group, 3-methoxycarbonylphenyl group Group, 1-naphthyl group, 2-naphthyl group, 2-pyridyl group, 4-pyridyl group, 2-thienyl group, 5-chloro-2
-Thienyl group, 2-benzothiazolyl group, 2-benzimidazolyl group, 4-chloro-1-naphthyl group, 4-bromo-1-naphthyl group, 1,3-phenylene group, 1,5-
Examples thereof include a naphthylene group, a 2,6-naphthylene group and a 2,7-naphthylene group.

In the above formula, B is a monoacid base or a diacid base having a pKa of 9 or more and a total number of carbon atoms of 12 or less.
x is 1 when R is a monovalent group and 2 when R is a divalent group. y is equal to x when B is a monoacid base, and B is
Is 1 when is a diacid base. Then, z is 2 when R is a monovalent group and B is a diacid group, and is 1 otherwise.

The base represented by B is particularly preferably a low-volatile organic base having a pKa of 10 or more and a boiling point of 150 ° C. or more.
Examples of particularly preferable bases include guanidines, cyclic guanidines, amidines, cyclic amidines, tetraalkylammonium hydroxides and the like.

The following are typical examples of the base part B of the base precursor used in the present invention.

(B1) Dimethylamine (B2) Diethylamine (B3) Piperidine (B4) Piperazine (B5) Ethylenediamine (B6) N, N'-Dimethylethylenediamine (B7) Acetamidine (B8) Diazabicyclononene (B9) Diazobicycloundecene (B10) Tetramethylammonium hydroxide (B11) Tetraethylammonium hydroxide (B12) (B13) (B14) (B15) (B16) (B17) (B18) Next, typical specific examples of the base precursor represented by the above formula, which can be preferably used in the light-sensitive material of the present invention, are shown below.

(1) (2) (3) (Four) (Five) (6) (7) (8) (9) (Ten) (11) (12) (13) (14) (15) (16) (17) (18) (19) (20) (twenty one) (twenty two) (twenty three) (twenty four) (twenty five) (26) (27) (28) (29) (30) (31) (32) (33) (34) (35) (36) (37) (38) (39) (40) (41) (42) (43) (44) (45) (46) (47) (48) (49) (50) (51) (52) (53) (54) (55) (56) (57) (58) (59) (60) (61) (62) (63) (64) (65) (66) (67) (68) (69) (70) (71) (72) (73) (74) (75) (76) (77) (78) (79) (80) The base precursor as described above can be easily produced by the production method described in JP-A-61-51139.

In the light-sensitive material of the present invention, the base precursor may be used alone or in combination of several kinds.
Further, it may be used in combination with another base precursor (for example, the base precursor described in the specification of "Photosensitive Material" filed on August 13, 1986 (5) by the present applicant).

The light-sensitive layer of the light-sensitive material of the present invention preferably contains the above-mentioned base precursor in the range of 0.01 g / m ^{2 to} 10 g / m ² , and in the range of 0.01 g / m ^{2 to} 3 g / m ^2. More preferable.

The light-sensitive layer of the light-sensitive material of the present invention contains, in addition to the base precursor described above, a compound having a melting point of 30 to 200 ° C. and a polar group.

The melting point of the heat-fusible compound is 30 ° C to 200 ° C, more preferably 50 ° C to 150 ° C.
The heat-meltable compound and the base precursor may be separately contained in the photosensitive layer, or the base precursor may be dispersed in the heat-meltable compound and contained in the photosensitive layer.

The polar group of the heat-meltable compound is not particularly limited as long as it has a function of dissolving the above-mentioned base precursor when heated. Examples of such a compound having a polar group include carboxylic acid amide derivatives, sulfonic acid amide derivatives, phosphoric acid amide derivatives, ketone compounds, ester compounds, ether compounds, urea derivatives, urethane compounds,
The compound etc. which have a hydroxyl group can be mentioned. Of these, carboxylic acid amide derivatives and urea derivatives are particularly preferable.

Hereinafter, typical specific examples of the heat-meltable compound having a melting point of 30 to 200 ° C. and having a polar group will be shown.

(A) Polyhydroxy compound: sorbitol, dulcitol, pentaerythritol, trimethylolethane, hexanediol, cyclohexanediol, saponin, vanillin, decanediol (B) Amide compound: acetamide, propionamide, toluenesulfonamide, benzamide (C) Urea compounds: methylurea, 1,3-dimethylurea, n-butylurea,
Dimethylol urea, tetramethyl urea, phenyl urea,
Benzoylurea, 1,1-diethylurea and other compounds (including those classified as A to C above)
Is shown as a structural formula in the following (1) to (38).

(1) (2) (3) (4) (5) (6) (7) (8) (9) (10) (11) (12) (13) (14) (15) (16) (17) (18) (19) (20) (21) (22) (23) (24) _{(25) H 2 N-SO} 2 -N (C 3 H 7) 2 (26) (27) (28) (29) (30) (31) (32) (33) (34) (35) (36) (37) n-C ₁₆ H ₃₃ OH (38) n-C ₁₈ H ₃₇ OH The heat-melting compounds as described above may be used alone or in combination of two or more kinds. The photosensitive layer of the photosensitive material of the present invention preferably contains the heat-fusible compound in the range of 3 to 30% by weight, more preferably 5 to 20% by weight.

The silver halide, the reducing agent, the polymerizable compound, and the support which compose the light-sensitive material of the present invention will be sequentially described below.

The light-sensitive material of the present invention contains silver chloride as silver halide,
Any grain of silver bromide, silver iodide or silver chlorobromide, silver chloroiodide, silver iodobromide, or silver chloroiodobromide can be used.

The halogen composition of the silver halide grains may be uniform or non-uniform on the surface and inside. Regarding silver halide grains having multiple structures having different compositions on the surface and inside, JP-A-57-154232 and 58-10853 are known.
3, 59-48755, 59-52237, U.S. Pat. No. 4,433,048 and European Patent No. 1.
No. 00984 is described in each specification. Also, Japanese Patent Application Sho 61
No. 25576, a silver halide grain having a high silver iodide ratio in the shell portion may be used.

There is also no particular limitation on the crystal habit of the silver halide grains. For example, tabular grains having an aspect ratio of 3 or more as in the light-sensitive material described in Japanese Patent Application No. 61-55509 may be used.

The silver halide used in the light-sensitive material of the present invention can be used in combination with two or more kinds of silver halide grains having different halogen compositions, crystal habits, grain sizes and the like.

The grain size distribution of silver halide grains is not particularly limited. For example, monodisperse silver halide grains having a substantially uniform grain size distribution may be used, as in the light-sensitive material described in Japanese Patent Application No. 61-55508.

In the light-sensitive material of the present invention, the average grain size of silver halide grains is preferably 0.001 to 5 μm, more preferably 0.001 to 2 μm.

The amount of silver halide contained in the photosensitive layer is 0.1 mg to 1 in terms of silver including an organic silver salt which is an optional component described later.
It is preferably in the range of 0 g / m ² . Further, in terms of silver equivalent of only silver halide, it is preferably 0.1 g / m ² or less, and particularly preferably 1 mg to 90 mg / m ² .

The reducing agent that can be used in the light-sensitive material of the present invention has a function of reducing silver halide and / or a function of accelerating (or suppressing) the polymerization of the polymerizable compound. There are various kinds of substances as the reducing agent having the above function.
Examples of the reducing agent include hydroquinones, catechols, p
-Aminophenols, p-phenylenediamines, 3
-Pyrazolidones, 3-aminopyrazoles, 4-amino-5-virazolones, 5-aminouracils, 4,5
-Dihydroxy-6-aminopyrimidines, reductones, aminoreductones, o- or p-sulfonamidophenols, o- or p-sulfonamidonaphthols, 2-sulfonamidoindanones, 4-sulfonamido-5- Examples include pyrazolones, 3-sulfonamidoindoles, sulfonamide pyrazolobenzimidazoles, sulfonamide pyrazolotriazoles, α-sulfonamido ketones, and hydrazines. By adjusting the type and amount of the reducing agent, it is possible to polymerize the polymerizable compound in the portion where the latent image of silver halide is formed or the portion where the latent image is not formed. In a system in which a polymerizable compound in a portion where a latent image of silver halide is not formed is polymerized, 1
It is particularly preferred to use -phenyl-3-pyrazolidones.

