JPH0587820B2 - - Google Patents

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a color photographic material, and more particularly to a color photographic material containing a dye-donating substance. Prior Art and its Problems Many methods are known for forming color images by transferring diffusible dyes. For example, US Pat. No. 3,134,764 describes a method using a dye developer in which a hydroquinone developer and a dye are linked. Furthermore, a method of releasing a diffusible dye by an intramolecular transesterification reaction is disclosed in JP-A-51-63618, and a method of releasing a diffusible dye by an intra-molecular rewinding reaction of the isoxazolone ring is disclosed in JP-A-49-111628. Are listed. In all of these methods, the dye diffuses into the image-receiving layer in areas where development has not occurred (unexposed areas), and no dye release or diffusion occurs in areas where development has occurred (exposed areas). However, these methods have the disadvantage that it is very difficult to obtain images with a high S/N ratio because development and dye release or diffusion occur in parallel. In addition, in order to improve this drawback, the coloring material is made into an oxidized form that does not have the ability to release the dye, and is allowed to coexist with the reducing agent precursor. A method for emitting is described in JP-A-53-110827. However, with this method, the S/N cannot be improved unless the development speed and the reduction speed of the coloring material by the reducing agent are strictly controlled.
This method has the disadvantage that images with high ratios cannot be obtained. On the other hand, as a method for releasing a diffusible dye in the area where development has occurred, a method in which the diffusible dye is released by the reaction between a coupler having a diffusible dye as a leaving group and an oxidized product of a color developer has been disclosed in a British patent.
No. 1330524, and U.S. Patent No. 3227550 discloses a method in which a diffusible dye is produced by the reaction between a coupler having a diffusion-resistant group as a leaving group and an oxidized color developer.
listed in the number. However, in systems using these color developers, image contamination due to oxidative decomposition products of the developer becomes an extremely serious problem. Also, the following (1) to (12) are known as dye-donating substances with reducing properties.

[ka] U.S. Patent No. 3928312, U.S. Patent No. 3993638

[ka] U.S. Patent No. 4053312

[ka] U.S. Patent No. 4055428

[ka] Japanese Patent Publication No. 51-104343

【formula】 Japanese Patent Publication No. 53-3819

[ka] Japanese Patent Publication No. 51-104343

【formula】 Japanese Patent Publication No. 51-104343

【formula】 Japanese Patent Publication No. 51-104343

【formula】 Research Disclosure Magazine 1978, No. 17465

[ka] US Patent No. 3725062

【formula】 U.S. Patent No. 3728113

[Formula] U.S. Patent No. 3443939 Among these, (1) to (9) are all oxidized by development treatment, and then a diffusible dye having a sulfamoyl group at the end is released by the action of an alkali. It is. However, when trying to obtain sufficient density using these dye-donating substances, there are problems such as increased fogging density. In addition, the compounds (10) to (12) have poor efficiency in the dye release process after being oxidized, and cannot be put to practical use. OBJECT OF THE INVENTION An object of the present invention is to provide a color photographic material that provides a high dye transfer density as a coloring material for diffusion transfer and contains a dye-donating substance that has excellent dye release efficiency, diffusivity, and stability over time. There is a particular thing. DISCLOSURE OF THE INVENTION These objects are achieved by the invention described below. That is, the present invention provides a color characterized by containing on a support at least a photosensitive silver halide, a binder, and a dye-donating substance represented by the following general formula () that releases a diffusible dye upon oxidation during development. It is a photographic material. General formula ()

[Formula] {In the above general formula (), R ₁ and R ₂ are
Hydrogen atom, halogen atom, cyano group, alkyl group, aryl group, heterocyclic group, alkoxy group, aryloxy group, acyloxy group, alkylsulfonyloxy group, arylsulfonyloxy group, acylamino group, anilino group, ureido group, respectively. represents an alkylsulfonylamino group, an arylsulfonylamino group, an alkylthio group, an arylthio group, an alkoxycarbonylamino group, an aryloxycarbonylamino group, a carbamoyl group, an acyl group, an alkylsulfonyl group, or an arylsulfonyl group, and among R ₁ and R ₂ At least one of the carbon atoms is 10 or more. Dye represents a dye group or a dye precursor group. } Specific Configuration of the Invention The specific configuration of the present invention will be described in detail below. The color photographic material of the present invention contains on a support at least a photosensitive silver halide, a binder, and a dye-providing substance represented by the following general formula () that releases a diffusible dye upon oxidation during development. In the present invention, "being oxidized and releasing a diffusible dye during development" refers to the fact that the compound of general formula () itself undergoes an oxidation-reduction reaction with exposed silver halide to release a diffusible dye; This refers to the release of diffusible dyes during development due to coupling reactions or oxidation-reduction reactions caused by the reducing agent used in combination. General formula ()

[Formula] In the above general formula (), R ₁ and R ₂ are
Each hydrogen atom, halogen atom, cyano group, or substituted or unsubstituted alkyl group, aryl group, heterocyclic group, alkoxy group, aryloxy group, acyloxy group, alkylsulfonyloxy group, arylsulfonyloxy group, acylamino group, represents an anilino group, ureido group, alkylsulfonylamino group, arylsulfonylamino group, alkylthio group, arylthio group, alkoxycarbonylamino group, aryloxycarbonylamino group, carbamoyl group, acyl group, alkylsulfonyl group or arylsulfonylamino group,
At least one of R ₁ and R ₂ has 10 or more carbon atoms. Note that among the above groups, the groups other than the cyano group include substituted groups. Preferred examples of R ₁ and R ₂ include alkyl groups, aryl groups, alkoxy groups, aryloxy groups, acylamino groups, alkyl or arylsulfonylamino groups, anilino groups, substituted ureido groups, alkoxycarbonylamino groups, etc. Among these, the most preferred are alkyl groups (e.g. methyl group, ethyl group, dodecyl group, 3-
(2,4-di-t-amylphenoxy)propyl group, etc.), aryl group (e.g. phenyl group, p-tolyl group, p-methoxyphenyl group, 2,4-di-
t-amyl phenyl group, p-tetradecanoylaminophenyl group, etc.), alkoxy groups (e.g. methoxy group, ethoxy group, isopropoxy group, t-butoxy group, dodecyloxyethoxy group, hexadecyloxy group, etc.), aryloxy groups (e.g. phenoxy group, 4-t-butylphenoxy group, 4-
t-octylphenoxy group, 2,4-di-t-butylphenoxy group), acylamino group (e.g. acetylamino group, benzoylamino group, octanoylamino group, α-(2,4-di-t-amylphenoxy group) ) butyroylamino group, γ-(3-t
-butyl-4-hydroxyphenoxy)butyroylamino group, etc.), anilino group (e.g., anilino group, 2-chloroanilino group, 2-methoxyanilino group, 2-chloro-5-tetradecanoylaminoanilino group) , N-acetylanilino group, 2-chloro-5-{α-(3-t-butyl-4-hydroxyphenoxy)lauroylamino}anilino group, etc.),
Substituted ureido groups (e.g., phenylureido groups,
N,N-dibutylureido group, octadecylureido group, etc.), alkoxycarbonylamino group (eg, ethoxycarbonylamino group, octadecylcarbonylamino group, etc.), and the like. Dye represents a dye group or a dye precursor group. Examples of dyes include azo dyes, azomethine dyes,
Examples include anthraquinone dyes, naphthoquinone dyes, styryl dyes, nitro dyes, quinoline dyes, carbonyl dyes, phthalocyanine dyes, and metal complex salts thereof. In addition, typical dye precursor groups include those that produce dyes through hydrolysis.
For example, JP 48-125818, U.S. Patent No. 3222196
Examples include dyes whose wavelengths are temporarily shortened by acylating the auxochrome of dyes described in No. 3307947 and the like. Temporarily shortened wavelengths are particularly preferred in high-sensitivity light-sensitive materials because desensitization of silver halide emulsions due to light absorption by dyes is reduced. It is particularly preferable that the dye part has a dissociable hydrophilic group such as a carboxyl group, a sulfonamide group, a phenolic hydroxyl group, or an imide group for the purpose of accelerating diffusion into the dye fixing layer. On the other hand, it is essential that the reducing site represented by the pyrazolotriazole bone core has a ballast group to prevent the dye-donating substance itself from diffusing into the dye-fixing layer. As the ballast group, a hydrophobic group having 10 or more carbon atoms, more preferably 15 or more carbon atoms is suitable, and specific examples include an alkyl group, an aralkyl group, an aryl group, an alkenyl group, an alkoxy group, an aryloxy group, etc. I can do it. Preferred specific examples of the ballast group are listed in preferred specific examples of R ₁ and R ₂ . Preferred specific examples of the dye-providing substance of the present invention are shown below.

