JPH0362254B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a dye fixing material for transferring a dye image formed on a heat-developable photosensitive material. More specifically, the present invention relates to a dye-fixing material for fixing an image that can be formed on a heat-developable photosensitive material to a dye-fixing layer, particularly by heating without supplying a solvent from the outside. Photography using silver halide is different from other photographic methods,
For example, compared to electrophotography and diazo photography, it has superior photographic characteristics such as sensitivity and gradation adjustment.
It has traditionally been the most widely used. In recent years, a technology has been developed that allows images to be formed easily and quickly on photosensitive materials using silver halide by changing from the conventional wet processing using a developing solution to a dry processing using heating, etc. It's here. Heat-developable photosensitive materials are well known in the art, and for information on heat-developable photosensitive materials and their processes, see
“For example, the basics of photographic engineering (published by Corona Publishing, 1979)
pages 553-555, video information published in April 1978, page 40,
Nebletts Handbook of Photography and
Reprography 7th Ed. (Van Nostrand Reinhold
Company) pages 32-33,
U.S. Patent Nos. 3152904, 3301678, 3392020
No. 3457075, British Patent No. 1131108, No.
No. 1167777 and Research Disclosure Magazine, June 1978, pages 9 to 15 (RD-17029). Many methods have already been proposed for obtaining color images using a dry method. Regarding a method of forming a color image by combining an oxidized form of a developer with a coupler, U.S. Pat. p-
Aminophenol reducing agent received Belgian patent no.
Issue 802519 and Research Disclosure Magazine
In the September 1975 issue, pages 31-32, sulfonamide phenolic reducing agents are described, and in U.S. Pat. No. 4,021,240,
A combination of a sulfonamidophenol reducing agent and a 4-equivalent coupler has been proposed. However, in such a method, a reduced silver image and a color image are simultaneously generated in the exposed area after thermal development, so that the color image becomes cloudy. To solve this problem, there are methods to remove the silver image by liquid processing or to transfer only the dye to another layer, such as a sheet with an image-receiving layer. It has the disadvantage that it is not easy to transfer. Another method is to introduce a nitrogen-containing heterocyclic group into a dye, form a silver salt, and release the dye by heat development.
Research Disclosure Magazine May 1978 Issue 54
Pages 58 to 58 (RD-16966). This method is not a common method because it is difficult to suppress the release of dye in areas not exposed to light, making it impossible to obtain clear images. Further, regarding the method of forming positive color images by thermal silver dye bleaching method, for example, Research Disclosure Magazine, April 1976 issue, pages 30-32 (RD-
14433), December 1976 issue of the same magazine, pages 14-15 (RD-
15227) and US Pat. No. 4,235,957, useful dyes and bleaching methods are described. However, this method requires extra steps and materials, such as stacking and heating activator sheets to accelerate the bleaching of the dye, and the resulting color image gradually deteriorates due to coexisting free silver, etc. Since it is reductively bleached, it has the disadvantage of not being able to withstand long-term storage. Furthermore, methods for forming color images using leuco dyes are described, for example, in U.S. Pat. The present inventors have already provided a new photosensitive material that can solve the drawbacks of these conventional methods, and developed an image forming method for it. (Special application 1982-
No. 157798, No. 56-177611, No. 57-31976). In these methods, it is necessary to transfer the imagewise generated mobile dye to a dye fixing layer, and for this purpose a solvent for dye transfer, e.g.
A solvent such as water, a basic aqueous solution, alcohol, dimethylacetamide, etc. is supplied, but in other methods, a hydrophilic thermal solvent is pre-impregnated in the material, making it unnecessary to supply a solvent from the outside. The latter is advantageous in that it is simple. Further, in the above image forming method, it is advantageous to use a dye release aid such as a base in combination in order to quickly form a color image with high density. However, many of these additives are chemically active, and if they are allowed to coexist with silver halide, they may impair photographic properties or change storage stability. Furthermore, since the above-mentioned hydrophilic thermal solvent is used in large quantities, when it is used in a photosensitive material, it inevitably tends to increase the film thickness, resulting in deterioration of film quality and reduction in image sharpness. . Accordingly, a first object of the present invention is to provide a dye fixing material that can be used to easily obtain dye images with stable photographic properties only by heating. A second object of the present invention is to provide a dye-fixing material for obtaining dye images with low minimum density and high maximum density by heating alone. A third object of the present invention is to provide a method of forming a color image with excellent sharpness by heat treatment. The objects of the present invention are to provide on a support at least a photosensitive silver halide, a binder, and a hydrophilic dye that is mobile in chemical relationship with the reaction when the silver halide is reduced to silver by heating. A photosensitive material containing a "dye-donating substance, etc." capable of forming a "dye-providing substance, etc." is heated after or simultaneously with imagewise exposure to form a mobile hydrophilic dye in an imagewise manner. A dye fixing material for fixing the dye fixing material includes a support and a compound formed on the support that is capable of reacting with or adsorbing at least the dye fixing agent and silver halide and/or organic silver salt oxidizing agent. This can be achieved by constructing a single layer or multiple layers containing. In the light-sensitive material used in the present invention, heating in a substantially water-free state after or simultaneously with imagewise exposure allows the exposed photosensitive silver halide to be used as a catalyst in the exposed or unexposed areas. A mobile hydrophilic dye image is also obtained at the same time as the silver image in either part. In the present invention, this development step is referred to as "heat development," but if this heat development is performed as it is, unreacted dye-providing substances, silver halide, developed silver, etc. will coexist, resulting in the formation of moieties. It is difficult to distinguish from the hydrophilic pigment image of
Moreover, the storage stability is also extremely poor, which is not preferable. However, in the present invention, since the dye of the dye image obtained at this time is a hydrophilic mobile dye, it cannot be moved to the dye fixed layer in an atmosphere to which the hydrophilic dye has affinity. As a result, a dye image with excellent image quality and storage stability can be obtained. This step is the "dye fixation" step in the present invention. It has already been disclosed that this process can be realized mainly by supplying a solvent (Japanese Patent Application No.
(No. 157798, No. 56-177611, No. 57-31976) Furthermore, in the present invention, by making a hydrophilic thermal solvent exist, an atmosphere having affinity with the hydrophilic dye is realized. It is possible to form a dye image with good color reproducibility by completely dry processing, which does not require any supply of solvent at all in all steps from exposure to heat development and fixation of the dye. This principle essentially applies whether a negative-tone emulsion or an auto-positive emulsion is used as the emulsion for a photosensitive material, the only difference being whether the area to be developed is an exposed area or an unexposed area. There is no difference, so even if an autopositive emulsion is used,
A dye image with good color reproducibility can be obtained in the same manner as when using a negative emulsion. In the present invention, heating in a state substantially free of water means heating at 80°C to 250°C, and
A substantially water-free state means that the reaction system is in equilibrium with moisture in the air, and no water is specifically supplied to trigger or promote the reaction. This condition is called “The
theory of the photographic process”4th Ed.
(Edited by THJames, Macmillan) on page 374. In the present invention, "forming a mobile dye by chemically relating to the reaction when silver halide is reduced to silver by heating" means, for example, in the case of a negative-working silver halide emulsion, when exposed to light, Development nuclei are formed in silver halide, and this silver halide causes an oxidation-reduction reaction with a reducing agent or a reducing dye-donating substance,
a reaction in which a reducing agent is oxidized to an oxidant, and this oxidant reacts with a compound that forms or releases a mobile dye to form or release a mobile dye;
A reaction in which a dye-donating substance that originally does not release a mobile dye when heated and a remaining reducing agent causes a redox reaction to release a mobile dye.Reducing property that originally releases a mobile dye when heated This refers to three reactions in which a dye-donating substance is oxidized and tends to release a mobile dye. When a positive silver halide emulsion is used instead of a negative silver halide emulsion, the above reaction occurs in the non-exposed area. In the case of , a dye image in a positive relationship to the silver image is obtained, and in the case of , a dye image in a negative relationship is obtained. Compounds that form or release mobile dyes that can be used in the present invention include the following. 1. A dye-donating substance that can release a mobile dye by reacting with an oxidized product of a reducing agent formed by a redox reaction with silver halide caused by heating (a compound that releases a mobile dye by the reaction) . The compound described in Japanese Patent Application No. 56-17761 falls under this category. This compound is represented by the general formula C-LD, where D represents an image-forming dye moiety described below, and L represents C during the reaction between the oxidized form of the reducing agent and C.
- Represents a linking group whose L bond is cleaved. C
represents a substrate that binds to the oxidized form of the reducing agent; for example, active methylene, active methine, phenol residue and naphthol residue, preferably represented by the following general formula (A) ~
Represented by (G). R ¹ , R ² , R ³ , and R ⁴ are each a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an alkoxy group, an aryloxy group, an aralkyl group, an acyl group, an acylamino group, an alkoxyalkyl group, and an aryloxyalkyl group. group, N-substituted carbamoyl group, alkylamino group, arylamino group, halogen atom, acyloxy group,
Represents a substituent selected from an acyloxyalkyl group and a cyano group, and these substituents further include a hydroxyl group, a cyano group, a nitro group, an N-substituted sulfamoyl group, a carbamoyl group, an N-substituted carbamoyl group, and an acylamino group. , alkylsulfonylamino group, arylsulfonylamino group, alkyl group, aryl group, alkoxy group,
It may be substituted with an aryloxy group, an aralkyl group, or an acyl group. Substrate C must have the function of releasing a mobile dye by combining with the oxidized form of the reducing agent, and must also have a ballast group to prevent the dye-donating substance itself from diffusing into the dye-receiving image-receiving layer. Must be. The ballast group is preferably a hydrophobic group such as an alkyl group, an alkoxyalkyl group, or an aryloxyalkyl group, and these ballast groups preferably have a total carbon number of 6 or more,
Further, the total number of carbon atoms in the substrate C is preferably 12 or more. 2. A coupler that can form a mobile dye through a coupling reaction with an oxidation product of a reducing agent formed by an oxidation-reduction reaction with silver halide caused by heating (corresponds to a compound that forms a mobile dye through the above reaction) . A patent application for this kind of coupler was made in 1983.