Regarding various reducing agents having the above functions, Japanese Patent Application Nos. 60-22980, 60-29894 and 60-
68874, 60-210657, 60-22
No. 6084, No. 60-227527, No. 60-227.
Nos. 528 and 61-42746 (including those described as developers or hydrazine derivatives)
There is. Regarding the reducing agent, see T. James, "The Th
eory of the Photographic Process "Fourth Edition, 291-
334 (1977), Research Disclosure Vol.170, June 1978, No. 17029 (9-).
15), and Vol.176, December 1978, No. 17643 (pages 22 to 31). Also,
As in the light-sensitive material described in Japanese Patent Application No. 61-55505, instead of the reducing agent, a reducing agent precursor capable of releasing the reducing agent under heating conditions or in contact with a base may be used. . Also in the light-sensitive material of the present invention, the reducing agents and reducing agent precursors described in the above specifications and references can be effectively used. Therefore, the “reducing agent” in the specification includes the reducing agents and reducing agent precursors described in the above-mentioned respective specifications and literatures.

These reducing agents may be used alone, or as described in each of the above specifications, two or more reducing agents may be mixed and used. When two or more reducing agents are used in combination, the reducing agents may interact with each other by first promoting the reduction of silver halide (and / or organic silver salt) by so-called superadditivity. To cause polymerization of the polymerizable compound via an oxidation-reduction reaction with another reducing agent in which the oxidant of the first reducing agent generated by reduction of silver halide (and / or organic silver salt) coexists (Or suppressing the polymerization) is considered. However, in actual use, it is difficult to specify which of the above actions because the above reactions can occur simultaneously.

Specific examples of the reducing agent include pentadecylhydroquinone, 5-t-butylcatechol, p- (N, N-diethylamino) phenol, 1-phenyl-4-methyl-
4-hydroxymethyl-3-pyrazolidone, 1-phenyl-4-methyl-4-heptadecylcarbonyloxymethyl-3-pyrazolidone, 2-phenylsulfonylamino-4-hexadecyloxy-5-t-octylphenol, 2-phenyl Sulfonylamino-4-t-butyl-5-hexadecyloxyphenol, 2- (N-butylcarbamoyl) -4-phenylsulfonylaminonaphthol, 2- (N-methyl-N-octadecylcarbamoyl) -4-sulfonylaminonaphthol , 1-acetyl-2-phenylhydrazine, 1-acetyl-2-
{(P or o) -aminophenyl} hydrazine, 1-
Formyl-2-{(p or o) -aminophenyl} hydrazine, 1-acetyl-2-{(p or o) -methoxyphenyl} hydrazine, 1-lauroyl-2-
{(P or o) -aminophenyl} hydrazine, 1-
Trityl-2- (2,6-dichloro-4-cyanophenyl) hydrazine, 1-trityl-2-phenylhydrazine, 1-phenyl-2- (2,4,6-trichlorophenyl) hydrazine, 1- {2- (2,5-di-t-pentylphenoxy) butyroyl} -2-{(p or o)
-Aminophenyl} hydrazine, 1- {2- (2,5-
Di-t-pentylphenoxy) butyroyl} -2-
{(P or o) -aminophenyl} hydrazine pentadecyl fluorocaprylate, 3-indazolinone,
1- (3,5-dichlorobenzoyl) -2-phenylhydrazine, 1-trityl-2-[{2-N-butyl-N
-Octylsulfamoyl) -4-methanesulfonyl}
Phenyl] hydrazine, 1- {4- (2,5-di-t-
Pentylphenoxy) butyroyl} -2-{(p or o) -methoxyphenyl} hydrazine, 1- (methoxycarbonylbenzohydryl) -2-phenylhydrazine, 1-formyl-2- [4- {2- (2, 4-di-t
-Pentylphenoxy) butylamido} phenyl] hydrazine, 1-acetyl-2- [4- {2- (2,4-di-t-pentylphenoxy) butylamido} phenyl]
Hydrazine, 1-trityl-2-[{2,6-dichloro-4- (N, N-di-2-ethylhexyl) carbamoyl} phenyl] hydrazine, 1- (methoxycarbonylbenzohydryl) -2- (2,2 4-dichlorophenyl)
Hydrazine, 1-trityl-2-[{2- (N-ethyl-N-octylsulfamoyl) -4-methanesulfonyl} phenyl] hydrazine, 1-benzoyl-2-tritylhydrazine, 1- (4-butoxybenzoyl ) -2
-Tritylhydrazine, 1- (2,4-dimethoxybenzoyl) -2-tritylhydrazine, 1- (4-dibutylcarbamoylbenzoyl) -2-tritylhydrazine, 1- (1-naphthoyl) -2-tritylhydrazine, etc. Can be mentioned.

In the light-sensitive material of the present invention, the reducing agent is preferably used in the range of 0.1 to 1500 mol% with respect to 1 mol of silver (including the above-described silver halide and an organic silver salt which is an optional component). .

The polymerizable compound that can be used in the light-sensitive material of the present invention is not particularly limited, and known polymerizable compounds can be used.
As a method of using the light-sensitive material, it is preferable to use a compound having a high boiling point (for example, a boiling point of 80 ° C. or higher) that is hard to volatilize during heating when a heat development process is planned.
Further, in the embodiment in which the photosensitive layer contains a color image-forming substance as an optional component described later, the color image-forming substance is immobilized by polymerizing and curing the polymerizable compound. It is preferable that the compound is a crosslinkable compound having a polymerizable functional group. Further, as described later, when a transfer image is formed using an image receiving material, Japanese Patent Application No.
It is preferable to use a highly viscous substance as the polymerizable compound as in the light-sensitive material described in the specification of No. 150079.

The polymerizable compounds that can be used in the light-sensitive material are described in the application specifications for a series of light-sensitive materials described above and below.

The polymerizable compound used in the light-sensitive material is generally a compound having addition polymerization or ring-opening polymerization. The compound having an addition-polymerizable group includes a compound having an ethylenically unsaturated group, and the compound having a ring-opening polymerizable group includes a compound having an epoxy group. A compound having an ethylenically unsaturated group is particularly preferable.

The compound having an ethylenically unsaturated group that can be used in the light-sensitive material of the present invention includes acrylic acid and salts thereof,
Acrylic acid esters, acrylamides, methacrylic acid and its salts, methacrylic acid esters, methacrylamides, maleic anhydride, maleic acid esters, itaconic acid esters, styrenes, vinyl ethers,
Examples include vinyl esters, N-vinyl heterocycles, allyl ethers, allyl esters and their derivatives.

Specific examples of the polymerizable compound that can be used in the present invention include acrylic acid esters, and include n-butyl acrylate, cyclohexyl acrylate, 2-ethylhexyl acrylate, benzyl acrylate, furfuryl acrylate, ethoxyethoxyethyl acrylate, dicyclohexyloxy. Ethyl acrylate, nonylphenyloxyethyl acrylate, hexanediol diacrylate, butanediol diacrylate, neopentyl glycol diacrylate, trimethylolpropane triacrylate, pentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol cyhexaacrylate, poly Oxyethylenated bisphenol A diacrylate, hydroxypo Polyacrylate of ether,
Examples thereof include polyester acrylate and polyurethane acrylate.

Other specific examples of methacrylic acid esters include methyl methacrylate, butyl methacrylate, ethylene glycol dimethacrylate, butanediol dimethacrylate, neopentyl glycol dimethacrylate, trimethylolpropane trimethacrylate, pentaerythritol trimethacrylate, and pentaerythritol tetramethacrylate. Methacrylate and dimethacrylate of polyoxyalkylenated bisphenol A and the like can be mentioned.