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embedded image The dye-donating substance of the present invention can be obtained by condensing a pyrazolotriazole having an amino group introduced into the active position and a sulfonic acid chloride of a dye (or a dye precursor) in the presence of a base. Amino-substituted pyrazolotriazoles are produced by nitrosation using a pyrazolotriazole coupler () useful in conventional photography as a starting material.
It can be easily obtained through a short reduction process. The pyrazolotriazole coupler as a starting material can be synthesized according to the method described in the specifications of JP-A-59-171956 and JP-A-59-27745. Next, a method for synthesizing the dye-donating substance of the present invention will be specifically listed and explained. Synthesis Example Synthesis of Dye Donor Substance (2) The synthesis route of Dye Donor Substance (2) is shown below.

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[Chemical formula] (1) Synthesis of intermediate (B) 6-methyl-2-(3-(4-(2)
-(2,4-di-t-amylphenoxy)octanamido)phenyl)propyl)-1H-pyrazolo[1,5-b][1,2,4]triazole (A)
31.0g was dissolved by heating. To this, 7.77 g of isoamyl nitrite was added at room temperature, and stirring was continued for 3 hours. After adding 300 ml of ethyl acetate, this reaction mixture was reduced to 1.5
After washing with water three times, it was dried over anhydrous magnesium sulfate. The oil obtained by distilling off the solvent under reduced pressure was fractionated using silica gel column chromatography (elution solvent: hexane: ethyl acetate = 3:1), and the eluate was concentrated to dryness to obtain an intermediate. Body (B) (7-nitroso-6-methyl-2-(3
-(4-(2-(2,4-di-t-amylphenoxy)octanamido)phenyl)propyl)-1H
-pyrazolo[1,5-b][1,2,4]triazole) 28.6 g (87%) were obtained. (2) Synthesis of intermediate (C) 6.8 g of the above intermediate (B) was dissolved in 560 ml of ethanol, and heated to reflux under a nitrogen atmosphere. A mixture of 67 g of stannous chloride and 140 ml of concentrated hydrochloric acid was added to this, and the mixture was further heated under reflux for 15 minutes. After the reaction solution was allowed to cool, it was poured into ice water and extracted with ethyl acetate. Wash the extract with water,
After drying over anhydrous magnesium sulfate, the solvent was distilled off under reduced pressure to obtain 7.2 g of intermediate (C). (3) Synthesis of dye-donating substance (2) 5.5 g of the above intermediate (C) was added to a mixture of 40 ml of dimethylacetamide and 10 ml of pyridine, and then the magenta dye sulfonyl chloride (D) was added under ice cooling.
4.4g was added in small portions. After stirring at 10-15°C for 1 hour, the reaction solution was poured into cold water containing a small amount of hydrochloric acid and extracted with ethyl acetate.
The extract was washed with water and dried (ethyl acetate was distilled off under reduced pressure, and the residue was purified by silica gel chromatography (eluent: hexane/ethyl acetate: 1/1) to obtain the dye-donating substance (2). 5.1g of orange-brown crystals
I got it. Other dye-donating substances (d) having a melting point of 163-167°C were synthesized in a similar manner. The compounds described above are just examples, and the invention is not limited thereto. In the present invention, the dye-providing substance can be contained in the same layer as the light-sensitive silver halide emulsion or in a layer adjacent thereto. The amount to be contained is usually per mole of silver halide.
The amount is from 0.01 mol to 4 mol, particularly preferably from 0.05 mol to 2 mol. The dye-providing compound of the present invention is disclosed in U.S. Pat.
It can be introduced into the layer of the photosensitive material by a known method such as the method described in No. 2322027. In this case, Japanese Patent Application Publication Nos. 59-83154, 59-178451,
No. 59-178452, No. 59-178453, No. 59-178454
If necessary, use a high boiling point organic solvent as described in No. 59-178455, No. 59-178457, etc.
It can be used in combination with a low boiling point organic solvent having a temperature of 160°C to 160°C. The amount of the high-boiling organic solvent is 10 g or less, preferably 5 g or less, per 1 g of the dye-providing substance used. 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 the case of a compound that is substantially insoluble in water, it can be dispersed and contained in the form of fine particles in the binder in addition to the method described above. Various surfactants can be used when dispersing in hydrophilic colloids. For example, JP-A-59-
The surfactants listed on pages (37) to (38) of No. 157636 can be used. These methods can also be applied to hydrophobic additives such as image formation accelerators, which will be described later. The color photographic light-sensitive material of the present invention is particularly advantageously used in a color image forming method in which a diffusible dye is released into an image, diffused, and then fixed. The above-mentioned color image forming methods include those in which development is performed using a developer at a temperature near room temperature [color diffusion transfer method] (for example, the method described in Belgian Patent No. 757959), and heat development in a substantially moisture-free state. [thermal development method] (e.g. European Patent No. 76492A2)
and Japanese Patent Application Publication No. 58-79247, No. 59-218443,
There are various forms such as those described in No. 60-79709, etc., and the color photographic material of the present invention can be used in any of them. In the present invention, a mordant is usually used in the dye fixing layer for fixing the diffusible dye, and it is particularly preferable to use a polymer mordant. Polymeric mordants are used alone or in combination with binders in mordant layers in photographic materials. A hydrophilic binder can be used for this binder. Hydrophilic binders are typically transparent or translucent hydrophilic colloids, such as proteins such as gelatin and gelatin derivatives, natural substances such as cellulose derivatives, starch, polysaccharides such as gum arabic, polyvinyl alcohol,