31976 and 57-32547, which have a leaving group which possesses a sufficient diffusion-resistant group to render the couplers diffusion-resistant. In this case, diffusion resistance refers to a state in which the movement of molecules in the hydrophilic binder is suppressed mainly due to the size and shape of the molecules. This diffusion resistance is achieved by incorporating a diffusion resistant ballast group into the leaving group of the coupler. On the other hand, the dye produced by the reaction of the coupler with the oxidized form of the reducing agent is highly mobile because it does not have a ballast group. Such diffusion-resistant couplers combine with an oxidized form of a reducing agent, such as a p-aminophenol derivative or a p-phenylenediamine derivative, produced by a reaction between silver halide and a reducing agent, such as a p-aminophenol derivative or p-phenylenediamine derivative.
It is a substrate that forms a pigment, and has the following general formula ()
It is represented by ~(). In the above formula, R ₁ to R ₄ are each a hydrogen atom,
Alkyl group, alkenyl group, cycloalkyl group, aryl group, aralkyl group, alkoxy group, aryloxy group, acyl group, acyloxy group, acylamino group, alkoxyalkyl group, aryloxyalkyl group, alkoxycarbonyloxy group, alkoxycarbonylamino group , alkoxycarbonyl group, carbamoyl group, substituted carbamoyl group, sulfamoyl group,
Substituted sulfamoyl group, amino group, alkylamino group, dialkylamino group, arylamino group, cycloalkylamino group, halogen atom,
Cyano group, acyloxyalkyl group, nitro group, alkylsulfonyl group, arylsulfonyl group, hydroxyl group, carboxyl group, sulfo group, ureido group, substituted ureido group, sulfamoylamino group, substituted sulfamoylamino group, alkylsulfonyloxy group , an arylsulfonyloxy group, an alkylsulfonylamino group, an arylsulfonylamino group, an alkylthio group, an arylthio group, a heterocyclic residue, an imide group, and a quaternary ammonium group, and these substituents Furthermore, hydroxyl group, carboxyl group, sulfo group, alkoxy group, cyano group,
Nitro group, alkyl group, aryl group, aryloxy group, acyloxy group, acyl group, sulfamoyl group, substituted sulfamoyl group, carbamoyl group, substituted carbamoyl group, acylamino group, alkylsulfonylamino group, arylsulfonylamino group, sulfamoylamino group base,
It may be substituted with a substituted sulfamoylamino group, imide group, halogen atom, or quaternary ammonium group, and the total number of carbon atoms of substituents R ₁ to _{R 4} is
The number of substituents is less than 12, and each substituent has 8 or less carbon atoms. X is a group that leaves when bonding with the oxidized form of the reducing agent, and includes an alkoxy group, an aryloxy group,
Acyloxy group, alkoxycarbonyloxy group, carbamoyloxy group, substituted carbamoyloxy group, alkylsulfonyloxy group, arylsulfonyloxy group, alkylsulfonylamino group, arylsulfonylamino group, perfluoroacylamino group, sulfamoylamino group, substituted Represents a substituent selected from a sulfamoylamino group, an alkylsulfonyl group, an arylsulfonyl group, an alkylthio group, an arylthio group, a heterocyclic thio group, an arylazo group, a heterocyclic residue, and an imide group; Substituents include alkyl groups, alkenyl groups, cycloalkyl groups, aralkyl groups, aryl groups, halogen atoms, alkoxy groups, aryloxy groups, acyl groups, acylamino groups, acyloxy groups, alkylsulfonylamino groups, arylsulfonylamino groups, and alkyl groups. May be substituted with a sulfonyloxy group, arylsulfonyloxy group, alkoxycarbonyl group, substituted ureido group, alkoxycarbonyloxy group and alkoxycarbonylamino group, and the total number of carbon atoms for X is 8
That's all. As mentioned above, the coupler combines with the oxidized form of the reducing agent to form a mobile dye, but the coupler itself is preferably not mobile. For that purpose, in the general formulas () to (),
The substituents R ₁ to _{R 4} are preferably those that do not inhibit diffusion in the hydrophilic binder, and specifically, those that are relatively hydrophilic and have a low molecular weight are desirable, while the substituent X suppresses the diffusion of the coupler itself. That is, it is desirable to have a high hydrophobicity and high molecular weight that acts as a ballast group. 3. Examples of diffusion-resistant compounds that do not inherently release mobile dyes but release mobile dyes upon reduction (if applicable to the above reaction) include the molecules described in U.S. Pat. No. 4,139,379. This includes compounds that undergo endonucleophilic reactions. Diffusion-resistant dye-donating substances that do not originally release hydrophilic dyes but release hydrophilic dyes upon reduction (hereinafter referred to as reducible dye-releasing agents) include, for example, intramolecular nucleophilic substitution. Examples include ballast-stabilized compounds that release mobile dyes upon receiving. The reducible dye-releasing agent is an electron donor (i.e., a reducing agent) that provides the necessary electrons to enable the reducible dye-releasing agent to be reduced to a form that undergoes intramolecular nucleophilic substitution. It is useful in combination with compounds that provide When the electron donor is rendered imagewise dispersed in the photographic element upon exposure, electrons are transferred from the electron donor to the ballast-stabilized electron-accepting nucleophilic substituted compound in accordance with the imagewise pattern. is provided, resulting in subsequent imagewise displacement and dye release. The above-described compounds of reducible dye releasing agents found to be particularly useful in heat-developable color photographic processes and photographic elements can be represented by the schematic formula shown below. (ballast stabilized carrier) x- (electrophilic leaving group) y- (mobile dye component) z, where x, y and z are positive integers, preferably 1 or 2; includes compounds having one or more mobile moieties attached to one ballast group or compounds having one or more ballasts attached to one mobile moiety;
A ballast-stabilized carrier is a group capable of rendering the compound immobile under thermal diffusion transfer conditions; the ballast-stabilized carrier, when accepting at least one electron, is a nucleophilic It contains a group that provides a functional group (a group that can undergo intramolecular nucleophilic substitution with the electrophilic cleavage group). The reducible dye-releasing agent contains an electrophilic leaving group in each linking group linking the ballast-stabilized carrier to its respective mobile component, and the nucleophilic group generated by reduction is As a result of reacting with the electrophilic leaving group, some groups remain with the ballast stabilized carrier and some groups remain with the mobile moiety. The reducible dye-releasing agent includes a nucleophilic precursor group and an electrophilic cleavage group bonded via a linking group. Preferred examples of reducible dye releasing agents include, for example, 1 to about 5 atoms, preferably 3 or 4 atoms, between the reaction center of the nucleophilic reaction and each atom serving as the reaction center of the electrophilic reaction. It can be represented by the following general formula. Single transport type (1) In the formula, w, x, y, z, n and m are positive integers 1
or 2; ENuP is an electron-accepting nucleophilic group precursor, such as a precursor of a hydroxyamino group [nitroso group (NO), stable nitroxyl free radical (N-O.), and preferably a nitro group. (NO ₂ )], or a precursor of a hydroxy group [preferably an oxo group (=O), etc.
Alternatively, it may be an imine group (which is hydrolyzed to an oxo group before accepting an electron in an alkaline environment) and R ¹ is an organic group containing up to 50 atoms, preferably up to 15 atoms. . ;
R ² and R ³ are divalent organic groups containing 1 to 3 atoms in the divalent bonding group, and may be alkylene groups, such as oxaalkylene, thiaalkylene, azaalkylene, alkyl, or aryl. - May be substituted nitrogen. This is a group containing at least 8 carbon atoms that contains a large group in the side chain on the linking group and can act as a ballast, and these groups are used when X ¹ itself is a ballast group is X ¹ ; E and Q provide electrophilic cleavable groups, where
E is the center of the electrophilic reaction; Q is a group that provides a monoatomic bond between E ^and Non-metal atoms of group a or group a, such as oxygen atoms, sulfur atoms and selenium atoms. These atoms provide two covalent bonds linking ^X2 to E, so that along with ^X2 5~
When forming a 7-membered ring and when these atoms are trivalent atoms, hydrogen atoms, 1 to
Alkyl groups (including substituted carbon atoms and carbocyclic groups) containing 20 carbon atoms, preferably 1 to 10 carbon atoms, or aryl groups (also including substituted aryl groups) containing 6 to 20 carbon atoms X ¹ can be mono-substituted by R ¹ ,
a substituent on at least one of R ² or R ³ and one of X ¹ or Q-X ² is of sufficient size to render the compound immobile in the layers of the photographic element. One represents a ballast group and the other is a photographically useful dye or its precursor. ^X1
and Q-X ² also include the linking groups necessary to link the respective moieties to E or R ¹ . ; R ¹ , R ² and R ³ are chosen to provide substantial proximity of E NuP to E to allow intramolecular nucleophilic release of Q from E. these are,
1 between the atom that is the reaction center of the nucleophilic reaction and the atom that is the reaction center of the electrophilic reaction.