The polymerizable compounds may be used alone or in combination of two or more. The light-sensitive material containing two or more polymerizable compounds in combination is described in Japanese Patent Application No. 61-55504. A substance obtained by introducing a polymerizable functional group such as a vinyl group or a vinylidene group into the chemical structure of the above-described reducing agent or an optional component of a color image forming substance described later can also be used as the polymerizable compound of the present invention. Needless to say, the use of a substance that serves as a reducing agent and a polymerizable compound or a color image forming substance and a polymerizable compound as described above is also included in the aspect of the present invention.

In the light-sensitive material of the present invention, the polymerizable compound is preferably used in the range of 0.05 to 1200% by weight based on silver halide. A more preferable range of use is 5 to 950% by weight.

The light-sensitive material of the present invention comprises a support and a light-sensitive layer containing the components described above. The support is not particularly limited, but when heat development processing is planned as a method of using the light-sensitive material, it is preferable to use a material that can withstand the processing temperature of the development processing. Examples of materials that can be used for the support include glass, paper, high-quality paper, coated paper, cast coated paper, synthetic paper, metal and its analogs, polyester, acetyl cellulose, cellulose ester, polyvinyl acetal, polystyrene, polycarbonate, polyethylene. Examples thereof include films such as terephthalate, and paper laminated with a resin material or a polymer such as polyethylene.

When the support is made of a porous material such as paper, it should have a certain level of smoothness like the support used in the photosensitive material described in Japanese Patent Application No. 61-52996. Is preferred. When a paper support is used, it is preferable to use a paper support having a low degree of water absorption, such as the photosensitive material described in the specification of "Photosensitive Material" filed on Aug. 4, 1986 by the present applicant. preferable.

Hereinafter, various aspects of the light-sensitive material of the present invention, arbitrary components that can be contained in the light-sensitive layer, auxiliary layers that can be optionally provided in the light-sensitive material, and the like will be sequentially described.

In the photosensitive material of the present invention, the polymerizable compound is preferably dispersed in the photosensitive layer in the form of oil droplets. For examples of the photosensitive material in which the polymerizable compound is dispersed in the photosensitive layer in the form of oil droplets,
It is described in Japanese Patent Application No. 60-218603. Other components in the photosensitive layer such as silver halide, a reducing agent, and a color image forming substance may be contained in the oil droplets. Regarding the light-sensitive materials containing silver halide in the oil droplets, Japanese Patent Application Nos. 60-261888 and 61-5751 disclose the light-sensitive materials further containing a reducing agent in the oil droplets. Each of them is described in the specification of Japanese Patent Application No. 61-25577. When the silver halide is included in the oil droplet, it is included in the oil droplet as described in the specification of "Photosensitive Material" filed on July 8, 1986 by the present applicant. The number of silver halide grains is preferably 5 or more.

The oil droplets of the polymerizable compound are more preferably in the form of microcapsules. Various known techniques can be applied to the microcapsules without particular limitation. An example of a light-sensitive material in which oil droplets of a polymerizable compound are in a microcapsule state is disclosed in Japanese Patent Application No. 60-11.
7089 specification.

There is no particular limitation on the wall material that constitutes the outer shell of the microcapsule. Regarding a photosensitive material using a microcapsule having an outer shell made of a polyamide resin and / or a polyester resin, Japanese Patent Application No. 61-53871 discloses a microcapsule having an outer shell made of a polyurea resin and / or a polyurethane resin. Japanese Patent Application No. 61-53872 for a light-sensitive material using the above, and Japanese Patent Application No. 61-538 for a light-sensitive material using a microcapsule having an outer shell made of an amino-aldehyde resin.
Japanese Patent Application No. 61-538 discloses a photosensitive material using microcapsules having an outer shell made of gelatin.
Japanese Patent Application No. 61-741 discloses a light-sensitive material using microcapsules having an outer shell made of an epoxy resin.
-53875 describes a photosensitive material using microcapsules having a composite resin outer shell containing a polyamide resin and a polyurea resin, see Japanese Patent Application No. 61-53877, which describes a composite resin containing a polyurethane resin and a polyester resin. The light-sensitive materials using microcapsules having shells are described in Japanese Patent Application No. 61-53878.

When the silver halide is contained in the microcapsules, it is preferable that the silver halide be present in the wall material that constitutes the outer shell of the microcapsules. Regarding the photosensitive material containing silver halide in the wall material of the microcapsule, Japanese Patent Application No. 61-61
It is described in the specification of -11556.

Further, two or more microcapsules in which at least one of the components contained in the microcapsules such as silver halide, a reducing agent, a polymerizable compound, and a color image forming substance which is an optional component described later are different may be used in combination. Good. In particular, in the case of forming a full-color image, it is preferable to use together three or more types of microcapsules in which the color image forming substance to be contained has different coloring hues. Regarding the light-sensitive material in which two or more kinds of microcapsules are used in combination, Japanese Patent Application No. 61-4
It is described in the specification of 2747.

The average particle size of the microcapsules is preferably 3 to 20 μm. The particle size distribution of the microcapsules is preferably uniform over a certain value, as in the light-sensitive material described in Japanese Patent Application No. 61-150080.

When accommodating silver halide in microcapsules, the average grain size of the silver halide grains described above is preferably one-fifth or less, and preferably one-tenth or less, of the average size of microcapsules. Is more preferable. By setting the average grain size of silver halide grains to be 1/5 or less of the average size of microcapsules,
It is possible to obtain a uniform and smooth image.

Optional components that can be contained in the light-sensitive layer of the light-sensitive material of the present invention include color image-forming substances, sensitizing dyes, organic silver salts, various image-forming accelerators (eg, oils, surfactants, anti-fogging function). And / or a compound having a development promoting function, a compound having an oxygen removing function, etc., a thermal polymerization inhibitor, a thermal polymerization initiator, a development terminator, a fluorescent brightening agent, an anti-fading agent, for preventing halation or irradiation. Examples include dyes or pigments, matting agents, anti-smudge agents, plasticizers, releasing agents, binders, photopolymerization initiators, and solvents for polymerizable compounds.

With the light-sensitive material of the present invention, a polymer image can be obtained with the above-described constitution of the light-sensitive layer, but a color image can be formed by incorporating a color image-forming substance as an optional component into the light-sensitive layer.

The color image-forming substance that can be used in the light-sensitive material of the present invention is not particularly limited, and various types can be used.
That is, the substance that is itself colored (dye or pigment)
Alternatively, a substance (color former) that is colorless or light-colored by itself but develops color by the contact of energy (heat, pressure, light irradiation, etc.) from the outside or another component (developing agent) is also a color image-forming substance. included. Incidentally, the general light-sensitive material using a color image forming substance is described in the above-mentioned JP-A-61-73145. Further, regarding a light-sensitive material using a dye or a pigment as a color image forming substance, Japanese Patent Application No. 61-29
No. 987, Japanese Patent Application No. 61-53876 for a photosensitive material using a leuco dye, and Japanese Patent Application No. 61-9633 for a photosensitive material using a triazene compound.
Regarding the light-sensitive material using the yellow color-forming leuco dye in the specification No. 9, Japanese Patent Application No. 61-133091 and 6
Each of them is described in the specification of 1-133092.

Dyes and pigments that are themselves colored substances are commercially available, as well as various documents (eg, "Handbook of Dyes" edited by the Society of Synthetic Organic Chemistry, published in 1970, "Handbook of Latest Pigments" edited by the Japan Pigment Technology Association, Known ones described in 1975 can be used. These dyes or pigments are used after being dissolved or dispersed.