Includes synthetic polymers such as polyvinylpyrrolidone and polyacrylamide. Among these, gelatin and polyvinyl alcohol are particularly preferred. This mordant layer may be present in a light-sensitive material or in a dye fixing material for color diffusion transfer or heat development photography. The mixing ratio of the polymer mordant and the binder and the coating amount of the polymer mordant can be easily determined by those skilled in the art depending on the amount of dye to be mordant, the type and composition of the polymer mordant, and the image forming method to be applied. Yes, but the mordant/binder ratio is
20/80 to 80/20 (weight ratio), the amount of mordant applied is approx.
0.2 to about 15g/ ^m2 is suitable, especially 0.5 to 8
Preference is given to using g/m ² . The mordant layer containing a polymer mordant can contain various surfactants to improve coating properties. A gelatin hardener can be used in combination with the solid polymer mordant in the mordant layer. Examples of gelatin hardeners that can be used in the present invention include aldehydes (formaldehyde, glyoxal, glutaraldehyde, etc.), N-methylol compounds (dimethylol urea,
methyloldimethylhydantoin, etc.), dioxane derivatives (2,3-dihydroxydioxane, etc.), active vinyl compounds [1,3,5-triacryloyl-hexahydro-s-triazine, bis(vinylsulfonyl)methyl ether, N,N'-
Ethylene-bis(vinylsulfonylacetamide),
N,N'-trimethylene-bis(vinylsulfonylacetamide)], active halogen compounds (2,
4-dichloro-6-hydroxy-s-triazine, etc.), mucohalogen acids (mucochloric acid, mucophenoxychloroic acid, etc.), epoxy compounds,
Isoxazoles, dialdehyde starch, 1-
Examples include chloro-6-hydroxytriazinylated gelatin. Specific examples include US Patent No. 1870354, US Patent No. 2080019, and US Patent No. 2726162.
No. 2870013, No. 2983611, No. 2983611, No. 2870013, No. 2983611, No.
No. 2992109, No. 3047394, No. 3057723, No. 3103437, No. 3321313, No. 3325287,
Same No. 3362827, Same No. 3490911, Same No. 3539644,
British Patent No. 3543292, British Patent No. 676628, British Patent No.
No. 825544, No. 1270578, German Patent No. 872153
No. 1090427, No. 2749260, Special Publication No. 1973-
It is described in No. 7133, No. 46-1872, etc. Among these gelatin hardeners, aldehydes, active vinyl compounds, active halogen compounds,
Epoxy compounds described in Japanese Patent Application No. 60-231093 are preferred. These hardeners may be added directly to the mordant layer coating solution, but they may also be added to other coating solutions and diffused into the mordant layer during multilayer coating. The amount of gelatin hardener used in the present invention is:
It can be selected arbitrarily depending on the purpose. Normally,
From about 0.1 to about 50 wt% of the gelatin used is suitable, preferably from 1 to 30 wt%. Polymeric mordants can be used in combination with metal ions in the dye-fixing material (element) to increase dye transfer density. This metal ion can be added to a mordant layer containing a mordant, or a layer adjacent thereto (either near or far from the support carrying the mordant layer etc.). The metal ions used here are preferably colorless and stable against heat and light. That is, Cu ²⁺ ,
Polyvalent ions of transition metals such as Zn ²⁺ , Ni ²⁺ , Pt ²⁺ , Pb ²⁺ , Co ³⁺ ions are preferable, and especially Zn ²⁺
is preferred. This metal ion is usually added in the form of a water-soluble compound, such as ZnSO ₄ or Zn(CH ₃ CO ₂ ) ₂ , and the amount added is suitably about 0.01 to about 5 g/m ² , preferably 0.1 ~1.5g/ ^m2 . A hydrophilic polymer can be used as a binder in the layer to which these metal ions are added. As the hydrophilic binder, transparent or translucent hydrophilic colloids such as those specifically listed above with respect to the mordant layer are useful. Since the compound of the present invention itself has reducing properties, it is not necessarily necessary to use a separate reducing agent, but it is desirable to use a reducing agent in combination for the purpose of increasing reactivity and improving image discrimination. Examples of reducing agents used in this invention include inorganic reducing agents such as sodium sulfite and sodium hydrogen sulfite, benzenesulfinic acids, hydroxyamines, hydrazines, hydrazides, borane-amine complexes, hydroquinones, and amylphenols. , catechols, p-phenylenediamines,
3-pyrazolidinones, hydroxytetronic acid,
In addition to ascorbic acid, 4-amino-5-pyrazolones, etc., TH James, “The theory
of the photographic process”4th.Ed., 291～
Reducing agents described on page 334 can also be used. Further, reducing agent precursors described in JP-A-56-138736, US Pat. No. 4,330,617, etc. can also be used. Examples of more preferable reducing agents include the following. 3-pyrazolidones and their precursors [e.g. 1-phenyl-3-pyrazolidone, 1-
Phenyl-4,4-dimethyl-3-pyrazolidone, 4-hydroxymethyl-4-methyl-1-phenyl-3-pyrazolidone, 1-m-tolyl-3
-pyrazolidone, 1-p-tolyl-3-pyrazolidone, 1-phenyl-4-methyl-3-pyrazolidone, 1-phenyl-5-methyl-3-pyrazolidone, 1-phenyl-4,4-bis-(hydroxymethyl )-3-pyrazolidone, 1,4-di-methyl-3-pyrazolidone, 4-methyl-3-pyrazolidone, 4,4-dimethyl-3-pyrazolidone, 1-(3-chlorophenyl)-4-methyl-3
-pyrazolidone, 1-(4-chlorophenyl)-4
-Methyl-3-pyrazolidone, 1-(4-tolyl)
-4-Methyl-3-pyrazolidone, 1-(2-tolyl)-4-methyl-3-pyrazolidone, 1-(4
tolyl)-3-pyrazolidone, 1-(3-tolyl)
-pyrazolidone, 1-(3-tolyl)-4,4-dimethyl-3-pyrazolidone, 1-(2-trifluoroethyl)-4,4-dimethyl-3-pyrazolidone, 5-methyl-3-pyrazolidone, 1 ,5-
Diphenyl-3-pyrazolidone, 1-phenyl-
4-Methyl-4-stearoyloxymethyl-3
-pyrazilidone, 1-phenyl-4-methyl-4
-lauroyloxymethyl-3-pyrazolidone,
1-phenyl-4,4-bis-(lauroyloxymethyl)-3-pyrazolidone, 1-phenyl-
2-acetyl-3-pyrazilidone, 1-phenyl-3-acetoxypyrazolidone]; Hydroquinones and their precursors [e.g. hydroquinone, toluhydroquinone, 2,
6-dimethylhydroquinone, t-butylhydroquinone, 2,5-di-t-butylhydroquinone, t-octylhydroquinone, 2,5-di-
t-octylhydroquinone, pentadecylhydroquinone, 5-pentadecylhydroquinone
Sodium 2-sulfonate, p-benzoyloxyphenol, 2-methyl-4-benzoyloxyphenol, 2-t-butyl-4-(4-chlorobenzoyloxy)phenol]; Sulfonamidophenol or naphthols [e.g.