or selected to provide 3 to 5 atoms, thereby rendering the compound 3- or 5- to 7-
A membered ring can be formed upon intramolecular nucleophilic substitution of the group Q-X ² from the electrophilic group. 4 A compound that originally releases a mobile dye when heated, but no longer releases a mobile dye due to an oxidation-reduction reaction with silver halide that occurs when heated (a compound used in the reaction) thing). Examples of such dye-donating substances include reduced forms of the nucleophilic group of the compounds described in US Pat. No. 4,139,379, and the general formula thereof is represented by A or B below. (Nu) ¹ and (Nu) ² each represent a nucleophilic group (e.g. -OH
Z represents a divalent atomic group (e.g., a sulfonyl group) that is electronegative with respect _to the carbon atom on which R ⁴ and R ⁵ are substituted;
Q represents a dye part. R ¹ , R ² and R ³ are each a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group or an acylamino group, and when R ¹ and R ² are located adjacent to each other on the ring, the rest of the molecule forms a fused ring. However, the remainder of the molecule of R ² and R ³ forms a fused ring, and each of R ⁴ and R ⁵ may be the same or different,
Represents hydrogen, a hydrocarbon group or a substituted hydrocarbon group,
At least one of R ¹ , R ² , R ³ , R ⁴ and R ⁵ contains a group of sufficient size to prevent migration of the compound in the layer, ie, a diffusion-resistant group. It will be done. Residues that confer diffusion resistance are residues that are capable of inhibiting the migration of compounds bearing them in hydrophilic colloids commonly used in photographic materials. Organic residues which generally bear straight-chain or branched aliphatic groups or which can bear carbocyclic or heterocyclic or aromatic groups, generally having from 8 to 20 carbon atoms, are preferably used for this purpose. Ru. These residues may be attached directly or indirectly to the rest of the molecule, e.g.
NHCO-, _-NHSO2- , -NR- (where R represents hydrogen or an alkyl group, -O-, -S- or -
Binds via SO ₂ −. The diffusion-resistant residues may further carry groups which confer solubility in water, such as sulfo groups or carboxyl groups, which may also be present in anionic form. Mobility is determined entirely by the size of the compound's molecules, so
In some cases, for example when the molecule as a whole is large enough, it is quite possible to have groups of shorter chain length as "diffusion-resistant residues". Other examples of dye-donating substances include those shown in general formula (). However, Nu is a nucleophilic group (e.g. -NH ₂ group, -OH
GH is an oxidizable group (e.g. amino (including alkylamino) group, sulfonamido group). GH is a cyclic group formed with R ¹¹ or R ¹³ or any arbitrary group specified for Nu. E is an electrophilic group and it is carbonyl-
It may be either CO- or thiocarbonyl-CS-; Q is a group providing a monoatomic bond between E and R ¹⁶ , where said monoatom is a group a of the periodic table or a non-metallic atom in the -2 or -3 valence state of group a, such as a nitrogen atom, an oxygen atom, a sulfur atom, a selenium atom, where said atom has two covalent bonds linking E to ^R16; and when Q is a trivalent atom, it is a hydrogen atom, an alkyl group (containing 1 to 10 carbon atoms)
(including substituted alkyl groups), aromatic groups (containing 5 to 20 carbon atoms) (including aryl groups and substituted aryl groups), or atomic groups necessary to form a 5- to 7-membered ring with R ¹⁶ (e.g. pyridine or piperidine group); R ¹⁴ is an alkylene group containing 1 to 3 carbon atoms in the bonding group (including alkylene groups having substituents), or at least one methylene in the bonding group is dialkyl or diarylmethylene is a linking group; n is an integer of 1 or 2; R ¹⁶ can be an aromatic group containing at least 5 atoms, preferably 5 to 20 atoms, including heterocyclic groups such as pyridine, tetrazole, Also included are groups containing a nucleus such as benzimidazole, benzotriazole or isoquinoline, or carbocyclic arylene groups containing from 6 to 20 carbon atoms (preferably phenylene or naphthylene substituted with phenylene or naphthylene groups). (including groups) are also included. Alternatively, ^R16 can be an aliphatic hydrocarbon group such as an alkylene group containing 1 to 12 carbon atoms. This also includes substituted alkylene groups;
R ¹⁵ is an alkyl group containing 1 to 40 carbon atoms (including substituted alkyl groups and cycloalkyl groups), 6 to 40 carbon atoms;
It can be an aryl group (including substituted aryl groups) containing 40 carbon atoms, or it can function as a ballast group. R ¹³ , R ¹¹ and R ¹² may each be a monoatomic substituent such as a hydrogen atom or a halogen atom, but preferably a polyatomic substituent such as an alkyl group containing 1 to 40 carbon atoms (substituted alkyl groups and cyclo alkyl groups), alkoxy groups, aryl groups containing 6 to 40 carbon atoms (including substituted aryl groups), carbonyl groups, sulfamyl groups, and sulfonamido groups. However, when R ¹⁶ is an aliphatic hydrocarbon group such as an alkylene group, R ¹² and R ¹¹ must be polyatomic substituents. and R ¹⁴ is selected to provide substantial proximity of the nucleophilic group to E, allowing intramolecular nucleophilic reaction with release of Q from E, whereby the compound An 8-membered ring, most preferably a 5- to 6-membered ring, can be formed by intramolecular nucleophilic substitution of the group -(Q-R ¹⁶ -x ³ ) from the electrophilic group. In this specification, when the compounds described in 1) to 4) above are collectively described, they are referred to as "dye-donating substances, etc.". The above reaction for forming a dye image in an imagewise manner proceeds particularly well in the presence of an organic silver salt oxidizing agent, resulting in high image density. Therefore, the coexistence of an organic silver salt oxidizing agent is a particularly preferred embodiment. The properties required of the diffusion-resistant "dye-donating substance, etc." used in the present invention include the following. 1. To efficiently form a mobile dye for image formation by a reaction involving a "dye-donating substance, etc." with a high reaction rate. 2. Diffusion-resistant "dye-donating substances, etc." must be immobilized in a hydrophilic or hydrophobic binder, and only the image-formed dye must be mobile. 3. Easy to synthesize. etc. can be mentioned. In the present invention, it is possible to select the dyes that form the image by selecting combinations of various compounds, so that various colors can be reproduced. Therefore, it is possible to create a multicolor image by selecting a combination thereof, so the dye image in the present invention includes not only a monochrome image but also a multicolor image, and a monochrome image also includes a monochrome image obtained by mixing two or more colors. Ru. Examples of dye moieties included in the "dye-donating substance etc." used in the present invention include azo dyes, azomethine dyes, anthraquinone dyes, naphthoquinone dyes, styryl dyes, nitro dyes, quinoline dyes,
Examples include groups such as carbonyl dyes, phthalocyanine dyes, and metal complex salts thereof. Typical dye precursors included in the "dye-donating substances, etc." used in the present invention are those that provide dyes by hydrolysis, such as JP
125818, U.S. Patent No. 3222196 and U.S. Patent No. 3307947
Examples include acylated auxochromes of dyes (temporary short-wave dyes), as described in the above. By temporarily shortening dye absorption during exposure through acylation, it is possible to prevent desensitization due to light absorption when these color image forming agents are mixed with light-sensitive emulsions and coated. can. Note that for this purpose, it is also possible to use a dye that has different hues when transferred onto the mordant and when present in the emulsion layer. The dye moiety can have a group that imparts water solubility, such as a carboxyl group or a sulfonamide group. Next, typical examples of dyes that can be used in the present invention are shown by hue. In the above formula, R ¹¹ to ^{R 16} are each a hydrogen atom, an alkyl group, a cycloalkyl group, an aralkyl group, an alkoxy group, an aryloxy group, an aryl group, an acylamino group, an acyl group, a cyano group, a hydroxyl group, an alkylsulfonylamino group, Arylsulfonylamino group, alkylsulfonyl group, hydroxyalkyl group, cyanoalkyl group, alkoxycarbonylalkyl group, alkoxyalkyl group, aryloxyalkyl group, nitro group, halogen atom,
sulfamoyl group, N-substituted sulfamoyl group,
Represents a substituent selected from a carbamoyl group, an N-substituted carbamoyl group, an acyloxyalkyl group, an amino group, a substituted amino group, an alkylthio group, and an arylthio group, and the alkyl group and aryl group portion of these substituents are Furthermore, halogen atoms,
hydroxyl group, cyano group, acyl group, acylamino group,
It may be substituted with an alkoxy group, a carbamoyl group, a substituted carbamoyl group, a sulfamoyl group, a substituted sulfamoyl group, a carboxyl group, an alkylsulfonylamino group, an arylsulfonylamino group, or a ureido group. The "dye-donating substance, etc." used in the present invention can be introduced into the layer of the photosensitive material by a known method such as the method described in US Pat. No. 2,322,027. In that case, the following high boiling point organic solvents and low boiling point organic solvents can be used. For example, phthalic acid alkyl esters (dibutyl phthalate, dioctyl phthalate, etc.), phosphoric acid esters (diphenyl phosphate, triphenyl phosphate, tricresyl phosphate, dioctyl butyl phosphate), citric acid esters (e.g. acetyl tributyl citrate) , benzoic acid esters (octyl benzoate), alkylamides (e.g. diethyl laurylamide), fatty acid esters (e.g. dibutoxyethyl succinate, dioctyl azelate), trimesic acid esters (e.g. tributyl trimesate), etc. Solvents, or organic solvents with a boiling point of about 30°C to 160°C, such as lower alkyl acetates such as ethyl acetate, butyl acetate, ethyl propionate, secondary butyl alcohol, methyl isobutyl ketone, β-
After dissolving in ethoxyethyl acetate, methyl cellosolve acetate, cyclohexanone, etc., it is dispersed in a hydrophilic colloid. These high boiling point organic solvents and low boiling point organic solvents may be used in combination. Further, the dispersion method using a polymer described in Japanese Patent Publication No. 51-39853 and Japanese Patent Application Laid-Open No. 51-59943 can also be used.