On the other hand, examples of the substance that develops color by some energy such as heating, pressurization, and light irradiation are thermochromic compounds,
Known are piezochromic compounds, photochromic compounds, and leuco bodies such as triarylmethane dyes, quinone dyes, indigoid dyes, and azine dyes. All of them develop color by heating, pressurizing, light irradiation or air oxidation.

Examples of the substance that develops a color upon contact with another component include various systems that develop a color by an acid-base reaction between two or more components, a redox reaction, a coupling reaction, a chelate formation reaction and the like. For example, pressure-sensitive copying paper (pages 29 to 58) and azography (87 to 87) described in "Introduction to Special Paper Chemistry" by Hiroyuki Moriga (published in 1975).
95), thermosensitive coloring due to chemical changes (118-120)
Page) and other well-known color development systems, or a seminar by Kinki Chemical Industry Association "Latest dye chemistry-Attractive utilization as a functional dye and new development-" Proceedings 26-32, (19
The coloring system described in June 19, 80) can be used. Specifically, a color-developing system composed of a colorant having a partial structure such as lactone, lactam, and spiropyran used for pressure-sensitive paper and an acidic substance (developing agent) such as acid clay or phenol; an aromatic diazonium salt or Diazotate, diazosulfonates and naphthols,
Systems utilizing azo coupling reactions of anilines and active methylenes; reactions of hexamethylenetetramine with ferric ions and gallic acid, reactions of phenolphthalein-complexones with alkaline earth metal ions, etc. Chelate forming reaction; a redox reaction such as a reaction between ferric stearate and pyrogallol or a reaction between silver behenate and 4-methoxy-1-naphthol can be used.

When two types of substances that cause a color reaction in a contact state are used as the above-mentioned color image forming substances, one of the substances that cause the color reaction and the polymerizable compound are contained in microcapsules. Then, a color image can be formed on the photosensitive layer by allowing another substance among the substances that cause the above-mentioned color forming reaction to exist outside the microcapsules containing the polymerizable compound. A light-sensitive material capable of obtaining a color image without using an image receiving material as described above is described in Japanese Patent Application No. 61-53881.

The sensitizing dye that can be used in the light-sensitive material of the present invention is
There is no particular limitation, and a silver halide sensitizing dye known in the photographic art can be used. The sensitizing dyes include methine dyes, cyanine dyes, merocyanine dyes, complex cyanine dyes, holopolar cyanine dyes, hemicyanine dyes, styryl dyes and hemioxonol dyes. These sensitizing dyes may be used alone or in combination. In particular, for the purpose of supersensitization, it is common to use a combination of sensitizing dyes. Further, together with the sensitizing dye, a dye which does not have a spectral sensitizing effect itself, or a substance which does not substantially absorb visible light but exhibits supersensitization may be used together. The addition amount of the sensitizing dye is generally about 10 ^{-8 to} 10 ^-2 mol per mol of silver halide. The sensitizing dye is preferably added at the stage of preparing a silver halide emulsion described below. Regarding a light-sensitive material obtained by adding a sensitizing dye in the step of forming silver halide grains, see Japanese Patent Application No. 60-13.
The light-sensitive material obtained by adding a sensitizing dye at the stage of preparing a silver halide emulsion after the formation of silver halide grains is described in Japanese Patent Application No. 61-55510. is there. Further, specific examples of sensitizing dyes that can be used in the light-sensitive material are described in the above-mentioned Japanese Patent Application Nos. 60-139746 and 61-55510.

The addition of the organic silver salt in the light-sensitive material of the present invention is particularly effective in the heat development processing. That is, when heated to a temperature of 80 ° C. or higher, the organic silver salt is considered to participate in the redox reaction using the latent image of silver halide as a catalyst.
In this case, it is preferable that the silver halide and the organic silver salt are in contact with or in close proximity to each other. Examples of the organic compound that constitutes the organic silver salt include an aliphatic or aromatic carboxylic acid, a thiocarbonyl group-containing compound having a mercapto group or α-hydrogen, and an imino group-containing compound. Among them, benzotriazole is particularly preferable. The above organic silver salt is generally used in an amount of 0.01 to 10 mol, preferably 0.01 to 1 mol, per mol of silver halide. The same effect can be obtained by adding an organic compound (for example, benzotriazole) constituting the organic silver salt to the photosensitive layer instead of the organic silver salt. Japanese Patent Application No. 60-141 for photosensitive materials using organic silver salts.
No. 799 specification.

Various image forming accelerators can be used in the light-sensitive material of the present invention. The image forming accelerator includes a silver halide (and / or an organic silver salt) and a reducing agent for promoting the redox reaction between the redox agent and the photosensitive material to the image receiving material or image receiving layer (these will be described later). It has the function of promoting the movement of image forming substances. The image forming accelerator is further classified into an oil, a surfactant, a compound having an antifoggant function and / or a development promoting function, a compound having an oxygen scavenging function, and the like from the viewpoint of physicochemical functions. However,
These substance groups generally have a complex function, and usually have some of the above-mentioned accelerating effects together. Therefore, the above classification is convenient, and in fact, one compound often has a plurality of functions.

Examples of the image forming accelerator include oils, surfactants, compounds having an antifoggant function and / or a development promoting function, and compounds having an oxygen removing function.

As the oil, a high boiling point organic solvent used as a solvent for emulsifying and dispersing a hydrophobic compound can be used.

Examples of the surfactant include pyridinium salts, ammonium salts, phosphonium salts described in JP-A-59-74547 and polyalkylene oxides described in JP-A-59-57231.

The compound having an antifoggant function and / or a development promoting function can be used for the purpose of obtaining a clear image (image having a high S / N ratio) having a high maximum density and a low minimum density. As for the photosensitive material using an antifoggant as a compound having an antifoggant function and / or a development accelerating function, Japanese Patent Application No. 60-294337 discloses a photosensitive material using a compound having a cyclic amide structure. Japanese Patent Application No. 60-294338 discloses a light-sensitive material using a thioether compound in Japanese Patent Application No.
Japanese Patent Application No. 60-294 discloses a light-sensitive material using a polyethylene glycol derivative.
No. 340, Japanese Patent Application No. 60-294341 for a photosensitive material using a thiol derivative, and Japanese Patent Application No. 61-2 for a photosensitive material using an acetylene compound.
Japanese Patent Application No. 61-25578 describes the light-sensitive material using the sulfonamide derivative.

The compound having a function of removing oxygen can be used for the purpose of eliminating the influence of oxygen during development (oxygen has a polymerization inhibiting action). Examples of the compound having an oxygen removing function include compounds having two or more mercapto groups. The photosensitive material using a compound having two or more mercapto groups is described in Japanese Patent Application No. 61-53880.

The thermal polymerization initiator that can be used in the light-sensitive material of the present invention is generally a compound that thermally decomposes under heating to generate a polymerization initiation species (particularly a radical), and is usually used as a radical polymerization initiator. is there. Regarding the thermal polymerization initiator, pages 6 to 18 of “Additional Polymerization / Ring-Opening Polymerization”, edited by Editorial Committee of Polymer Society for Polymer Science, 1983, Kyoritsu Publishing)
It is described in the page etc. Specific examples of the thermal polymerization initiator include azobisisobutyronitrile, 1,1′-azobis (1-cyclohexanecarbonitrile), dimethyl-
Azo compounds such as 2,2′-azobisisobutyrate, 2,2-azobis (2-methylbutyronitrile) and azobisdimethylvaleronitrile, benzoyl peroxide, di-t
-Organic peroxides such as peroxide, dicumyl peroxide, t-butylhydroperoxide, cumene hydroperoxide, inorganic peroxides such as hydrogen peroxide, potassium persulfate, ammonium persulfate, sodium p-toluenesulfinate Etc. can be mentioned. The thermal polymerization initiator is preferably used in the range of 0.1 to 120% by weight, more preferably 1 to 10% by weight, based on the polymerizable compound. In the system in which the polymerizable compound in the portion where the latent image of silver halide is not formed is polymerized, it is preferable to add a thermal polymerization initiator to the photosensitive layer. Further, a light-sensitive material using a thermal polymerization initiator is described in Japanese Patent Application No. 60-210657.