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Paraphenylenediamines [e.g. N,N-diethylparaphenylenediamine, N,N-diethyl-3-methyl-p-phenylenediamine,

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[For example, 4-amino-2, etc.]; Aminophenols [e.g. 4-amino-2,
6-dichlorophenol, 4-amino-2,6-
Dibromophenol, 4-amino-2-methylphenol sulfate, 4-amino-3-methylphenol sulfate, 4-amino-2,6-
dichlorophenol hydrochloride, etc.]. Combinations of various reducing agents can also be used in the present invention, such as those disclosed in US Pat. No. 3,039,869. In the present invention, the amount of the reducing agent added is 0.01 to 20 mol, particularly preferably 0.1 to 10 mol, per mol of silver. The silver halide that can be used in the color photographic light-sensitive material of the present invention may be silver chloride, silver bromide, silver chlorobromide, silver chloroiodide, or silver chloroiodobromide. Specifically, U.S. Pat.
Any of the silver halide emulsions described in No. 225176, No. 60-228267, etc. can be used. The silver halide emulsion used in the present invention may be of the surface latent image type in which latent images are mainly formed on the grain surfaces, or may be of the internal latent image type in which the latent images are formed inside the grains. It may also be a so-called core-shell emulsion in which the inside of the grain and the surface layer of the grain have different phases. Further, in the present invention, a direct reversal emulsion in which an internal latent image type emulsion and a nucleating agent are combined can also be used. Although the silver halide emulsion may be used unripe, it is usually used after being chemically sensitized. For emulsions for conventional light-sensitive materials, known sulfur sensitization methods, reduction sensitization methods, noble metal sensitization methods, etc. can be used alone or in combination. These chemical sensitizations can also be carried out in the presence of a nitrogen-containing heterocyclic compound (Japanese Patent Application Laid-open No. 1986-1999).
126526, 58-215644). The coating amount of the photosensitive silver halide used in the present invention is in the range of 1 mg to 10 g/m ² in terms of silver. The silver halide used in the present invention may be spectrally sensitized with methine dyes or others. The dyes used include cyanine dyes, merocyanine dyes, complex cyanine dyes, complex merocyanine dyes, holopolar cyanine dyes, hemicyanine dyes, styryl dyes and hemioxonol dyes. Specifically, JP-A-59-180550, JP-A No. 60-
No. 140335, Research Disclosure Magazine 1978
Sensitizing dyes described in June issue, pages 12-13 (RD17029), Japanese Patent Application Laid-Open No. 111239/1982, and Patent Application No. 172967/1983
Examples include thermally decolorizable sensitizing dyes described in No. These sensitizing dyes may be used alone or in combination, and combinations of sensitizing dyes are often used particularly for the purpose of supersensitization. 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, U.S. Pat. No. 2,933,390). No., same No.
3635721, 3743510, 3615613, 3615641, 3617295, 3635721). These sensitizing dyes may be added to the emulsion during or before chemical ripening, or before or after nucleation of silver halide grains according to US Pat. No. 4,183,756 and US Pat. No. 4,225,666. The amount added is generally 10 ^-8 per mole of silver halide.
to about 10 ^-2 mol. The color photographic light-sensitive material of the present invention, that is, the light-sensitive element, may be provided on a support separate from the image-receiving (dye-fixing) element, or may be a film unit combined with the image-receiving element. A typical form of a film unit is one in which the image receiving element and the photosensitive element described above are laminated on one transparent support, and there is no need to separate the photosensitive element from the image receiving element after the transferred image is completed. It is. More specifically, the image-receiving element comprises at least one mordant layer, and in preferred embodiments of the light-sensitive element, a combination of a blue-sensitive emulsion layer, a green-sensitive emulsion layer and a red-sensitive emulsion layer, or a green-sensitive emulsion layer. , a combination of a red-sensitive emulsion layer and an infrared-sensitive emulsion layer,
Alternatively, a combination of a blue-sensitive emulsion layer, a red-sensitive emulsion layer, and an infrared-sensitive emulsion layer, and a yellow dye-providing substance, a magenta dye-providing substance, and a cyan dye-providing substance are combined in each of the above emulsion layers, respectively. (Here, "infrared light-sensitive emulsion layer refers to an emulsion layer that is sensitive to light of 700 nm or more, especially 740 nm or more.") This mordant layer and photosensitive layer or dye-donating substance Between the containing layers,
A white reflective layer containing a solid pigment such as titanium oxide is provided so that the transferred image can be viewed through the transparent support. A light-shielding layer may be further provided between the white reflective layer and the photosensitive layer so that the development process can be completed in a bright place. Further, if desired, a release layer may be provided at an appropriate position so that all or part of the photosensitive element can be peeled off from the image receiving element. 674082). In another form that does not require peeling, the photosensitive element described above is coated on one transparent support, a white reflective layer is coated on it, and an image-receiving layer is further laminated thereon. An embodiment in which an image receiving element, a white reflective layer, a release layer, and a photosensitive element are laminated on the same support and the photosensitive element is intentionally peeled off from the image receiving element is described in US Pat. No. 3,730,718. On the other hand, there are two typical forms in which a photosensitive element and an image-receiving element are separately coated on two supports, one of which is a peelable type and the other a peelable type. To explain these in detail, a preferred embodiment of the peelable film unit has a light reflecting layer on the back surface of the support and at least one image receiving layer coated on the surface thereof. In addition, the photosensitive element is coated on a support having a light-shielding layer, and the surface coated with the photosensitive layer and the surface coated with the mordant layer do not face each other before the end of exposure, but after the end of exposure (for example, during development) the surface coated with the photosensitive layer is The coating surface is designed so that it turns over and overlaps the image-receiving layer coating surface.
Immediately after the transfer image is completed with the mordant layer, the photosensitive element is peeled off from the image receiving element. In a preferred embodiment of the peel-free film unit, at least one mordant layer is coated on a transparent support, a photosensitive element is coated on a support having a transparent or light-shielding layer, and The layer-applied surface and the mordant layer-applied surface are faced and overlapped. All of the above-mentioned forms can be applied to both the color diffusion transfer method and the heat development method, but in the former case in particular, a pressure-rupturable container (processing element) containing an alkaline processing liquid is also combined. It's okay. In particular, in a peel-free film unit in which an image-receiving element and a photosensitive element are laminated on one support, the processing element is preferably disposed between the photosensitive element and a cover sheet superimposed thereon. Further, in a case where a photosensitive element and an image receiving element are separately coated on two supports, it is preferable that the processing element is placed between the photosensitive element and the image receiving element at the latest during development processing. Depending on the form of the film unit, a light shielding agent (carbon, etc.) may be applied to the processing element.