In addition, various surfactants can be used when dispersing "dye-donating substances, etc." in hydrophilic colloids, and these surfactants are listed elsewhere in this specification as surfactants. You can use what you have. The amount of the high boiling point organic solvent used in the present invention is 10 g or less, preferably 5 g or less per 1 g of the dye-providing substance used. Silver halides used in the present invention include silver chloride,
Silver chlorobromide, silver chloroiodide, silver bromide, silver iodobromide, silver chloroiodobromide, silver iodide, etc. In the present invention, when silver halide is used alone without an organic silver salt oxidizing agent, it is preferable to use silver halide containing silver iodide crystals in some of its grains. Such silver halide exhibits a pattern of pure silver iodide as its X-ray diffraction pattern. Silver halide containing two or more types of halogen atoms is used in photographic light-sensitive materials, and in ordinary silver halide emulsions, the silver halide grains form perfect crystals. For example, when measuring X-ray diffraction of a silver iodobromide emulsion, no pattern of silver iodide crystals or silver bromide crystals appears, but an X-ray diffraction pattern appears at positions corresponding to the mixing ratio. In the present invention, particularly preferred silver halides include silver iodide crystals in their grains, and therefore silver chloroiodide, silver iodobromide, and silver chloroiodobromide exhibit an X-ray pattern of silver iodide crystals. be. Such silver halide, for example silver iodobromide, can be obtained by first forming silver bromide grains by adding a silver nitrate solution to a potassium bromide solution, and then adding potassium iodide. It will be done. Two or more types of silver halides having different sizes and/or halogen compositions may be used in combination. The average grain size of the silver halide used in the present invention is from 0.001 μm to 10 μm, preferably from 0.001 μm to 5 μm. The silver halide used in the present invention may be used as it is, but it may also be compounded with chemical sensitizers such as compounds such as sulfur, selenium, tellurium, etc., compounds such as gold, platinum, palladium, rhodium and iridium, and halogenated silver halide. Chemical sensitization may also be achieved through the use of reducing agents such as tin or combinations thereof. For more information, see “The
Theory of the Photographic Process” 4th edition,
TH James, Chapter 5, pages 149-169. In a particularly preferred embodiment of the present invention, an organic silver salt oxidizing agent is used in combination, but the silver halide used in this case is characterized by containing pure silver iodide crystals when silver halide is used alone. All silver halides known in the art can be used. When the organic silver salt oxidizing agent used in the present invention is heated to a temperature of 80°C or higher, preferably 100°C or higher in the presence of photosensitive silver halide, the above-mentioned image-forming substance or, if necessary, the image-forming substance A silver image is formed by reacting with a reducing agent coexisting with the silver. By coexisting with an organic silver salt oxidizing agent, it is possible to obtain a photosensitive material that develops color with higher density. Examples of such organic silver salt oxidizing agents include silver salts of organic compounds having a carboxyl group, and typical examples include silver salts of aliphatic carboxylic acids and silver salts of aromatic carboxylic acids. There is. Examples of aliphatic carboxylic acids include silver behenic acid, silver stearic acid, silver oleic acid, silver lauric acid, silver capric acid, silver myristic acid, and silver palmitic acid. , silver salt of maleic acid, silver salt of fumaric acid, silver salt of tartaric acid, silver salt of furoic acid, silver salt of linoleic acid, silver salt of oleic acid,
Examples include silver salts of adipic acid, silver salts of sebacic acid, silver salts of succinic acid, silver salts of acetic acid, silver salts of butyric acid, and silver salts of camphoric acid. Also, silver salts substituted with halogen atoms or hydroxyl groups are also effective. Silver salts of aromatic carboxylic acids and other carboxyl group-containing compounds include silver salts of benzoic acid, 3,
Silver salt of 5-dihydroxybenzoic acid, silver salt of o-methylbenzoic acid, silver salt of m-methylbenzoic acid, p-
Silver salts of substituted benzoic acids such as silver salts of methylbenzoic acid, silver salts of 2,4-dichlorobenzoic acid, silver salts of acetamidobenzoic acid, silver salts of p-phenylbenzoic acid,
Silver salt of gallic acid, silver salt of tannic acid, silver salt of phthalic acid, silver salt of terephthalic acid, silver salt of salicylic acid,
Silver salts of phenylacetic acid, silver salts of pyromellitic acid, silver salts of 3-carboxymethyl-4-methyl-4-thiazoline-2-thione described in US Pat. No. 3,785,830, and silver salts of 3-carboxymethyl-4-methyl-4-thiazoline-2-thione described in US Pat. There are silver salts of aliphatic carboxylic acids having a thioether group as described. In addition, there are silver salts of compounds having a mercapto group or a thione group and derivatives thereof. For example, 3-mercapto-4-phenyl-1,
Silver salt of 2,4-triazole, Silver salt of 2-mercaptobenzimidazole, 2-mercapto-5-
Silver salts of aminothiadiazole, silver salts of 2-mercaptobenzthiazole, silver salts of 2-(s-ethylglycolamido)benzthiazole, s-alkyl (alkyl group having 12 to 22 carbon atoms) thioglycol acetic acid, etc. Silver salt of thioglycolic acid, silver salt of dithiocarboxylic acid such as silver salt of dithioacetic acid, silver salt of thioamide, 5-
silver salt of carboxy-1-methyl-2-phenyl-4-thiopyridine, silver salt of mercaptotriazine, silver salt of 2-mercaptobenzoxazole,
Silver salt of mercaptooxadiazole, U.S. Patent No.
Silver salts described in 4123274, for example 1,2,4
-Silver salt of 3-amino-5-benzylthio 1,2,4-triazole, which is a mercaptotriazole derivative, the 3-mercaptotriazole derivative described in U.S. Pat.
It is a silver salt of a thione compound such as a silver salt of (2-carboxyethyl)-4-methyl-4-thiazoline-2-thione. In addition, there are silver salts of compounds having imino groups. For example, silver salts of benzotriazole and its derivatives described in Japanese Patent Publication No. 44-30270 and Publication No. 45-18416, silver salts of alkyl-substituted benzotriazoles such as benzotriazole silver salts, methylbenzotriazole silver salts, 5- Silver salts of halogen-substituted benzotriazoles such as silver salts of chlorobenzotriazole, silver salts of carboimidobenzotriazoles such as silver salts of butylcarboimidobenzotriazole, 1, 2, 4 described in U.S. Pat. No. 4,220,709; Examples include silver salts of -triazole and 1-H-tetrazole, silver salts of carbazole, silver salts of saccharin, and silver salts of imidazole and imidazole derivatives. In addition, in the present invention, organic metal salts such as silver salts and copper stearate described in Research Disclosure Vol. 170, No. 17029, June 1978 can also be used as well as the various silver salts mentioned above. It can be used. Two or more types of organic silver salt oxidizing agents can be used in combination. In the present invention, a reducing agent can be used if necessary. Color developers that form images by oxidative coupling are useful as such reducing agents. As reducing agents used in heat-developable color photosensitive materials, p-phenylenediamine color developers represented by N,N-diethyl-3-methyl-p-phenylenediamine are described in U.S. Pat. No. 3,531,286. ing. A further useful reducing agent is aminophenol, which is described in US Pat. No. 3,761,270. Particularly useful aminophenol reducing agents include 4-amino-2,6-dichlorophenol, 4-amino-2-methylphenol sulfate, 4-amino-3-methylphenol sulfate, and 4-amino-2,6-dichlorophenol. Examples include 2,6-dichlorophenol hydrochloride. Furthermore, Research Disclosure No. 151 No. 15108 and U.S. Pat. No. 4,021,240 describe 2,6-dichloro-4-substituted sulfonamidophenol
4-substituted sulfonamidophenols and the like are described and useful. In addition to the above phenolic reducing agents, naphthol reducing agents such as 4-amino-1
-naphthol derivatives and 4-substituted sulfonamide-1-naphthol derivatives are also useful. Furthermore, as a general reducing agent that can be applied, U.S. Pat.
Aminohydroxypyrazole derivatives described in US Pat. No. 2895825, aminopyrazoline derivatives described in US Pat.