The development terminator that can be used in the light-sensitive material of the present invention is a compound or silver and a silver salt which, after proper development, rapidly neutralize the base or react with the base to lower the concentration of the base in the film and stop the development. It is a compound that interacts and suppresses development. Specific examples thereof include an acid precursor that releases an acid when heated, an electrophilic compound that causes a substitution reaction with a coexisting base when heated, a nitrogen-containing heterocyclic compound, and a mercapto compound. Examples of acid precursors include oxime esters described in JP-A-60-108837 and JP-A-60-192939, and JP-A-60-230.
Examples thereof include compounds that release an acid by the Rossen rearrangement described in Japanese Patent No. 133 publication. In addition, as an example of an electrophilic compound which undergoes a substitution reaction with a base upon heating, Japanese Patent Application Laid-Open No.
Examples thereof include compounds described in 0-230134.

Dyes or pigments may be added to the light-sensitive layer of the light-sensitive material of the present invention for the purpose of preventing halation or irradiation. Regarding the photosensitive material in which a white pigment is added to the photosensitive layer for the purpose of preventing halation or irradiation, the applicant of the present invention, July 2, 1986
It is described in the specification of "Photosensitive Material" filed on the 3rd.

The anti-smudge agent used in the light-sensitive material of the present invention is preferably solid particles at room temperature. As a specific example, starch particles described in British Patent No. 12322347,
Polymer fine powder described in U.S. Pat. No. 3,625,736, microcapsule particles containing no color-developing agent described in U.K. Pat. No. 1,235,991, U.S. Pat. No. 2711.
375, cellulose fine powder, talc, kaolin, bentonite, pyrophyllite, zinc oxide, titanium oxide,
Inorganic particles such as alumina can be used. The average particle size of the particles is preferably in the range of 3 to 50 μm in volume average diameter, and more preferably in the range of 5 to 40 μm. As described above, when the oil droplets of the polymerizable compound are in the microcapsule state, it is more effective that the particles are larger than the microcapsules.

The binder which can be used in the light-sensitive material of the present invention and the image-receiving material described later can be contained in the light-sensitive layer or the image-receiving layer (described later) alone or in combination. It is preferable to mainly use a hydrophilic binder. As the hydrophilic binder, a transparent or translucent hydrophilic binder is typical, and examples thereof include natural substances such as gelatin, gelatin derivatives, cellulose derivatives, starch, and arabic gum, and polyvinyl alcohol, polyvinylpyrrolidone, acrylamide polymers and the like. Includes synthetic polymeric materials such as water soluble polyvinyl compounds. Other synthetic polymeric materials include dispersed vinyl compounds in the form of latices, which increase the dimensional stability of photographic materials in particular. In addition,
Regarding a light-sensitive material using a binder, Japanese Patent Laid-Open No. 61-
It is described in Japanese Patent No. 69062. The light-sensitive material using a binder together with microcapsules is described in Japanese Patent Application No. 61-52994.

A photopolymerization initiator may be added to the photosensitive layer of the photosensitive material of the present invention for the purpose of polymerizing the unpolymerized polymerizable compound after image transfer. A light-sensitive material using a photopolymerization initiator is described in Japanese Patent Application No. 61-3025.

When a solvent for a polymerizable compound is used in the light-sensitive material of the present invention, it is preferably used by encapsulating it in a microcapsule different from the microcapsule containing the polymerizable compound. For the photosensitive material using an organic solvent miscible with the polymerizable compound encapsulated in microcapsules, see Japanese Patent Application No.
It is described in the specification of -52993.

In addition to the above, examples of optional components that can be contained in the photosensitive layer and the usage thereof are also described in the application specification regarding the series of photosensitive materials described above, and Research Disclosure Vol. 170, June 1978. The 17th
No. 029 (pages 9 to 15).

Examples of layers that can be optionally provided in the light-sensitive material of the present invention include an image receiving layer, a heating element layer, an antistatic layer, an anti-curl layer, a peeling layer, a cover sheet or a protective layer.

Instead of using an image receiving material described later as a method of using the photosensitive material, the image receiving layer may be provided on the photosensitive material and an image may be formed on this layer. The image receiving layer provided on the photosensitive material may have the same structure as the image receiving layer provided on the image receiving material. Details of the image receiving layer will be described later.

For the photosensitive material using the heating element layer, Japanese Patent Application No.
Japanese Patent Application No. 61-55507 discloses a light-sensitive material having a cover sheet or a protective layer. In addition, examples of other auxiliary layers and usage modes thereof are also described in the specification of the above-mentioned series of photosensitive materials.

The method for producing the photosensitive material of the present invention will be described below.

Although various methods can be used as a method for producing a light-sensitive material, a general production method is to prepare a coating solution by dissolving, emulsifying or dispersing the components of the photosensitive layer in an appropriate solvent, and applying the solution. It comprises a step of obtaining a light-sensitive material by applying the liquid to the support as described above and drying.

Generally, each coating solution is prepared by preparing a liquid composition containing each component for each component, and then mixing each liquid composition. The liquid composition may be prepared for each component, or may be prepared to contain a plurality of components. A part of the components of the photosensitive layer may be added and used at the stage of preparing the liquid composition or the coating solution or after the preparation. Furthermore, as described below, an oily (or aqueous) composition containing one or more components is
Further, a method of preparing a secondary composition by emulsifying in an aqueous (or oily) solvent can also be used.

With respect to the main components contained in the photosensitive layer, a method for preparing a liquid composition and a coating liquid is shown below.

In the production of the light-sensitive material of the present invention, silver halide is preferably prepared as a silver halide emulsion. There are various methods known in the photographic art for the preparation of silver halide emulsions, but there is no particular limitation regarding the production of the light-sensitive material of the present invention. The silver halide emulsion can be prepared by any of the acidic method, the neutral method and the ammonia method. The reaction mode of the soluble silver salt and the soluble halogen salt may be a one-sided mixing method, a simultaneous mixing method, or a combination thereof. A back-mixing method in which grains are mixed under an excess of silver ions and a controlled double jet method in which pAg is kept constant can also be adopted. Further, the silver halide emulsion may be a surface latent image type in which a latent image is mainly formed on the surface of a grain, or an internal latent image type in which a latent image is formed inside the grain. A direct reversal emulsion in which an internal latent image type emulsion and a nucleating agent are combined can also be used.

In the preparation of the silver halide emulsion used for producing the light-sensitive material of the present invention, it is preferable to use a hydrophilic colloid (eg gelatin) as the protective colloid. By preparing a silver halide emulsion using a hydrophilic colloid, the sensitivity of the light-sensitive material of the present invention produced using this emulsion is improved. The silver halide emulsion contains ammonia, an organic thioether derivative (see JP-B-47-386) and a sulfur-containing compound (JP-A-53-14431) as a silver halide solvent in the step of forming silver halide grains.
No. 9), etc. can be used. Further, in the process of grain formation or physical ripening, a cadmium salt, a zinc salt, a lead salt, a thallium salt or the like may be allowed to coexist. Further, for the purpose of improving the high illuminance failure and the low illuminance failure, a water-soluble iridium salt such as iridium chloride (III valence or IV valence), hexachloroiridium ammonium salt, or a water-soluble rhodium salt such as rhodium chloride can be used.

Soluble salts may be removed from the silver halide emulsion after formation of a precipitate or after physical ripening. In this case, it can be carried out according to the Nudell washing method or the sedimentation method. The silver halide emulsion may be used without ripening, but it is usually chemically sensitized before use. In the emulsion for a conventional type photosensitive material, known sulfur sensitizing method, reduction sensitizing method, noble metal sensitizing method and the like can be used alone or in combination.