It is preferable that the material contains black or a dye whose color changes depending on pH) and/or a white pigment (such as titanium oxide). Further, in color diffusion transfer film units, a neutralization timing mechanism comprising a combination of a neutralization layer and a neutralization timing layer is preferably incorporated into the cover sheet, the image receiving element, or the photosensitive element. On the other hand, in a heat-developable film unit, a heat-generating layer containing fine metal particles, conductive particles such as carbon black or graphite is provided at appropriate positions on the support, photosensitive element, or image-receiving element. For diffusion transfer of the dye, Joule heat generated when electricity is applied may be used. A semiconductive inorganic material (for example, silicon carbide, molybdenum silicide, lanthanum chloride, barium titanate ceramics, tin oxide, zinc oxide, etc.) may be used instead of the conductive particles. The case where the present invention is applied to a heat-developable photosensitive material will be described below. When the present invention is applied to a heat-developable photosensitive material, an organic metal salt can be used together with silver halide as an oxidizing agent. In this case, the photosensitive silver halide and the organic metal salt need to be in contact or at a close distance. Among such organic metal salts, organic silver salts are particularly preferably used. Examples of organic compounds that can be used to form the above-mentioned organic silver salt oxidizing agent include Japanese Patent Application No. 59-228551 No. 37
There are compounds described on pages 39, 52 and 53 of US Pat. No. 4,500,626. Also, patent application 1986-113235
Silver salts of carboxylic acids having an alkynyl group such as silver phenylpropiolate described in No.
Acetylene silver described in No. 90089 is also useful. Two or more types of organic silver salts may be used in combination. The above organic silver salts can be used together in an amount of 0.01 to 10 mol, preferably 0.01 to 1 mol, per mol of photosensitive silver halide. The total coating amount of photosensitive silver halide and organic silver salt is suitably 50 mg to 10 g/m ² in terms of silver. In the present invention, a compound that activates development and simultaneously stabilizes images can be used in the photosensitive element. Specific compounds preferably used are described in columns 51-52 of US Pat. No. 4,500,626. Various antifoggants or photographic stabilizers can be used in the present invention. Examples include azoles and azaindenes described in Research Disclosure Magazine, December 1978 issue, pages 24-25, nitrogen-containing carboxylic acids and phosphoric acids described in JP-A-59-168442, or special 1977-
Mercapto compounds and metal salts thereof described in No. 111636, acetylene compounds described in Japanese Patent Application No. 60-228267, and the like can be used. In the present invention, the photosensitive element may contain an image toning agent if necessary. Specific examples of effective toning agents include compounds described in Japanese Patent Application No. 59-268926, pages 92-93. In order to obtain a wide range of colors in the chromaticity diagram using the three primary colors yellow, magenta, and cyan, it is necessary to use a light-sensitive element having at least three silver halide emulsion layers each sensitive to a different spectral region. good. For example, there are three layers: a blue-sensitive layer, a green-sensitive layer, and a red-sensitive layer.
There are combinations of layers, combinations of green-sensitive layers, red-sensitive layers, and infrared-sensitive layers. Each of these photosensitive layers may be divided into two or more layers, if necessary. The photosensitive element used in the present invention may contain various additives known for heat-developable photosensitive elements and layers other than the photosensitive layer, such as a protective layer, an intermediate layer, an antistatic layer, an antihalation layer, and a dye fixing layer, as necessary. It can have a release layer, matte layer, etc. to facilitate peeling off from the element. Various additives are listed in Research Disclosure Magazine, June 1978 issue, p.9.
Plasticizers, matting agents, dyes for sharpness improvement, antihalation dyes, surfactants, optical brighteners, anti-slip agents, antioxidants, and fading as described in Japanese Patent Application No. 59-209563, page 15, etc. There are additives such as inhibitors. In particular, the protective layer usually contains an organic or inorganic matting agent to prevent adhesion. Further, this protective layer may contain a mordant and an ultraviolet absorber. Each of the protective layer and the intermediate layer may be composed of two or more layers. Further, the intermediate layer may contain a reducing agent to prevent color fading and color mixing, an ultraviolet absorber, and a white pigment such as titanium dioxide. A white pigment may be added not only to the intermediate layer but also to the emulsion layer for the purpose of improving sensitivity. The image receiving element (hereinafter referred to as dye fixing element) may be provided with auxiliary layers such as a protective layer, a peeling layer, and an anti-curl layer, if necessary. In particular, it is useful to provide a protective layer. One or more layers of the upper turtle layer include a hydrophilic heat solvent, a plasticizer, an anti-fading agent,
UV absorber, slip agent, matte agent, antioxidant,
Dispersed vinyl compounds, surfactants, optical brighteners, etc. may be included to increase dimensional stability. In addition, especially in a system in which thermal development and dye transfer are performed simultaneously in the presence of a small amount of water, it is preferable for the dye fixing element to contain a base and/or a base precursor, which will be described later, in order to improve the storage stability of the photosensitive element. . Specific examples of these additives are described on pages 101 to 120 of Japanese Patent Application No. 59-209563. In the present invention, an image formation accelerator can be used in the photosensitive element and/or the dye fixing element. Image formation accelerators include accelerating redox reactions between silver salt oxidizing agents and reducing agents, accelerating reactions such as generation of dyes from dye-donating substances, decomposition of dyes, and release of diffusible dyes, and photosensitive material layers. It has functions such as promoting the movement of the dye from the dye fixing layer to the dye fixing layer, and from a physicochemical function, it has the following functions: bases or base precursors, nucleophilic compounds, high-boiling organic solvents (oils),
It is classified into thermal solvents, surfactants, and compounds that interact with silver or silver ions. However, these substance groups generally have multiple functions and usually have some of the above-mentioned promoting effects. For details of these, please refer to Japanese Patent Application No. 59-213978, 67~
It is described on page 71. There are various other methods of generating bases.
Any of the compounds used in the method are useful as base precursors. For example, in the 1980s,
A poorly soluble metal compound described in No. 169585 and a compound capable of complex-forming reaction with the metal ion constituting this poorly soluble metal compound (referred to as a complex-forming compound)
A method of generating a base by mixing
There is a method of generating a base by electrolysis, as described in No. 74702. The former method is particularly effective. Slightly soluble metal compounds include zinc, aluminum, calcium,
Examples include carbonates such as barium, hydroxides, and oxides. Regarding complex-forming compounds, for example, see ``Critical Stability Constances'', co-authored by AEM Martell and RM Smith.
Stability Constants, Volumes 4 and 5, Plenum Press. Specifically, aminocarboxylic acids, imidinoacetic acids, pyridylcarboxylic acids, aminophosphoric acids,
Carboxylic acids (mono, di, tri, and tetracarboxylic acids and compounds with substituents such as phosfluoro, hydroxy, oxo, ester, amide, alkoxy, mercapto, alkylthio, and phosphino), hydroxamic acids, polyacrylates, polyphosphoric acids, etc. and salts with alkali metals, guanidines, amidines or quaternary ammonium salts. It is advantageous to add the poorly soluble metal compound and the complex-forming compound to the light-sensitive element and the dye-fixing element separately. Various development stoppers can be used in the photosensitive element and/or dye fixing element of the present invention in order to always obtain a constant image despite fluctuations in processing temperature and processing time during development. The development stopper referred to here is a compound that neutralizes the base immediately after proper development or reacts with the base to lower the base concentration in the film and stop development, or a compound that inhibits development by interacting with silver and silver salts. It is a compound that Specific examples include acid precursors that release acids when heated, electrophilic compounds that undergo a substitution reaction with coexisting bases when heated, nitrogen-containing heterocyclic compounds, mercapto compounds, and their precursors (for example, No. 58-216928, No. 59-