-19412, RD-19415) describe hydrazone derivatives. In the above reducing agent, hydrophilic groups (e.g. -SO ₃ ^- , -
COO ⁻ , —OH, —SONH ₂ , —CONH ₂ groups, etc.) are preferably used. These reducing agents may be used alone or in combination of two or more. The reducing agent can be used in a certain concentration range. Generally useful reducing agent concentrations range from about 0.01 moles of reducing agent to about 20 moles of reducing agent per mole of oxidizing agent or coupler.
mol, particularly preferably from 0.1 mol to about 4 mol. These reducing agents may be used alone or in combination of two or more. In the present invention, in addition to the above-mentioned reducing agents, reducing agents described below can also be used as auxiliary developers, if necessary. Useful auxiliary developers include hydroquinone, t-
Alkyl-substituted hydroquinones such as butylhydroquinone and 2,5-dimethylhydroquinone, catechols, pyrogallols, halogen-substituted hydroquinones such as chlorohydroquinone and dichlorohydroquinone, alkoxy-substituted hydroquinones such as methoxyhydroquinone, and polyhydroxy such as methylhydroxynaphthalene. There are benzene derivatives. Furthermore, methyl gallate, ascorbic acid, ascorbic acid derivatives, N,N'-di-(2
Hydroxylamines such as -ethoxyethyl) hydroxylamine, 1-phenyl-3-pyrazolidone, 4-methyl-4-hydroxymethyl-1-
Pyrazolidones such as phenyl-3-pyrazolidone, reductones, hydroxytetronic acids, and the like are useful. Auxiliary developers can be used in a concentration range. A useful concentration range is 0.0005 times molar to 20 times molar relative to silver, particularly useful concentration ranges include:
It is 0.001 times mole to 4 times mole. When an organic silver salt oxidizing agent is used in combination, it is necessary that the silver halide and the organic silver salt oxidizing agent exist at a substantially effective distance in order to promptly initiate the reaction. It is desirable that the silver halide and the organic silver salt oxidizing agent exist in the same layer. Development by heating differs from so-called wet development in that the reaction requires time because the diffusion of reactive molecular species is restricted. However, if too much time is spent on heating for development, the thermal reaction in the unexposed areas cannot be ignored and so-called fog occurs, which is undesirable. In the present invention, a hot solvent can be used as one means for improving such disadvantages. The term "thermal solvent" as used herein refers to a non-hydrolyzable organic material that is solid at ambient temperature but exhibits a mixed melting point with other components at or below the heat treatment temperature used. When heat development is performed in the presence of a hot solvent, the development speed can be increased and the image quality can be improved. As such a thermal solvent used in the present invention, a compound that can serve as a solvent for a developer, a compound that is a substance with a high dielectric constant and is known to accelerate the physical development of a silver salt, and the like are useful. Useful heat solvents include polyglycols described in U.S. Pat. No. 3,347,675, such as polyethylene glycol with an average molecular weight of 1,500 to 20,000, derivatives of polyethylene oxide such as oleate ester, beeswax,
Monostearin, -SO ₂ -, high dielectric constant compounds with -CO- groups, such as acetamide, succinimide, ethyl carbamate, urea, methylsulfonamide, ethylene carbonate, polar substances described in U.S. Pat. No. 3,667,959, 4-hydroxy Butanoic acid lactone, methylsulfinylmethane,
Tetrahydrothiophene-1,1-dioxide, 1,10-decanediol described in Research Disclosure, December 1976, pages 26 to 28, methyl anisate, biphenyl suberate, and the like are preferably used. Although the role of the thermal solvent in the present invention is not necessarily clear, it is understood that its main role is to promote the diffusion of reactive molecular species during development. The photosensitive silver halide, organic silver salt oxidizing agent of the present invention is prepared in the following binder. A dye-providing substance and the like are also dispersed in the binder described below. The binders used in the present invention can be used alone or in combination. A hydrophilic binder can be used for this binder. Hydrophilic binders are typically transparent or translucent hydrophilic colloids, such as proteins such as gelatin, gelatin derivatives, cellulose derivatives, starch, gum arabic, pullulan, etc.
These include natural substances such as polysaccharides such as dextrins, and synthetic polymeric substances such as water-soluble polyvinyl compounds such as polyvinyl alcohol, polyvinylpyrrolidone, and acrylamide polymers. Other synthetic polymeric compounds include dispersed vinyl compounds which, in the form of luxes, particularly increase the dimensional stability of photographic materials. The silver halide used in the present invention may be spectrally sensitized with methine dyes and others. The pigments used include cyanine pigments, merocyanine pigments, composite cyanine pigments, composite merocyanine pigments,
Holopolar cyanine dye, hemicyanine dye,
Included are styryl dyes and hemioxonol dyes. Particularly useful dyes are those belonging to the cyanine dyes, merocyanine dyes and complex merocyanine dyes. Any of the nuclei commonly used for cyanine dyes can be used as the basic heterocyclic nucleus for these dyes. That is, pyrroline nucleus, oxazoline nucleus, thiazoline nucleus, pyrrole nucleus, oxazole nucleus, thiazole nucleus, selenazole nucleus, imidazole nucleus, tetrazole nucleus, pyridine nucleus, etc.; a nucleus in which an alicyclic hydrocarbon ring is fused to these nuclei; and these. A nucleus in which an aromatic hydrocarbon ring is fused to the nucleus of Nucleus, quinoline nucleus, etc. can be applied. These nuclei may be substituted on carbon atoms. The merocyanine dye or composite merocyanine dye includes a pyrazolin-5-one nucleus, a thiohydantoin nucleus, a 2-thioxazolidine-2,4-dione nucleus, a thiazolidine-2,4-dione nucleus, a rhodanine nucleus, as a nucleus having a ketomethylene structure. A 5- to 6-membered heteroartic ring nucleus such as a thiobarbituric acid nucleus can be applied. Useful sensitizing dyes include, for example, German patent no.
929080, U.S. Patent No. 2231658, U.S. Patent No. 2493748
No. 2503776, No. 2519001, No. 2519001, No. 2503776, No. 2519001, No.
No. 2912329, No. 3656959, No. 3672897, No. 3694217, No. 4025349, No. 4046572,
British Patent No. 1242588, Special Publication No. 14030/1973, No. 52
-24844 can be mentioned. These sensitizing dyes may be used alone or in combination, and combinations of sensitizing dyes are often used particularly for the purpose of supersensitization. Representative examples are U.S. Patent No. 2688545 and U.S. Patent No. 2977229.
No. 3397060, No. 3522052, No. 3522052, No. 3397060, No. 3522052, No.
No. 3527641, No. 3617293, No. 3628964, No. 3666480, No. 3672898, No. 3679428,
Same No. 3703377, Same No. 3769301, Same No. 3814609,
No. 3837862, No. 4026707, British Patent No.
No. 1344281, No. 1507803, Special Publication No. 43-4936,
No. 53-12375, JP-A No. 52-110618, No. 52-
Described in No. 109925. Along with the sensitizing dye, the emulsion may contain a dye that itself does not have a spectral sensitizing effect or a substance that does not substantially absorb visible light and exhibits supersensitization. For example, aminostyl compounds substituted with nitrogen-containing heterocyclic groups (e.g., U.S. Pat. No. 2,933,390
No. 3,635,721), aromatic organic acid formaldehyde condensates (e.g., U.S. Pat.
3743510), cadmium salts, azaindene compounds, etc. US Patent No.
The combinations described in No. 3615613, No. 3615641, No. 3617295, and No. 3635721 are particularly useful. In the present invention, a base or a base precursor can be used to promote the dye-forming reaction.
Particularly when the photosensitive material is of a type that releases a hydrophilic dye in an imagewise manner, these bases or base precursors promote the dye release reaction and function as a dye release aid. When these bases or base precursors are contained in a photosensitive material, it is necessary to select a base that does not impair the storage stability of the photosensitive material. Examples of preferable bases that can be used in photosensitive materials include amines, including trialkylamines, hydroxylamines, aliphatic polyamines, N-alkyl substituted aromatic amines, N-
Mention may be made of hydroxyalkyl-substituted aromatic amines and bis[p-(dialkylamino)phenyl]methanes. Also US Patent No. 2410644
No. 3, US Pat. No. 3,506,444 describes useful organic compounds containing amino acids such as urea and 6-aminocaproic acid. The base precursor releases a basic component when heated. Examples of typical base precursors are described in British Patent No. 998949. Preferred base precursors are salts of carboxylic acids and organic bases, useful carboxylic acids include trichloroacetic acid, trifluoroacetic acid, useful bases include anidine, piperidine, morpholine, p-toluidine,
2-picoline, etc. Guanidine trichloroacetic acid, described in US Pat. No. 3,220,846, is particularly useful. Aldonamides described in JP-A-50-22625 are preferably used because they decompose at high temperatures to produce bases. These bases or base precursors can be used in a wide range of ways. A useful range is 50% by weight or less, preferably from 0.01% to 40% by weight of the coated dry film of the photosensitive material. In the heat-developable light-sensitive material of the present invention, it is especially advantageous to use a compound represented by the following general formula because development is accelerated and dye formation is also promoted. [General formula] In the above formula, A ₁ , A ₂ , A ₃ , and A ₄ may be the same or different, and each represents a hydrogen atom, an alkyl group, a substituted alkyl group, a cycloalkyl group, an aralkyl group, an aryl group, a substituted aryl group, and a substituted aryl group. Represents a substituent selected from heterocyclic residues, and also represents A ₁ and
A ₂ or A ₃ and A ₄ may be linked to form a ring. Specific examples include H ₂ NSO ₂ NH ₂ , H ₂ NSO ₂ N
( _{CH3 ) 2 , H2NSO2N} ( _{C2H5 ) 2} , _{H2NSO2NHCH3 ,
H2NSO2N ( C2H4OH ) 2 , CH3NHSO2NHCH3 ,} etc. The above compounds can be used in a wide range of applications. A useful range is 20% by weight or less of the coated dry film of the photosensitive material, more preferably,
It is 0.1-15% by weight. In the present invention, it is advantageous to use water-releasing compounds to accelerate the dye-forming reaction or assist in the migration of imagewise formed hydrophilic dyes. A water-releasing compound is a compound that decomposes and releases water during thermal development. These compounds are particularly known for transfer printing of textiles, and are
NH ₄ Fe(SO ₄ ) 2.12H ₂ O described in _Publication No. 88386 is useful. The support for the photosensitive material used in the present invention is one that can withstand processing temperatures. Common supports include glass, paper, metal and their analogs, as well as cellulose acetate film, cellulose ester film, polyvinyl acetal film, polystyrene film, polycarbonate film, polyethylene terephthalate film and related materials. Includes film or resin materials. US Patent No.