When a sensitizing dye is added to the silver halide emulsion,
The aforementioned Japanese Patent Application Nos. 60-139746 and 61-5.
It is preferably added at the stage of preparing a silver halide emulsion as in the light-sensitive material described in Japanese Patent No. 5510. When a nitrogen-containing heterocyclic compound is added as the compound having the fog-preventing function and / or the development-accelerating function, it should be added in the step of forming silver halide grains or the ripening step in the preparation of a silver halide emulsion. Is preferred. The method for producing a light-sensitive material in which a nitrogen-containing heterocyclic compound is added in the step of forming silver halide grains or the step of ripening is described in Japanese Patent Application No. 61-3024.

When the above-mentioned organic silver salt is contained in the photosensitive layer, the organic silver salt emulsion can be prepared by a method similar to the method for preparing the silver halide emulsion.

In the production of the light-sensitive material of the present invention, the polymerizable compound can be used as a medium for preparing the composition of other components in the light-sensitive layer. For example, a silver halide (including a silver halide emulsion), a reducing agent, a color image-forming substance and the like can be dissolved, emulsified or dispersed in a polymerizable compound and used for producing a light-sensitive material. In particular, when a color image forming substance is added, it is preferable to include it in the polymerizable compound. Further, as described later, when oil droplets of the polymerizable compound are microencapsulated, components such as wall material necessary for microencapsulation may be included in the polymerizable compound.

The photosensitive composition containing a polymerizable compound containing silver halide can be prepared using a silver halide emulsion.
In addition to the silver halide emulsion, a silver halide powder prepared by freeze-drying or the like can be used for the preparation of the photosensitive composition. The photosensitive composition containing these silver halides can be obtained by stirring with a homogenizer, a blender, a mixer, or another commonly used stirrer.

In addition, it is preferable to dissolve a copolymer composed of a hydrophilic repeating unit and a hydrophobic repeating unit in the polymerizable compound used for preparing the photosensitive composition. For a photosensitive composition containing the above copolymer, Japanese Patent Application No.
-261887 specification.

Further, instead of using the above copolymer, microcapsules containing a silver halide emulsion as a core substance may be dispersed in a polymerizable compound to prepare a photosensitive composition. The photosensitive composition containing the microcapsules containing the silver halide emulsion as a core substance is described in Japanese Patent Application No. 61-5750.

The polymerizable compound (including those containing other constituents such as the above-mentioned photosensitive composition) is preferably used as an emulsion emulsified in an aqueous solvent. Also, Japanese Patent Application Sho 60
When the oil droplets of the polymerizable compound are microencapsulated as in the light-sensitive material described in JP-A-117089, the wall material necessary for microencapsulation is added to the emulsion, and the microcapsules are removed. The shell-forming treatment can also be carried out at this emulsion stage. Further, a reducing agent or any other component may be added at the stage of the above emulsion.

As an example of the microencapsulation method, a method utilizing coacervation of the hydrophilic wall-forming material described in US Pat. Nos. 2,800,457 and 2,800,458; US Pat. No. 3,287,154 and British Patent No. 990443. Each specification and Japanese Patent Publication No. 38-1957
No. 4, 42-446 and 42-771; interfacial polymerization method; method by polymer precipitation described in US Pat. Nos. 3,418,250 and 3,660,304; US Pat. No. 3,796,669. Method using the described isocyanate-polyol wall material; Method using the isocyanate wall material described in US Pat. No. 3,914,511; US Pat. Nos. 4,001,140, 4;
No. 087376 and U.S. Pat. No. 4,089,802, a method of using a urea-formaldehyde-based or urea-formaldehyde-resilicinol-based wall forming material; walls of melamine-formaldehyde resin, hydroxypropyl cellulose, etc. described in US Pat. No. 4,025,455. In situ method by polymerization of monomers described in JP-B-36-9168 and JP-A-51-9079; Polymerization-dispersion cooling described in British Patents 927807 and 965074. Law; U.S. Pat. No. 3,111,407 and British Patent No. 930422.
The spray drying method described in each specification can be used. The method of microencapsulating the oil droplets of the polymerizable compound is not limited to the above, but a method of forming a polymer film as a microcapsule wall after emulsifying the core substance is particularly preferable.

Regarding the photosensitive microcapsules that can be used for producing the photosensitive material, Japanese Patent Application No. 61-11556,
No. 61-11557, No. 61-53871, No. 61
-53872, 61-53873, 61-53
874, 61-53875, 61-53877.
No. 61-53878.

When the polymerizable compound is a photosensitive composition containing silver halide in the emulsion of the polymerizable compound (including the microcapsule liquid subjected to the microencapsulation treatment) described above, the coating liquid for the photosensitive material is used as it is. Can be used as Emulsions other than the above can be mixed with the composition of other components such as a silver halide emulsion and optionally an organic silver salt emulsion to prepare a coating solution. Other components may be added at the stage of this coating solution as in the case of the above emulsion.

The base precursor and the heat-fusible compound used in the light-sensitive material of the present invention can be added at any stage of the manufacturing process of the coating solution for the light-sensitive layer as described above.

The photosensitive material of the present invention is manufactured by applying the coating solution for the photosensitive layer prepared as described above to a support and drying. The coating of the coating liquid on the support can be easily carried out according to known techniques.

The method of using the light-sensitive material of the present invention will be described below.

The light-sensitive material of the present invention is subjected to a developing treatment at the same time as the imagewise exposure or after the imagewise exposure before use.

Although various exposing means can be used as the exposing method, a latent image of silver halide is generally obtained by imagewise exposure of radiation including visible light. The type of light source and the amount of exposure are
Sensitive wavelength of silver halide (when dye sensitization is performed,
It can be selected according to the sensitized wavelength) and the sensitivity. The original image may be a monochrome image or a color image.

The light-sensitive material of the present invention is subjected to development processing simultaneously with the above imagewise exposure or after the imagewise exposure. The light-sensitive material of the present invention may be subjected to development processing using a developing solution described in Japanese Patent Publication No. 45-11149. As described above, the method described in Japanese Patent Application Laid-Open No. 61-69062, which carries out heat development processing, has the advantage that the operation is simple and the processing can be performed in a short time because it is a dry processing. Therefore, the latter is particularly excellent in the development processing of the light-sensitive material of the present invention.

As a heating method in the heat development treatment, various conventionally known methods can be used. Further, as in the light-sensitive material described in Japanese Patent Application No. 60-135568, the light-sensitive material may be provided with a heating element layer and used as a heating means. Further, as in the image forming method described in Japanese Patent Application No. 61-55506, the heat development treatment may be carried out while suppressing the amount of oxygen present in the photosensitive layer. The heating temperature is generally 80 ° C to 200 ° C, preferably 100 ° C to 160 ° C. The heating time is generally 1 second to 5 seconds.
Minutes, preferably 5 seconds to 1 minute.

The light-sensitive material of the present invention is subjected to the heat development treatment as described above to polymerize the polymerizable compound in the portion where the latent image of silver halide is formed or the portion where the latent image of silver halide is not formed. it can. In the light-sensitive material of the present invention, the polymerizable compound in the portion in which the latent image of silver halide is formed is generally polymerized in the heat development treatment, but the light-sensitive material described in Japanese Patent Application No. 60-210657 described above is used. It is also possible to polymerize the polymerizable compound in the portion where the latent image of silver halide is not formed, by adjusting the type and amount of the reducing agent, like the material.

As described above, the photosensitive material of the present invention can obtain a polymer image on the photosensitive layer. Further, a dye or a pigment may be fixed to the polymer to obtain a dye image.

The light-sensitive material of the present invention was prepared according to the above-mentioned Japanese Patent Application No. 61-53881.
In the case of the light-sensitive material described in the specification, the light-sensitive material subjected to the development treatment is pressed to destroy the microcapsules and bring two kinds of substances which cause a color-forming reaction into contact with each other. A color image can be formed on it.

Further, the image receiving material can be used to form an image on the image receiving material.