Compounds described in No. 48305, No. 59-85834, or No. 59-85836, etc. ) Also useful are compounds that release mercapto compounds when heated;
No. 59-268926, No. 59-246468, No. 60-26038
No. 60-22602, No. 60-26039, No. 60-
There are compounds described in No. 24665, No. 60-29892, and No. 59-176350. A hydrophilic binder can be used for the photosensitive element and/or dye fixing element of the present invention. Typical hydrophilic binders are transparent or translucent hydrophilic binders, such as gelatin, proteins such as gelatin derivatives, cellulose derivatives, and natural substances such as starch, polysaccharides such as gum arabic, polyvinylpyrrolidone, Includes synthetic polymeric materials such as water-soluble polyvinyl compounds such as acrylamide polymers. Dispersed vinyl compounds, which are used in latex form and increase the dimensional stability of the photographic material, can also be used. These binders can be used alone or in combination. In the present invention, the binder is applied in an amount of 20 g or less per m ² , preferably 10 g or less, more preferably 7 g or less. The ratio of the high boiling point organic solvent dispersed in the binder together with a hydrophobic compound such as a dye-donating substance and the binder is 1 c.c. of solvent or less, preferably 0.5 cc or less, more preferably 0.3 cc or less of solvent per 1 g of binder.
cc or less is appropriate. The constituent layers (photographic emulsion layer, dye fixing layer, etc.) of the light-sensitive element and/or dye fixing element of the present invention may contain an inorganic or organic hardening agent. Specific examples of hardeners can be found in Japanese Patent Application No. 59-268926.
Examples include those described on pages 94 to 95 and on page (38) of JP-A-59-157636, and these can be used alone or in combination. Further, in order to promote dye transfer, a hydrophilic thermal solvent that is solid at room temperature and soluble at high temperature may be incorporated into the photosensitive element or dye fixing element. The hydrophilic thermal solvent may be incorporated into either the photosensitive element or the dye fixing element, or may be incorporated into both. Further, the layer to be incorporated may be an emulsion layer, an intermediate layer, a protective layer, or a dye fixing layer, but it is preferably incorporated in the dye fixing layer and/or a layer adjacent thereto. Examples of hydrophilic heat solvents include ureas, pyridines, amides, sulfonamides, imides,
There are alnyls, oximes, and other heterocycles. Further, in order to promote dye transfer, a high boiling point organic solvent may be contained in the photosensitive element and/or the dye fixing element. The support used in the light-sensitive element and/or dye-fixing element of the present invention is one that can withstand processing temperatures. Common supports include glass, paper, polymer films, metals and their analogues;
The supports described on pages 95 to 96 of the specification can be used. The photosensitive element and/or the dye fixing element may be in the form of an electrically conductive heating layer as a heating means for thermal development or diffusion transfer of the dye. The transparent or opaque heating element in this case can be made using conventionally known techniques for producing resistive heating elements. As a resistance heating element, there are two methods: a method using a thin film of an inorganic material exhibiting semiconductivity, and a method using a thin film of an organic material in which conductive fine particles are dispersed in a binder. Materials that can be used in these methods include those described in Japanese Patent Application No. 151,815/1983. In the present invention, the method described in columns 55 to 56 of U.S. Pat. No. 4,500,626 can be applied to the coating method of the heat-developable photosensitive layer, protective layer, intermediate layer, undercoat layer, back layer, dye fixing layer, and other layers. . Radiation, including visible light, can be used as a light source for imagewise exposure to record an image on the photosensitive element. In general, light sources used for ordinary color printing, such as tungsten lamps, mercury lamps, halogen lamps such as iodine lamps, xenon lamps, laser light sources, CRT light sources, light emitting diodes (LEDs), etc. The light sources described in US Pat. No. 4,500,626, column 56, can be used. In the present invention, the steps of thermal development and dye transfer may be performed independently or simultaneously. Further, it may be continuous in the sense that development is followed by transfer in one step. For example, (1) a method in which a photosensitive element is imagewise exposed and heated, and then a dye-fixing element is superimposed and, if necessary, the mobile dye is transferred to the dye-fixing element with heating;
There is a method in which a photosensitive element is imagewise exposed, and a dye-fixing element is superimposed and heated. The methods (1) and (2) above can be carried out in the absence of substantially water;
It can also be carried out in the presence of trace amounts of water. The heating temperature in the heat development process is approximately 50℃ to approximately 250℃
It can be developed at a temperature of about 80°C to about 180°C. When heating in the presence of a trace amount of water, the upper limit of the heating temperature is below the boiling point. When the transfer process is performed after the heat development process, the heating temperature in the transfer process can be in the range from the temperature in the heat development process to room temperature, but in particular, the heating temperature in the transfer process is 50°C or higher, which is about 10°C lower than the temperature in the heat development process. More preferably up to temperature. A preferred image forming method in the present invention involves heating in the presence of a trace amount of water and a base and/or a base precursor after or simultaneously with image exposure, and at the same time as development, diffusion is generated in a portion corresponding to or inversely corresponding to a silver image. The coloring matter is transferred to the dye fixing layer. According to this method, the release reaction of the diffusible dye proceeds extremely quickly, and the movement of the diffusible dye to the dye fixing layer also proceeds rapidly, so that a high-density color image can be obtained in a short time. The amount of water used in this embodiment is at least 0.1 of the weight of the total coating of the light-sensitive element and the dye-fixing element.
times, preferably 0.1 times or more, but not more than the weight of the solvent corresponding to the maximum swelling volume of the entire coating (particularly less than the weight of the solvent corresponding to the maximum swelling volume of the entire coating minus the weight of the entire coating) A small amount is enough. The state of the film during swelling is unstable, and depending on the conditions, local bleeding may occur.To avoid this, the volume of maximum swelling of the total coating film thickness of the photosensitive element and dye fixing element must be adjusted. The amount of water is preferably equal to or less than the amount of water. Specifically, 1 g to 50 g, especially 2 g per square meter of the total area of the photosensitive element and dye fixing element.
A range of 35g to 35g, more preferably 3g to 25g. The base and/or base precursor used in this embodiment can be incorporated into both the photosensitive element and the dye fixing element. It can also be supplied dissolved in water. In the above embodiment, the image forming reaction system contains, as a base precursor, a basic metal compound that is sparingly soluble in water and a compound that can undergo a complex formation reaction with metal ions constituting the sparingly soluble metal compound using water as a medium; It is preferable to raise the pH of the system by reaction of these two compounds upon heating. Here, the image reaction system means a region where an image forming reaction occurs. Specifically, layers belonging to both the photosensitive element and the dye fixing element can be mentioned. If two or more layers are present, any of the layers may be used. It is necessary to add the poorly soluble metal compound and the complex-forming compound to at least separate layers in order to prevent them from reacting before the development process. For example, in a so-called monosheet material in which a photosensitive element and a dye-fixing element are provided on the same support, it is preferable that the above-mentioned two additive layers are separate layers, with one or more layers interposed between them. A more preferred embodiment is one in which the poorly soluble metal compound and the complex-forming compound are contained in layers provided on separate supports. for example,