The polyesters described in No. 3634089 and No. 3725070 are preferably used. Particularly preferably, polyethylene terephthalate film is used. The coating solution used in the present invention can be prepared by mixing separately formed silver halide and organometallic salt oxidizing agent before use, but it is also possible to prepare the coating solution by mixing the two separately. Mixing in a ball mill for hours is also effective. Also effective is a method in which a halogen-containing compound is added to the prepared organic silver salt oxidizing agent to form halogen silver with the silver in the organic silver salt oxidizing agent. For information on how to make these silver halides and organic silver salt oxidizing agents, how to mix them, etc., see Research Disclosure No. 17029 and JP-A-1973
No. 32928, No. 51-42529, U.S. Patent No. 3700458,
It is described in JP-A-49-13224, JP-A-50-17216, etc. In the present invention, the coating amount of the photosensitive silver halide and organic silver salt oxidizing agent is suitably 50 mg to 10 g/m ² in total in terms of silver. The photographic emulsion layer or other hydrophilic colloid layer of the light-sensitive material used in the present invention contains coating aids, antistatic properties, smoothness improvement, emulsification dispersion, adhesion prevention, and improvement of photographic properties (e.g., development acceleration, high contrast, sensitization). ) may contain various surfactants for various purposes. For example, saponins (steroids), alkylene oxide derivatives (e.g. polyethylene glycol, polyethylene glycol/polypropylene glycol condensates, polyethylene glycol alkyl ethers or polyethylene glycol alkyl aryl ethers, polyethylene glycol esters, polyethylene glycol sorbitan esters, polyalkylene glycols Nonionic surfactants such as alkylamines or amides, polyethylene oxide adducts of silicone), glycidol derivatives (e.g. alkenylsuccinic acid polyglycerides, alkylphenol polyglycerides), fatty acid esters of polyhydric alcohols, alkyl esters of sugars, etc. agent; alkyl carboxylate,
Alkyl sulfonates, alkylbenzene sulfonates, alkylnaphthalene sulfonates, alkyl sulfates, alkyl phosphates, N-acyl-N-alkyl taurines, sulfosuccinates, sulfoalkyl polyoxyethylene alkyl phenyl Anionic surfactants containing acidic groups such as carboxy groups, sulfo groups, phospho groups, sulfate ester groups, phosphoric ester groups such as ethers, polyoxyethylene alkyl phosphates; amino acids, aminoalkylsulfonic acids Ampholytic surfactants such as , aminoalkyl sulfates or phosphates, alkyl betaines, and amine oxides; heterocyclic quaternary surfactants such as alkylamine salts, aliphatic or aromatic quaternary ammonium salts, pyridinium, imidazolium, etc. Cationic surfactants such as ammonium salts and phosphonium or sulfonium salts containing aliphatic or heterocycles can be used. Among the above-mentioned surfactants, it is preferable to include a polyethylene glycol type nonionic surfactant having an ethylene oxide repeating unit in the molecule in the photosensitive material. Particularly preferred are those having 5 or more repeating units of ethylene oxide. Nonionic surfactants that meet the above conditions are
It is widely used outside the field, and its structure, properties, and synthesis method are well known. Representative known documents include Surfactant Science Series
Volume1.Nonionic Surfactants (Edited by
Martin J. Shick, Marcel Dekker Inc.1967),
Surface Active Ethylene Oxide Adducts
(Schoufeldt.N, Pergamon Press 1969), and the nonionic surfactants described in these documents that satisfy the above conditions are preferably used in the present invention. These nonionic surfactants can be used alone,
It can also be used as a mixture of two or more types. The polyethylene glycol type nonionic surfactant is used in an amount equal to or less than the weight of the hydrophilic binder, preferably 50% or less. The photosensitive material used in the present invention can contain a cationic compound having a pyridinium salt. Examples of cationic compounds with pyridinium groups include PSA Journal, Section B36 (1953),
USP2648604, USP3671247, Special Publication Showa 44-30074,
It is described in Special Publication No. 44-9503, etc. In the light-sensitive material used in the present invention, a compound that activates development and simultaneously stabilizes the image can be used. Among them, isothiuroniums represented by 2-hydroxyethyl isothiuronium and trichloroacetate described in U.S. Pat. No. 3,301,678, and 1,8-(3,
Bisisothiuroniums such as 6-dioxaoctane)bis(isothiuronium trifluoroacetate), thiol compounds described in West German Patent No. 2162714, and 2-amino-2-thiazolium trichloro described in U.S. Patent No. 4012260. acetate, thiazolium compounds such as 2-amino-5-bromoethyl-2-thiazolium trichloroacetate, bis(2
-amino-2-thiazolium)methylenebis(sulfonylacetate), 2-amino-2-thiazolium phenylsulfonylacetate, etc. Compounds having α-sulfonylacetate as an acidic moiety; , compounds having 2-carboxycarboxamide as the acidic moiety, etc. are preferably used. In the case of the present invention, since the "dye-donating substance, etc." is colored, it is not so necessary to further contain an anti-irradiation substance, an anti-halation substance, or various dyes in the light-sensitive material.
In order to improve the sharpness of images,
Public Relations No. 3692, U.S. Patent No. 3253921, U.S. Patent No. 2527583
It is possible to contain filter dyes, absorbent substances, etc., which are described in various specifications such as No. 2,956,879. Furthermore, it is preferable that these dyes are thermally decolorizable, such as those described in US Pat. No. 3,769,019;
Dyes such as those described in Japanese Patent No. 3745009 and Japanese Patent No. 3615432 are preferred. The photosensitive material used in the present invention may optionally contain various additives known as heat-developable photosensitive materials and layers below the photosensitive layer, such as an antistatic layer, a conductive layer, a protective layer, an intermediate layer, an AH It can contain layers, release layers and the like. Various additives include those described in Research Disclosure Magazine Vol. 170, No. 17029, June 1978, such as plasticizers, sharpness improving dyes, AH dyes, sensitizing dyes, Additives include matting agents, surfactants, fluorescent whitening agents, and anti-fading agents. In the present invention, as well as the heat-developable photosensitive layer, coating solutions for the protective layer, intermediate layer, undercoat layer, back layer, and other layers are prepared for each layer using the dipping method, the air knife method, the curtain coating method, or the U.S. Patent No.
Hopper coating method described in specification No. 3681294, etc.
A photosensitive material can be produced by sequentially coating a support material using various coating methods and drying it. Furthermore, if desired, two or more layers can be applied simultaneously by the methods described in US Pat. No. 2,761,791 and British Patent No. 837,095. In the present invention, the latent image obtained after exposure to a light-sensitive material is exposed to light over the entire element for about 0.5 seconds to about 300 seconds at a moderately elevated temperature, e.g. It can be developed by heating. As long as the temperature is within the above range, it can be used at either high or low temperatures by increasing or shortening the heating time. Especially about 110℃~approx.