The image receiving material will be described below. An image forming method using an image receiving material or an image receiving layer is generally described in Japanese Patent Application No. 60-112284.

As a support for the image receiving material, in addition to the support that can be used for the light-sensitive material described later, variator paper can be used. When a porous material such as paper is used as the support of the image receiving material, it preferably has a certain smoothness like the image receiving material described in Japanese Patent Application No. 61-52990. . An image receiving material using a transparent support is described in Japanese Patent Application No. 61-52991.

The image receiving material generally has an image receiving layer provided on a support. The image receiving layer is in accordance with the coloring system of the color image forming substance described above,
Various compounds can be used to make up any form. When a polymer image is formed on an image receiving material, a dye or a pigment is used as a color image forming substance, the image receiving material may be composed of only the above support.

For example, when a color-developing system comprising a color-developing agent and a color-developing agent is used, the image-receiving layer may contain the color-developing agent. Further, the image receiving layer may be configured as a layer containing at least one mordant. The mordant can be selected from known compounds in the photographic art and the like in consideration of the conditions such as the type of color image forming substance and used. If necessary, a plurality of mordants having different mordant powers may be used to form two or more image receiving layers.

The image receiving layer preferably contains a polymer as a binder. As the binder, the binder that can be used in the photosensitive layer of the photosensitive material described above can be used. A polymer having low oxygen permeability may be used as a binder, such as the image receiving material described in Japanese Patent Application No. 61-53879.

The image receiving layer may contain a thermoplastic compound. When the image receiving layer contains a thermoplastic compound, it is preferable that the image receiving layer itself is formed as an aggregate of thermoplastic compound fine particles. The image-receiving layer having the above-described structure has an advantage that a transfer image can be easily formed and a glossy image can be obtained by heating after the image formation. The thermoplastic compound is not particularly limited and can be arbitrarily selected and used from known plastic resins (plastics) and waxes. However, the glass transition point of the thermoplastic resin and the melting point of the wax are preferably 200 ° C. or lower. Regarding the image receiving material having the image receiving layer containing the above-mentioned thermoplastic compound fine particles, Japanese Patent Application No. 61-12
Nos. 4952 and 61-124953 are described.

The image receiving layer may contain a photopolymerization initiator or a thermal polymerization initiator. In the image formation using the image receiving material of the present invention, the color image forming substance is transferred together with the unpolymerized polymerizable compound as described later. Therefore, a photopolymerization initiator or a thermal polymerization initiator can be added to the image-receiving layer for the purpose of smoothly proceeding the curing treatment (fixing treatment) of the unpolymerized polymerizable compound. An image receiving material having an image receiving layer containing a photopolymerization initiator is described in Japanese Patent Application No. 61-3025, and an image receiving material having an image receiving layer containing a thermal polymerization initiator is described in Japanese Patent Application No. 61-55502. Are described in each.

The dye or pigment may be contained in the image receiving layer for the purpose of writing characters, symbols, frames, etc. on the image receiving layer or for the purpose of making the background of the image a specific color. Further, a dye or a pigment may be included in the image receiving layer for the purpose of facilitating the front / back discrimination of the image receiving material. As the dye or pigment, various known substances including dyes or pigments that can be used in image formation can be used, but the dye or pigment may impair the image formed in the image receiving layer. In some cases, it is preferable to lower the dyeing density of the dye or pigment (for example, the reflection density is 1 or less), or to use the dye or pigment having the property of being decolorized by heating or light irradiation.
An image receiving material having an image receiving layer containing a dye or pigment having a property of being decolorized by heating or light irradiation is described in Japanese Patent Application No. 61-96339.

Further, when a white pigment such as titanium dioxide or barium sulfate is added to the image receiving layer, the image receiving layer can function as a white reflective layer. When the image receiving layer is made to function as a white reflective layer, the white pigment is 10 g per 1 g of the thermoplastic compound.
It is preferably used in the range of 100 to 100 g.

When the dye or pigment as described above is contained in the image receiving layer, it may be uniformly contained or may be partially distributed. For example, a support described below is made of a material having a light-transmitting property, and a part of the reflection image can be a projection image by including the white pigment in a part of the image receiving layer. By doing so, unnecessary image information in the projected image can be written as a reflected image in the image receiving layer portion containing the white pigment.

The image receiving layer may be composed of two or more layers depending on the functions as described above. The thickness of the image receiving layer is 1 to 1
The thickness is preferably 00 μm, more preferably 1 to 20 μm.

A protective layer may be further provided on the image receiving layer. Further, a layer made of an aggregate of fine particles of a thermoplastic compound may be further provided on the image receiving layer. An image receiving material having a layer comprising an aggregate of fine particles of a thermoplastic compound provided on the image receiving layer is described in Japanese Patent Application No. 61-55503.

Further, a layer containing an adhesive or an adhesive and release paper may be sequentially laminated on the surface of the support opposite to the surface on which the image receiving layer is provided. The sticker-shaped image receiving material having the above structure is described in the specification of "Image receiving material" filed on July 17, 1986 by the present applicant.

The light-sensitive material of the present invention is subjected to development processing as described above,
By pressing the above image receiving materials in a superposed state,
The unpolymerized polymerizable compound can be transferred to the image receiving material to obtain a polymer image on the image receiving material. Various conventionally known methods can be used for the pressing means.

Further, in the embodiment in which the photosensitive layer contains a color image-forming substance,
By carrying out a developing treatment in the same manner, the polymerizable compound is polymerized and cured, and thereby the color image forming substance in the cured portion is immobilized. Then, by pressing the photosensitive material and the image receiving material in a superposed state, the color image forming substance in the uncured portion is transferred to the image receiving material, and a color image can be obtained on the image receiving material.

After the image is formed on the image receiving material as described above, the image receiving material may be heated as in the image forming method described in Japanese Patent Application No. 61-55501. The above method also has an advantage that the unpolymerized polymerizable compound transferred onto the image receiving material is polymerized and the storability of the obtained image is improved.

The light-sensitive material of the present invention is a black-and-white or color photographing and printing sensitive material, printing sensitive material, printing plate, X-ray sensitive material, medical sensitive material (for example, ultrasonic diagnostic machine CRT photographing sensitive material), computer graphic hard copy. There are many applications such as light-sensitive materials and light-sensitive materials for copying machines.

The present invention will be described in more detail with reference to the following examples, but the present invention is not limited thereto.

Example 1 Preparation of Silver Halide Emulsion 40 g of gelatin and 23.8 g of potassium bromide were dissolved in 3 of water, heated to 50 ° C., and stirred for 3 times of silver nitrate.
What melt | dissolved 4 g in 200 m of water was added in 10 minutes. Then, a solution prepared by dissolving 3.3 g of potassium iodide in 100 m of water was added over 2 minutes. The pH of the silver iodobromide emulsion thus obtained was adjusted, precipitated to remove excess salt, and then adjusted to pH 6.0 to obtain a silver iodobromide emulsion with a yield of 400 g.

Preparation of Photosensitive Composition 0.40 g of the following copolymer and 6.00 g of Pergasscript Red I-6-B (manufactured by Ciba-Geigy) were dissolved in 100 g of trimethylolpropane triacrylate. To 18.00 g of the above solution, 0.61 g of the following hydrazine derivative (reducing agent) and the following developing agent (reducing agent)
A solution of 1.22 g dissolved in 1.80 g of methylene chloride was added. Further, 4.06 g of the silver halide emulsion prepared as described above was added, and 1 minute was added using a homogenizer.
The mixture was stirred at 5000 rpm for 5 minutes to obtain a photosensitive composition (emulsion average particle size: about 1 μm).

(Copolymer) (Hydrazine derivative) (Developer) Preparation of microcapsule solution 18.6% aqueous solution of Isoban (manufactured by Kuraray Co., Ltd.)
51 g was added to 48.56 g of a 2.89% aqueous solution of pectin to obtain an aqueous solution whose pH was adjusted to 4.0 with 10% sulfuric acid, and the photosensitive composition was added to this aqueous solution, followed by a homogenizer. The mixture was stirred at 7,000 rpm for 2 minutes, and the photosensitive composition was emulsified in an aqueous solvent (emulsion average particle size: 8 μm).

