JPS6374055A - Color photographic sensitive material - Google Patents

Abstract

PURPOSE:To obtain the titled material capable of giving high dye transfer density and having improved dye releasing efficiency, diffusivity and stability in the lapse of time by incorporating a photosensitive silver halide, a binder and a specific dye donating substance capable of releasing a diffusive dye by oxidizing it at the time of developing on a substrate. CONSTITUTION:The titled material comprises the photosensitive silver halide, the binder and the dye donating substance which is capable of releasing the diffusive dye by oxidizing it at the time of developing and is shown by formula I on a substrate body. In formula I, R1 and R2 are each hydrogen or halogen atom, cyano or a substd. or an unsubstd. alkyl group, etc., at least one of R1 and R2 is >=10C alkyl group, Dye is a dye group or its precursor. Thus, image density is increased and fogging is decreased, since the titled material includes the dye donating substance, which gives high dye transfer density and is excellent in dye releasing efficiency, difflusivity, and in storage stability, as the coloring material for diffusion transfer.

Description

Detailed Description of the Invention (1) Background Technical Field of the Invention The present invention relates to a color photographic light-sensitive material, and more particularly to a color photographic light-sensitive material containing a dye-providing substance.

PRIOR ART AND THEIR PROBLEMS Many systems are known for forming color images by transferring diffusible dyes.

For example, US Pat. No. 3,134,764 describes a system 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 No. 51-63618, and a method of releasing a diffusible dye by an intra-molecular exchange reaction of an inoxacilone ring is disclosed in JP-A-49-111628. It is described in. In both of these methods, the dye diffuses into the image-receiving layer in areas where no development has occurred (unexposed areas), and no dye is released or diffused in areas where development has not occurred (exposed areas). . However, in these methods, development and dye release or diffusion occur in parallel, so S/
This method has the disadvantage that it is very difficult to obtain an image with a high N ratio. In addition, in order to improve these shortcomings,
Japanese Patent Application Laid-Open No. 1983-1997 discloses a method in which the coloring material is made into an oxidized form without dye-releasing ability in advance, is allowed to coexist with a reducing agent precursor, and is reduced by the reducing agent that remains unoxidized after development to release a diffusible dye.
No. 110827. However, this method has the disadvantage that it is difficult to obtain images with a high S/N ratio unless the development speed and the reduction speed of the coloring material by the reducing agent are strictly controlled.

On the other hand, as a method for releasing a diffusible dye in the area where development occurs, a method has been patented in the UK 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. No. 1,330,524, and U.S. Pat. No. 3,227,550 describes a system in which a diffusible dye is produced by the reaction of a coupler having a diffusion-resistant group as a leaving group with an oxidized color developer. has been done. but,
In systems using these color developers, image contamination due to oxidative decomposition products of the developer becomes an extremely serious problem.

In addition, as dye-donating substances with reducing properties, the following (1) to
(12) etc. are known.

U.S. Patent No. 3,928,312, U.S. Patent No. 3.993.6
No. 38 U.S. Patent No. 4,053,312 U.S. Patent No. 4,055,428t JP-A-51-104343ll JP-A-53-3819 ■ JP-A-51-104343 Amount R JP-A-51 -104343 Japanese Patent Publication No. 51-104343 Research Disclosure Magazine 1978, 17,465 U.S. Patent No. 3,725,062 U.S. Patent No. 3,728,113 and U.S. Patent No. 3,443,939 Of these, (1) to (9) are all oxidized during development, and then a diffusible dye having a sulfamoyl group at the end is released by the action of an alkali. However, when trying to obtain sufficient density using these dye-donating substances, there are problems such as increased fogging density.

Moreover, the compounds (lO) to (12) have poor efficiency in the dye release process after being oxidized, and cannot be used for practical use.

■ Purpose of the Invention The purpose of the present invention is to provide a color photographic material containing a dye-donating substance that provides a high dye transfer density as a coloring material for diffusion transfer and has excellent dye release efficiency, diffusivity, and stability over time. It's about doing.

■Disclosure of invention These objects are achieved by the invention described below.

That is, the present invention is characterized in that the support contains at least a photosensitive silver halide, a binder, and a dye-donating substance represented by the following general formula (I) that releases a diffusible dye upon oxidation during development. It is a color photographic material.

General formula (I) 82 (In the above general formula (I), R1 and R2 are each a hydrogen atom, a halogen atom, a cyano group, an alkyl group,
Aryl group, heterocyclic group, alkoxy group, aryloxy group, acyloxy group, alkylsulfonyloxy group,
Arylsulfonyloxy group, acylamino group, anilino group, ureido group, alkylsulfonylamino group, arylsulfonylamino group, alkylthio group, arylthio group, alkoxycarbonylamino group, aryloxycarbonylamino group, carbamoyl group, acyl group, alkyl It represents a sulfonyl group or an arylsulfonyl group, and at least one of R1 and R2 has 10 or more carbon atoms.