A temperature range of 160°C is useful. As the heating means, ordinary means such as a simple hot plate, an iron, a hot roller, a heating element using carbon, titanium white, etc., or a similar method can be used. In the image forming method of the present invention in which an image formed by a mobile hydrophilic dye is transferred to a dye fixing layer under high temperature conditions in the presence of a hydrophilic thermal solvent, the transfer of the mobile dye is initiated simultaneously with the release of the dye. It may also be done after the release of the dye has been completed. Therefore, heating for transfer may be performed after or simultaneously with heat development. Simultaneously with thermal development means that the heating for development also acts as the heating for the transfer of the released dye at the same time. Since the optimal temperature for development, the optimal temperature for dye migration, and the heating time required for each do not necessarily match, the temperatures can be set independently. In the present invention, "under a high temperature condition in which a hydrophilic thermal solvent is present" means under a condition in which an atmospheric temperature is 60° C. or higher in the presence of a hydrophilic thermal solvent. Heating for dye migration improves the storage stability of photosensitive materials,
From the viewpoint of workability, etc., the temperature is between 60℃ and 250℃, so
In the present invention, it is possible to appropriately select a solvent that can function as a hydrophilic thermal solvent within this temperature range. It goes without saying that hydrophilic thermal solvents must be able to quickly assist the movement of dyes upon heating, but if we also consider the heat resistance of photosensitive materials, the requirements for hydrophilic thermal solvents are The melting point is 40
The temperature is preferably 40°C to 200°C, more preferably 40°C to 150°C. In the present invention, a "hydrophilic thermal solvent" is a compound that is in a solid state at room temperature but becomes a liquid state when heated, and has an (inorganic/organic) value>1, and
It is defined as a compound with one or more solubility in water at room temperature. Inorganicity and organicity are concepts for predicting the properties of compounds, and the details thereof are described in, for example, Chemistry Region 11, p. 719 (1957). Since the hydrophilic thermal solvent has the role of assisting the movement of the hydrophilic dye, it is considered preferable that it is a compound that can act as a solvent for the hydrophilic dye. It is generally known from experience that preferred solvents for dissolving organic compounds have an (inorganic/organic) value close to the (inorganic/organic) value of the organic compound. On the other hand, the ((inorganic/organic)
The value is approximately 1, and the (inorganic/organic) value of the hydrophilic dye formed by these "dye-donating substances, etc." /organic) has a value greater than the
It preferably has a value of 1.5 or more, particularly preferably 2 or more. Since it is preferable that the hydrophilic thermal solvent used in the present invention moves only the hydrophilic dye and does not move the "dye-donating substance, etc.", its (inorganic/organic) value is etc"
(inorganic/organic) value. That is, as a hydrophilic thermal solvent, (inorganic/
It is an essential condition that the (organic) value is 1 or more, preferably 2 or more. On the other hand, from the viewpoint of molecular size, it is considered preferable that molecules that can move by themselves without inhibiting the movement exist around the moving dye. Therefore, the molecular weight of the hydrophilic heat solvent is preferably small, about 200 or less, and more preferably about 100 or less. The hydrophilic hot solvent of the present invention only needs to be able to substantially assist the movement of the hydrophilic dye generated by heat development to the dye fixing layer, so it can not only be included in the dye fixing layer, but also A part of the hydrophilic thermal solvent necessary for dye transfer may be contained in the light-sensitive material, or an independent layer containing the hydrophilic thermal solvent may be provided in an independent dye-fixing material having a dye-fixing layer. I can do it. From the viewpoint of increasing the transfer efficiency of the dye to the dye fixing layer, it is preferable that the hydrophilic thermal solvent is contained in the dye fixing layer and/or the layer adjacent thereto. The hydrophilic thermal solvent is usually dissolved in water and dispersed in the binder, but it can also be used dissolved in alcohols such as methanol, ethanol, etc. The hydrophilic heat solvent used in the present invention is 5 to 500% by weight, preferably 20 to 200% by weight, particularly preferably 20 to 200% by weight of the total coating amount of the photosensitive material and/or dye fixing material
It can be used in a coating amount of 30 to 150% by weight. Examples of the hydrophilic heat solvent used in the present invention include ureas, pyridines, amides, sulfonamides, imides, alcohols, oximes, and other heterocycles. Next, specific examples of the hydrophilic heat solvent used in the present invention will be shown. (34) CH ₃ SO ₂ NH ₂ , (35) HOCH ₂ SO ₂ NH ₂ (36) H ₂ NSO ₂ NH ₂ , (37) 3HCNHSO ₂ NH ₂ (47) HOCH ₂ (CHOH) ₃ CH ₂ OH, (48) CH ₃ C (CH ₂ OH) ₃ , (49) C ₂ H ₅ C (CH ₂ OH) ₃ (50) O ₂ NC (CH ₂ OH) ) ₃ , (51) Sorbitsuto (54) HOCH ₂ −CH=CH−CH ₂ OH (55) CH ₃ CH=NOH, (56) HON=CHCH=NOH (58) HOCH ₂ CH=NOH Among these, ureas (1), (2), (3), (10), pyridines (17), (19), amides (26),
(30), (33), sulfonamides (34), (36),
Imides (40), (41), (43), (44) and alcohols (46) and (54) are particularly preferred. Further, the hydrophilic heat solvent used in the present invention can be used alone or in combination of two or more. In the present invention, a hydrophilic mobile dye generated in an imagewise manner is moved by heat development simultaneously with imagewise exposure or subsequent to imagewise exposure, and a dye image is fixed by receiving this mobile dye. layers are required. For this purpose, in general, a photosensitive layer () containing at least silver halide, a "dye-donating substance, etc." and a binder, and optionally an organic silver salt oxidizing agent on a support, and a hydrophilic layer () formed by A dye-fixing layer (2) is required that can accept mobile dyes. The above-mentioned photosensitive layer () and dye fixing layer () are:
Although they can be formed on the same support, as in the case of the present invention, a photosensitive material in which the photosensitive layer ( ) is coated on the support and a fixing material in which the fixing layer ( ) is coated on the support are used. They can also be formed separately. In this case, after the light-sensitive material is imagewise exposed and uniformly heated, the fixing material is placed on top of the fixing material and the mobile dye can be transferred to the fixing layer. There is also a method in which only the photosensitive material (2) is imagewise exposed, and then a dye fixing layer (2) is superimposed and uniformly heated. A conventional method such as using a pressure roller can be used to bring the photosensitive material and the dye-fixing material into close contact with each other, but in order to achieve sufficient contact, heating can also be used during the time of the close contact. After image exposure or after heat development at the same time as image exposure, the surface of the photosensitive material and the dye-receiving surface of the dye-fixing material are brought into close contact in order to transfer the formed mobile hydrophilic dye to the dye-fixing layer. In the case of heating, it is sufficient that the heating contributes only to dye migration, and from this point of view, the heating temperature and heating time can be set independently of the heating for development. When this method is adopted, it is preferable that the heating for development completes the reaction for development within a short period of time so as not to contribute to dye migration as much as possible, while at the same time allowing the dye to be released in an imagewise manner. In order to obtain a clear image, it is preferable to keep the heating for transferring the dye to the dye transfer layer as low as possible within an appropriate transfer time range so as not to cause a thermal reaction in the unexposed area. The dye fixing layer () may have a white reflective layer. For example, a layer of titanium dioxide dispersed in gelatin can be provided on a mordant layer on a transparent support. The titanium dioxide layer forms a white opaque layer, and by viewing the transferred color image from the transparent support side, a reflective color image can be obtained. A dye transfer aid can be used if necessary for dye transfer from the photosensitive layer to the dye fixing layer. As the dye transfer aid, water or a basic aqueous solution containing caustic soda, caustic potash, or an inorganic alkali metal salt is used. Also used are low boiling point solvents such as methanol, N,N-dimethylformamide, acetone and diisobutyl ketone, or mixed solutions of these low boiling point solvents and water or basic aqueous solutions.
The dye transfer aid may be used by moistening the image-receiving layer with a solvent, or may be incorporated into the material in the form of crystal water or microcapsules. The dye fixing layer contains a dye mordant for fixing the dye,
It may contain a hydrophilic heat solvent to assist in the movement of the dye, a base and/or a base precursor to promote the dye-forming reaction, and a binder to bind them together. In the case of the present invention in which the dye fixing layer is provided on a support separate from the light-sensitive material, it is a particularly preferred embodiment that the dye fixing layer contains a base and/or a base precursor. When the dye mordant is a polymer mordant,
Since this also functions as a binder, the amount of binder may be reduced or no binder may be used in such cases. Conversely, if the binder also functions as a mordant,
Similarly, dye mordants can also be omitted.
As the binder, the same kind of binder as used in photosensitive materials can be used. The mordant used in the dye fixing layer of the present invention can be arbitrarily selected from commonly used mordants, and among them, polymer mordants are particularly preferred. Here, polymer mordants refer to secondary and tertiary mordants.
Polymers containing a class amino group, polymers having a nitrogen-containing heterocyclic moiety, and polymers containing these quaternary cation groups, with a molecular weight of 5,000 to 200,000, especially
10,000 to 50,000. For example, U.S. Pat.
Vinylpyridine polymers and vinylpyridinium cationic polymers disclosed in US Pat. No. 2548564, US Pat. No. 2484430, US Pat. No. 3148061, US Pat.
No. 4128538, British Patent No. 1277453, etc. Polymer mordant crosslinkable with gelatin etc.; US Patent No. 3958995, British Patent No. 2721852
No. 2798063, Japanese Unexamined Patent Application Publication No. 115228/1983, No. 54
-145529, 54-126027, etc.; water-insoluble mordant disclosed in US Pat. No. 3,898,088; US Pat. No.) Reactive mordant capable of forming a covalent bond with the dye disclosed in the specification, etc.; furthermore, U.S. Pat.
No. 3788855, No. 3642482, No. 3488706, No. 3557066, No. 3271147, No. 3271148,
JP-A No. 50-71332, No. 53-30328, No. 52-
155528, No. 53-125, and No. 53-1024;
Also included are the mordants described in No. 2675316 and No. 2882156. Among these mordants, for example, those that crosslink with the matrix such as gelatin, water-insoluble mordants, and aqueous sol (or latex dispersion) type mordants can be preferably used. Particularly preferred polymer mordants are shown below. (1) Groups that have a quaternary ammonium group and can be covalently bonded to gelatin (e.g., aldehyde group, chloroalkanoyl group, chloroalkyl group, vinylsulfonyl group, pyridiniumpropionyl group, vinylcarbonyl group, alkylsulfonoxy group, etc.) Polymers with e.g. (2) A reaction product of a copolymer consisting of a repeating unit of a monomer represented by the following general formula and a repeating unit of another ethylenically unsaturated monomer, and a crosslinking agent (for example, bisalkanesulfonate, bisarenesulfonate).