To 72.5 g of this aqueous emulsion, an aqueous solution of 40% urea 8.3
2 g, resorcin 11.3% aqueous solution 2.82, formalin 37% aqueous solution 8.56 g, ammonium sulfate 8.76
% Aqueous solution 2.74 g was sequentially added, and heating was continued at 60 ° C. for 2 hours while stirring. Thereafter, the pH was adjusted to 7.0 with a 10% aqueous sodium hydroxide solution, 3.62 g of a 30.9% aqueous sodium hydrogen sulfite solution was added, and a dispersion liquid of photosensitive microcapsules having an outer shell made of an amino-formaldehyde resin was added. Was prepared.

Preparation of photosensitive material 10.0 g of microcapsule solution prepared as described above
To the above, 0.4 g of the following base precursor and 0.03 g of a solution prepared by dispersing 0.3 g of acetamide (heat-soluble compound) in 10 g of a 5 wt% aqueous solution of polyvinyl alcohol were prepared to prepare a coating solution. This coating solution was applied onto a polyethylene terephthalate film using a # 30 coating rod and dried to prepare a light-sensitive material according to the present invention.

(Base precursor) Preparation of image receiving material To 125 g of water, 11 g of 40% sodium hexametaphosphate aqueous solution was added, and further 34 g of zinc 3,5-di-α-methylbenzylsalicylate and 82 g of 55% calcium carbonate slurry were mixed and roughly dispersed by a mixer. The liquid was dispersed with a Dynamill disperser, and to 200 g of the obtained liquid, 6 g of 50% SBR latex and 55 g of 8% polyvinyl alcohol were added and uniformly mixed. An image receiving material was prepared by uniformly applying this mixed solution onto art paper having a weight of 43 g / m ² so as to have a wet film thickness of 30 μm, and then drying.

Evaluation of Photosensitive Material The photosensitive material prepared as described above was exposed with a halogen lamp at an illuminance of 2000 lux for 2 seconds, and then the photosensitive layer surface was brought into close contact with a hot plate heated to 125 ° C. and heated for 30 seconds. Then, the light-sensitive material was brought into close contact with the image-receiving material and passed through a pressure roller of 350 kg / cm ² . When the density of the magenta positive color image obtained on the image receiving material was measured with a reflection densitometer, the reflection density of the unexposed area was 1.3, and the reflection density of the exposed area was 0.1. It turned out that an image was obtained.

Example 2 A photosensitive material according to the present invention in the same manner as in Example 1 except that 1,3-dimethylurea was used in the same amount instead of 0.3 g of acetamide used in the preparation of the photosensitive material of Example 1. It was created.

An image was formed in the same manner as in Example 1 using the above light-sensitive material, and a clear image could be obtained in almost the same manner as in Example 1.

Comparative Example 1 A photosensitive material for comparison was prepared in the same manner as in Example 1 except that 0.3 g of acetamide used in preparing the photosensitive material of Example 1 was not added.

When an image was formed in the same manner as in Example 1 using the comparative light-sensitive material, only a blurred image was obtained. Then, in order to obtain a clear image (the reflection density of the unexposed portion is 1.3 and the reflection density of the exposed portion is 0.3), the heating time must be extended from 30 seconds in Example 1 to 100 seconds. did not become.

[Example 3] 0.61 g of the hydrazine derivative (reducing agent) used in the preparation of the photosensitive composition of Example 1 and a developing agent (reducing agent)
Phenidone (reducing agent) 0.1 g instead of 1.22 g,
A light-sensitive material according to the present invention was prepared in the same manner as in Example 1 except that 0.2 g of 1,1'-azobis (1-cyclohexanecarbonitrile) (thermal polymerization initiator) and 0.1 g of benzotriazole were used.

An image was formed in the same manner as in Example 1 using the above light-sensitive material, and a magenta negative image was obtained on the image-receiving material. When the densities of the above color images were measured with a reflection densitometer, it was found that a very clear image having a reflection density of 1.3 in the exposed portion and a reflection density of 0.1 in the unexposed portion was obtained.

[Example 4] A photosensitive material according to the present invention was prepared in the same manner as in Example 1 except that 0.3 g of acetamide used in the preparation of the photosensitive composition of Example 1 was replaced by the same amount of propionamide. did.

An image was formed in the same manner as in Example 1 using the above light-sensitive material. As a result, a clear image could be formed in the same manner as in Example 1 by heating at 125 ° C. for 30 seconds.

Example 5 A photosensitive material according to the present invention was prepared in the same manner as in Example 1 except that 0.3 g of acetamide used in the preparation of the photosensitive composition of Example 1 was replaced by the same amount of ε-caprolactam. Created.

An image was formed in the same manner as in Example 1 using the above light-sensitive material. As a result, a clear image could be formed in the same manner as in Example 1 by heating at 125 ° C. for 30 seconds.

[Example 6] A photosensitive material according to the present invention was prepared in the same manner as in Example 1 except that 0.3 g of acetamide used in the preparation of the photosensitive composition of Example 1 was replaced by the same amount of sorbitol. .

An image was formed in the same manner as in Example 1 using the above light-sensitive material. As a result, a clear image could be formed in the same manner as in Example 1 by heating at 125 ° C. for 30 seconds.

Claims (9)

[Claims] 1. A photothermographic material having a photosensitive layer containing a silver halide, a reducing agent and a polymerizable compound on a support, wherein the photosensitive layer is a base precursor represented by the following formula:
And a photothermographic material having a melting point of 30 ° C. to 200 ° C. and containing a polar group-containing heat-meltable compound: {R (SO ₂ CH ₂ CO ₂ H) _x } _z · B _y [In the above formula, R is a monovalent or divalent group selected from the group consisting of an alkyl group, an alkylene group, an alkylene group-Q-alkylene group, an aryl group, an arylene group-Q-arylene group, and a heterocyclic residue. (Each group may have one or more substituents), Q is a divalent group selected from the group consisting of —O—, —S—, —SO—, and —SO ₂ —. B is a monoacid or diacid base having a pKa of 9 or more and a total number of carbon atoms of 12 or less, and x is 1 when R is a monovalent group and when R is divalent. 2, y is equal to x when B is a monoacidic base, and when B is a diacidic base. , And the and z is the R is a monovalent radical, and when B is a diacid base 2,
Otherwise it is 1.] 2. The melting point of the heat-fusible compound is 50 ° C. to 1
The photosensitive material for heat development according to claim 1, which has a temperature of 50 ° C. 3. The heat-meltable compound is a carboxylic acid amide derivative, a sulfonic acid amide derivative, a phosphoric acid amide derivative, a ketone compound, an ester compound, an ether compound,
The photothermographic material according to claim 1, which is a compound selected from the group consisting of a urea derivative, a urethane compound and a compound having a hydroxyl group. 4. The photothermographic material according to claim 3, wherein the heat-meltable compound is a carboxylic acid amide derivative or a urea derivative. 5. A photosensitive layer containing the above base precursor in an amount of 0.0
The photosensitive material for heat development according to claim 1, which is contained in the range of 1 g / m ^{2 to} 10 g / m ² . 6. The photosensitive layer contains 0.01% of the above heat-fusible compound.
g / m ² to the first claims, including in the range of 10 g / m ²
A heat-developable photosensitive material as described in the item. 7. The photothermographic material according to claim 1, wherein the photosensitive layer further contains a color image forming substance. 8. The photothermographic material according to claim 7, wherein the polymerizable compound and the color image-forming substance are contained in the photosensitive layer in a state of being contained in microcapsules. 9. The photosensitive material for heat development according to claim 1, wherein the photosensitive layer further contains a thermal polymerization initiator.