It is preferable that the poorly soluble metal compound is contained in the photosensitive element and the complex-forming compound is contained in the dye fixing element having a support separate from the photosensitive element. The complex-forming compound may be supplied after being dissolved in water to be coexisting. Slightly soluble metal compounds are disclosed in JP-A-56-174830 and JP-A No. 53-102733.
It is desirable to contain it in the form of a fine particle dispersion prepared by the method described in No. 1, etc., and the average particle size thereof is preferably 50 microns or less, particularly 5 microns or less. The poorly soluble metal compound may be added to any layer of the photosensitive element, such as the photosensitive layer, intermediate layer, or protective layer.
It may be added by dividing into more than one layer. When a poorly soluble metal compound or a complex-forming compound is contained in the layer on the support, the amount added depends on the type of compound,
Although it depends on the particle size of the poorly soluble metal compound, the rate of complex formation reaction, etc., each coated film is converted into weight.
Suitably, it is used in an amount of 50 weight percent or less, and more preferably a range of 0.01 weight percent to 40 weight percent. In addition, when supplying the complex-forming compound dissolved in water, 0.005 mol to 5 mol per liter, especially 0.05 mol to 5 mol per liter.
A concentration of 2 mol is preferred. Furthermore, in the present invention, the content of the complex-forming compound in the reaction system is from 1/100 to 100 times the molar ratio of the content of the poorly soluble metal compound.
It is preferably 1/10 to 20 times. As a method of applying water to the photosensitive layer or the dye fixing layer, for example, Japanese Patent Application No. 1982-268926, page 101, 9
There is a method described in line 4 on page 102. As heating means in the development and/or transfer step, there are the means described on page 102, line 14 to page 103, line 11 of Japanese Patent Application No. 59-268926, such as a hot plate, an iron, and a hot roller. It is also possible to apply a layer of conductive material such as graphite, carbon black, metal, etc. to the photosensitive element and/or dye fixing element, and heat the conductive layer directly by passing an electric current through the conductive layer. good. The pressure conditions and method of applying pressure when overlapping the photosensitive element and the dye fixing element and bringing them into close contact are disclosed in the patent application.
The method described on pages 103 to 104 of No. 59-268926 can be applied. Any of a variety of thermal development equipment can be used to process the photographic elements of this invention. For example, JP-A-59-
No. 75247, No. 59-177547, No. 59-181353, No. 59-181353, No.
Apparatuses such as those described in No. 60-18951, Japanese Utility Model Application No. 116734/1980, etc. are preferably used. Specific Effects of the Invention According to the present invention, since it contains a dye-donating substance represented by the general formula () which is oxidized during development and releases a diffusible dye, it can be used as a coloring material for diffusion transfer. Since it contains a dye-providing substance that imparts transfer density and is excellent in dye release efficiency, diffusivity, and stability over time, a color photographic light-sensitive material with high image density and low fog can be obtained. Specific Examples of the Invention Hereinafter, specific examples of the present invention will be shown, and the effects of the present invention will be explained in further detail. Example 1 First, a method for preparing a benzotriazole silver emulsion will be described. 28g gelatin and 13.2g benzotriazole in water
Dissolved in 3000ml. This solution was kept at 40°C and stirred. A solution prepared by dissolving 17 g of silver nitrate in 100 ml of water was added to this solution over a period of 2 minutes. The pH of this benzotriazole silver emulsion was adjusted, sedimented, and excess salt removed. Thereafter, the pH was adjusted to 6.30, and a yield of 400 g of benzotriazole silver emulsion was obtained. This article describes how to make a silver halide emulsion. A well-stirred gelatin aqueous solution (containing 20 g of gelatin and 3 g of sodium chloride in 1000 ml of water at 75°C)
600 ml of an aqueous solution containing sodium chloride and potassium bromide and an aqueous silver nitrate solution (0.59 mol of silver nitrate dissolved in 600 ml of water) were simultaneously added at equal flow rates over 40 minutes. In this way, a monodisperse cubic silver chlorobromide emulsion (80 mol % bromine) with an average grain size of 0.35 μm was prepared. After washing with water and desalting, 5 mg of sodium thiosulfate
and 4-hydroxy-6-methyl-1,3,3a,
Chemical sensitization was carried out at 60° C. by adding 20 mg of 7-tetrazaindene. The yield of emulsion was 600g. A method for preparing gelatin dispersion A of a dye-donating substance will be described. 5 g of the magenta dye-donating substance (2) of the present invention,
As a surfactant, 0.5 g of sodium succinate-2-ethyl-hexyl ester sulfonate and 5 g of tri-iso-nonyl phosphate were weighed, 15 ml of cyclohexanone was added, and the mixture was heated and dissolved at approximately 60°C.
A homogeneous solution was obtained. This solution and 100 g of a 10% solution of lime-treated gelatin were stirred and mixed, and then dispersed using a homogenizer at 10,000 rpm for 10 minutes. This dispersion is called magenta dye-providing substance dispersion A. A method for preparing photosensitive coatings will be described. a Benzotriazole silver emulsion 10g b Photosensitive silver chlorobromide emulsion 15g c Dye-providing substance dispersion A 25g d 5% aqueous solution of the following compound C ₉ H ₁₉ 〓O(-CH ₂ CH ₂ O) ₈ H 5ml e 10% methanol solution of benzenesulfonamide 5 ml f p-chlorophenylsulfonyl 5% aqueous solution of guanidine acetate 25 ml Mix above a) to f) and add a thickener (e.g. polystyrene-p-sodium sulfonate). and add water
The volume was reduced to 100ml. This solution was applied to a wet film thickness of 50 μm on a 180 μm thick polyethylene terephthalate film. Next, the following protective layer coating composition was prepared. Protective layer coating composition g 10% gelatin 400g h p-chlorophenylsulfonyl 5% aqueous solution of guanidine acetate 430ml i 4% aqueous solution of hardener with the following structural formula 50ml CH ₂ =CHSO ₂ CH ₂ CONH (CH ₂ ) ₂ NHCOCH ₂ SO ₂ CH=CH ₂ was mixed and made up to 1000ml with thickener and water. This coating composition is applied onto the above photosensitive coating.
After coating to a thickness of 30 μm, it dries to form photosensitive material No.
1 was produced. Using these photosensitive materials with a tungsten light bulb,
Imagewise exposure was made for 1 second at 5000 lux. Then 30 minutes on a heat block heated to 150℃.
Heat evenly for seconds. Next, a method for forming a dye-fixing material having an image-receiving layer will be described. 10 g of poly(methyl acrylate-co-N,N,N-trimethyl-N-vinylbenzylammonium chloride) (ratio of methyl acrylate and vinylbenzylammonium chloride is 1:1)
100g 10% lime processed gelatin dissolved in 180ml water
and 20 ml of a 4% aqueous solution of 1,4-bis(2',3'-epoxypropoxy)butane.
This mixed solution was uniformly applied to a wet film thickness of 20 μm on a paper support laminated with polyethylene.
After drying, this sample was used as a dye fixing material. After soaking the dye-fixing material in water, the above-mentioned heated photosensitive material was placed on top of the other so that the film surfaces were in contact with each other. In addition, the dye-donating substance (2) used in photosensitive material No. 1
A dispersion of a yellow dye-providing substance was prepared in the same manner except that 7 g of yellow dye-providing substance (3) was used in place of , and using this dispersion was prepared in the same manner as in Photosensitive Material No. 1 to prepare Photosensitive Material No. 2. I made it. Similarly, using 4.5g of cyan dye-donating substance (5),
Created photosensitive material No. 3. After 30 seconds, the dye fixing material was peeled off from the light-sensitive material, and negative magenta, yellow, and cyan dye images were obtained. The density of the negative image is measured using a Macbeth reflection densitometer.
Measurements were made using green light, blue light, and red light, respectively. The results are shown in the table below.