[Formula] R ^b ₁ : H, alkyl group R ^b ₂ : H, alkyl group, aryl group Q: divalent group R ^b ₃ , R ^b ₄ , R ^b ₅ : alkyl group, aryl group, or R ^b ₃ ~ At least two of R ^b ₅ may be combined to form a heterocycle. X: Anion (The above alkyl groups and aryl groups include substituted ones.) (3) Polymer represented by the following general formula x: about 0.25 to about 5 mol% y: about 0 to about 90 mol% z: about 10 to about 99 mol% A: monomer having at least two ethylenically unsaturated bonds B: copolymerizable ethylenically unsaturated Monomer Q: N, P R ^b ₁ , R ^b ₂ , R ^b ₃ : Alkyl group, cyclic hydrocarbon group, or at least two of R ^b ₁ to ^{R b} ₃ may be combined to form a ring . (These groups and rings may be substituted.) (4) Copolymer consisting of (a), (b) and (c)

【formula】 or

[Liquid A]

(a) 2 g of urea (b) 2 g of N-methylurea (c) 10 ml of water (d) 10% of polyvinyl alcohol (saponification degree 98%)
Weight% aqueous solution 12g (e) Compound with the following structure 100mg (f) 0.5ml of a 5% aqueous solution of sodium dodecylbenzenesulfonate (0.3g of the compound (43) of the present invention represented by the following structural formula was added to the solution [A]). [Liquid B]) was prepared, and a dye fixing material (B sheet) was obtained in the same manner as above. Using photosensitive material E-1 with a tungsten light bulb,
After imagewise exposure at 2000 lux for 10 seconds, the film was uniformly heated for 40 seconds on a heat block heated to 140°C. Next, the dye-fixing material A sheet or B sheet and the heat-developed photosensitive material were brought into close contact with each other so that the film surfaces faced each other, and heated for 30 minutes on a heat block at 120°C.
heated for seconds. When the dye-fixing material was peeled off from the light-sensitive material, a negative magenta color image was obtained on the dye-fixing material.
The density of these negative images was measured using a Macbeth reflection densitometer (RD).
-519). The results are shown in Table-1.

[Table] The above results demonstrate that by using the dye-fixing material of the present invention, images having low minimum density and high maximum density can be obtained. Example 2 Preparation of photosensitive material E-2 Preparation of an emulsion of coupler (M-1) having the following structural formula To 100 g of a 10% gelatin aqueous solution dissolved at 40°C,
Add 0.5 g of sodium dodecylbenzenesulfonate and stir to dissolve. Diffusion-resistant coupler of the present invention (M-1) 10g, tricresyl phosphate 10
g and 20 ml of ethyl acetate and heat to dissolve. A gelatin solution containing a surfactant and a solution containing a coupler were emulsified and dispersed using a homogenizer at 12,000 RPM for 3 minutes to prepare a coupler emulsion. Photosensitive material E-2 was produced as follows. (a) Silver iodobromide emulsion (described in Example 1) 5.5 g (b) 10% aqueous gelatin solution 2 g (c) Dispersion of coupler (M-1) 2.5 g (d) 10% ethanol solution of guanidine trichloroacetic acid 0.5ml (e) 10% of 2.6 dichloro-4-aminophenol
Methanol aqueous solution 0.5ml (f) 5% aqueous solution of the compound with the following structure 1ml (g) Water (a) to (g) are mixed, heated and dissolved, and placed on a 130 μm thick polyethylene terephthalate film to a thickness of 85 μm.
It was applied to a wet film thickness of . Furthermore, 1.5 g/m ² of gelatin was coated as a protective layer on this film to prepare a photosensitive material E-2. After exposing the photosensitive material E-2 described above imagewise for 10 seconds at 2000 lux using a tungsten bulb,
The mixture was heated uniformly for 30 seconds on a heat block heated to 130°C. Next, this photosensitive material was closely attached to the same dye fixing material sheet A or B as in Example 1 so that the film surfaces faced each other, and heated for 30 seconds in a heat block heated to 120°C. When the dye-fixing material was peeled off from the light-sensitive material, a negative magenta color image was obtained on the dye-fixing material. The density of these negative images was measured using a Macbeth reflection densitometer (RD-519). Table 2 shows the results.
It was shown to.

[Table] The above results demonstrate that by using the dye-fixing material of the present invention, images having low minimum density and high maximum density can be obtained. Example 3 Preparation of photosensitive material E-3 Preparation of a dispersion of dye-donating substance 5 g of a reduced form of dye-donating substance A-(9) having the following structural formula, 2-ethyl-hexyl succinate sodium sulfonate 0.5 g and 15 g of tricresyl phosphate (TCP) were weighed out, 30 ml of ethyl acetate was added thereto, and the mixture was heated and dissolved at about 60°C. 100g of this homogeneous solution and a 10% solution of lime-processed gelatin
After stirring and mixing, use a homogenizer for 10 minutes.
Dispersed at 10000RPM. This dispersion is referred to as a dye-donating substance dispersion DP-1. Next, a method for producing a photosensitive coating will be described. (a) Photosensitive silver iodobromide emulsion (described in Example 1) 25 g (b) Dye-providing substance dispersion DP-1 33 g (c) 10% ethanol solution of guanidine trichloroacetic acid 15 ml (d) The following 10ml of 2.5% aqueous solution of compound (e) N,N-dimethylsulfonamide 10% aqueous solution
After mixing and dissolving 4 ml or more of (a) to (e), it was applied onto a polyethylene terephthalate film to a wet film thickness of 30 μm and dried. Furthermore, the following composition was applied as a protective layer on this film. (f) 35 g of 10% gelatin aqueous solution (g) 6 ml of guanidine trichloroacetic acid 10% ethanol solution (h) 4 ml of 1% aqueous solution of sodium sulfonate (i) Apply a mixture of 55 ml of water to a wet film thickness of 25 μm. After that, it was dried to produce a photosensitive material E-3. After exposing the photosensitive material E-3 described above imagewise for 10 seconds at 2000 lux using a tungsten bulb,
The mixture was heated uniformly for 30 seconds on a heat block heated to 130°C. Next, this photosensitive material and the dye fixing material sheet A or B prepared in Example 1 were brought into close contact with each other so that the film surfaces faced each other, and heated uniformly for 30 seconds on a heat block heated to 120°C. . When the dye-fixing material was peeled off from the light-sensitive material, a positive magenta color image was obtained on the dye-fixing material. The density of these positive images was measured using a Macbeth reflection densitometer (RD-
519). The results are shown in Table 3.

[Table] The above results demonstrate that images with low minimum density and high maximum density can be obtained by using the dye fixing material of the present invention. Example 4 Preparation of photosensitive material E-4 5 g of the dye-donating substance A-(9), 4 g of the electron-donating substance ED-(22) having the following structural formula, and sodium succinate-2-ethyl-hexyl ester sulfonate Add 20ml of cyclohexanone to 0.5g, 10g of tricresyl phosphate (TCP),
The mixture was heated and dissolved at approximately 60°C. This solution and gelatin
After stirring and mixing with 100 g of 10% solution, disperse with a homogenizer for 10 minutes at 10,000 RPM. This dispersion is referred to as a dye-donating substance dispersion DP-1. electron donating substance Next, a method for producing a photosensitive coating will be described. (a) Photosensitive silver iodobromide emulsion (described in Example-1)
25g (b) Dispersion of dye-donating substance DP-1 33g (c) 10% ethanol solution of guanidine tricloacetic acid 15ml (d) 2.5% aqueous solution of the following compound 10ml (e) N,N-dimethylsulfonamide 10% aqueous solution
Add 2 ml of water to 4 ml or more of (a) to (e), mix, heat and dissolve, and then apply on polyethylene terephthalate film to a wet film thickness of 60 μm.
Dry. Furthermore, the following composition was applied as a protective layer thereon. (a) 35 g of 10% gelatin aqueous solution (b) 6 ml of guanidine trichloroacetic acid 10% ethanol solution (c) 4 ml of 1% aqueous solution of sodium succinate-2-ethyl-hexyl ester sulfonate (d) 25 μm of a mixture of 55 ml of water The photosensitive material E-4 was prepared by coating the film to a wet film thickness of 1,000 yen, and then drying it. The photosensitive material E-4 described above was imagewise exposed for 10 seconds at 2000 lux using a tungsten bulb. Next, this photosensitive material and the same dye fixing material sheet A or B prepared in Example 1 were brought into close contact with each other so that the film surfaces faced each other, and heated for 30 seconds on a heat block heated to 120°C. When the dye-fixing material was peeled off from the light-sensitive material, a positive magenta color image was obtained on the dye-fixing material. The density of this positive image was measured using a Macbeth reflection densitometer ((RD-519)).
Measured using The results are shown in Table 4.

[Table] The above results demonstrate that images with low minimum density and high maximum density can be obtained by using the dye fixing material of the present invention.

Claims (1)

[Claims] 1 By heating a heat-developable photosensitive material that can react with photosensitive silver halide to form a hydrophilic dye by heating in a substantially water-free state after or simultaneously with imagewise exposure. A dye fixing material for fixing a movable hydrophilic dye formed in an imagewise manner onto a dye fixing layer by heating, the dye fixing material comprising: a support;
and a single layer or a plurality of layers formed on a support and containing at least a dye fixing agent and a compound capable of reacting with or adsorbing a silver halide and/or an organic silver salt oxidizing agent. Dye-fixing material.