[Table] It was found that transferred dye images with sufficient distinguishability could be obtained using the dye-providing substance of the present invention. Example 2 A photosensitive material was prepared in the same manner as in Example 1, except that 1 g of the reducing agent shown below was added to the dispersion of each dye-donating substance used in Example 1 (it was dissolved in triisononyl phosphate at the same time as the dye-donating substance). I made materials No. 4, 5, and 6. This was treated in the same manner as in Example 1, and the results obtained are shown in the following table.

[ka]

[Table] It can be seen that image discrimination is improved by using a reducing agent in combination. Example 3 Photosensitive materials were prepared by changing the dye-providing substances as shown in the table below, and processed in the same manner as in Example 1. The results are shown below.

[Table] Dosage ** Same as in Example 2 Example 4 Using the emulsion of Example 1 and the dye-donor dispersion (2), the following photosensitive coatings were prepared. a Benzotriazole silver emulsion 10g b Photosensitive silver chlorobromide emulsion 15g c Dye-providing substance dispersion A 25g d 5% aqueous solution of the following compound

[Chemical] Mix the above a) to d), add a thickener (for example, polystyrene-p-sodium sulfonate) and water.
The volume was reduced to 100ml. This solution was applied to a wet film thickness of 50 μm on a 180 μm thick polyethylene terephthalate film. Next, the following protective layer coating composition was prepared. e 10% gelatin 400g f Zinc hydroxide (average size 0.2μm) 14g g 4% aqueous solution of hardener with the following structural formula 50ml CH ₂ = CHSO ₂ CH ₂ CONH (CH ₂ ) ₂ NHCOCH ₂ SO ₂ CH=CH ₂ were mixed and made up to 1000 ml by adding a thickener and water. This coating composition is applied onto the above photosensitive coating.
After coating to a thickness of 30 μm, it dries to form photosensitive material No.
11 were made. A reducing agent (Example 2) was added to the dispersion of the dye-donating substance (2).
Photosensitive material No. 12 was prepared with exactly the same structure as photosensitive material No. 11, except that 1 g of the same material was added. Next, we will discuss how to make the dye fixing material. Dissolve 63 g of gelatin, 130 g of a mordant with the following structure, and 80 g of guanidine picolinate in 1300 ml of water, and spread it on a paper support laminated with polyethylene to a thickness of 45 μm.
After applying the film uniformly to a wet film thickness of

[Chemical] Furthermore, on top of this, add 35 g of gelatin and 1.05 g of 1,2-bis(vinylsulfonylacetamidoethane).
A dye-fixing material was prepared by applying a solution dissolved in 800 ml of water to a wet film thickness of 17 μm and drying. Using a tungsten bulb as the photosensitive material above, 5000
Imagewise exposure was made for 1 second at lux. 10 ml/m ² of water was supplied to the emulsion surface of this exposed light-sensitive material using a wire bar, and then the material was superimposed so that the dye-fixing material and the film surface were in contact with each other. The film was heated for 30 seconds using a heat roller whose temperature was adjusted so that the temperature of the water-absorbed film was 95°C. When it was then peeled off from the dye-fixing material, a magenta image was obtained on the fixing material. The results of concentration measurements are shown in the table below.

[Table] Example 5 Light-sensitive materials Nos. 13 to 22 were prepared in the same manner as in Example 4, except that the dye-donating substance was changed as shown in the table below, and processed in the same manner as in Example 4. The results are shown in the table below.

【table】

[Table] The effects of the present invention are clear from the above examples.

Claims (1)

[Claims] 1. At least photosensitive silver halide on a support,
1. A color photographic material comprising a binder and a dye-donating substance represented by the following general formula () which is oxidized during development and releases a diffusible dye. General formula () [Formula] {In the above general formula (), R ₁ and R ₂ are
Hydrogen atom, halogen atom, cyano group, alkyl group, aryl group, heterocyclic group, alkoxy group, aryloxy group, acyloxy group, alkylsulfonyloxy group, arylsulfonyloxy group, acylamino group, anilino group, ureido group, respectively. represents an alkylsulfonylamino group, an arylsulfonylamino group, an alkylthio group, an arylthio group, an alkoxycarbonylamino group, an aryloxycarbonylamino group, a carbamoyl group, an acyl group, an alkylsulfonyl group, or an arylsulfonyl group, and among R ₁ and R ₂ At least one of the carbon atoms is 10 or more. Dye represents a dye group or a dye precursor group. }