Dye represents a dye group or a dye precursor group. ) ■Specific structure of the invention Hereinafter, a specific configuration of the present invention will be explained in detail.

The color photographic light-sensitive material of the present invention comprises at least a photosensitive silver halide, a binder and the following general formula (I) on a support.
) contains a dye-donating substance that is oxidized during development and releases a diffusible dye.

In the present invention, "being oxidized and releasing a diffusible dye during development" refers to the fact that the compound of general formula (I) itself undergoes an oxidation-reduction reaction with exposed silver halide to release a diffusible dye. This refers to the release of a diffusible dye during development by causing a coupling reaction or redox reaction in relation to the transition agent used in combination.

General Formula (I) In the above General Formula (I), R and R2 are each a hydrogen atom, a halogen atom, a cyano group, or a substituted or unsubstituted alkyl group, aryl group, heterocyclic group, alkoxy group, or aryl group. Oxy group, acyloxy group, alkylsulfonyloxy group, arylsulfonyloxy group, acylamino group, anilino group, ureido group, alkylsulfonylamino group, arylsulfonylamino group, alkylthio group, arylthio group, alkoxycarbonylamino group, aryloxycarbonylamino group group, carbamoyl group, acyl group, alkylsulfonyl group or arylsulfonyl group, and at least one of R1 and R2 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 R1 and R2 include an alkyl group, an aryl group, an alkoxy group, an aryloxy group, an acylamino group, an alkyl or arylsulfonylamino group,
Anilino group, substituted ureido group, alkoxycarbonylamino group, etc., and 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-zyl7-amyl phenyl group, p- detoratecanoylaminophenyl group, etc.)
, alkoxy groups (e.g. methoxy group, ethoxy group, impropoxy group, t-butoxy group, dodecyloxyethoxy group, hexadecyloxy group, etc.), aryloxy group (
For example, phenoxy group, 4-t-butylphenoxy group, 4
-t-octylphenoxy group, 2,4-di-t-butylphenoxy group, etc.), acylamino group (e.g. acetylamino group, benzoylamino group, octanoylamino group,
a-(2,4-di-t-amylphenoxy)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 group (
Examples include phenylureido group, N,N-dibutylureido group, octadecylureido group, etc.), alkoxycarbonylamino group (eg, ethoxycarbonylamino group, octadecylsulfonylamino group, etc.).

Dye represents a dye group or a dye precursor group.

Examples of dyes include azo dyes, azomethine dyes, anthraquinone dyes, naphthoquinone dyes, styryl dyes, nitro dyes, quinoline dyes, carbonyl dyes, phthalocyanine dyes, and metal complex salts thereof. Typical dye precursor groups are those that produce dyes by hydrolysis, such as those described in JP-A-48-125゜818;
U.S. Patent No. 3,222,196, U.S. Patent No. 3,307,9
Examples include dyes described in No. 47, etc., which have temporarily shortened wavelengths by acylating the auxochrome.

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 portion 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.

Suitable ballast groups are hydrophobic groups having 10 or more carbon atoms, more preferably 15 or more carbon atoms, and specific examples include alkyl groups, aralkyl groups, aryl groups, alkenyl groups, alkoxy groups, aryloxy groups, etc. Can be done.
Preferred specific examples of the palaste group are listed in the preferred specific examples of R1 and R2.

Preferred specific examples of the dye-providing substance of the present invention are shown below.

^ =-U The dye-donating substance of the present invention can be obtained by condensing a pyrazolotriazole having an amine group introduced into the active position and a sulfonic acid chloride of a dye (or a dye precursor) in the presence of a base.

Amine-substituted pyrazolotriazoles are useful pyrazolotriazole couplers (II) in conventional photography.
) can be easily obtained in a short process of nitrosation and reduction using as a starting material.

The pyrazolotriazole coupler as a starting material was disclosed in Japanese Patent Application Publication No. 5
It can be synthesized according to the methods described in specifications such as No. 9-171956 and No. 59-27745.

Next, the method for synthesizing the dye-donating substance of the present invention will be explained by giving specific examples.

Synthesis example: Synthesis of dye-donating substance (2) The synthetic route for the dye-donating substance (2) is shown below.

(1) Synthesis of intermediate (B) 6-methyl-2-' (3-(4-(
2-(2,4-di-amylphenoxy)octanamido)phenyl)propyl)-1H-pyrazolo(1,5
-b) (1°2.4) Triazole (A) 31.0g
was dissolved by heating. To this, isoamyl nitrite 7.77
g was added at room temperature and stirring was continued for 3 hours. ethyl acetate 3
After adding 00 rgll, the reaction mixture was reduced to 1.52
After washing with water three times, it was dried over anhydrous magnesium sulfate. The oily substance 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 the intermediate. (B) (7-nidroso6-
Methyl-2- (3-(1-(2-(2゜4-di-t-
amylphenoxy)octanamido)phenyl)propyl)-1H-pyrazolo(1,5-b)(1,2,4)
28.6 g (87%) of triazole) were obtained.

(2) Synthesis of intermediate (C) 6.8 g of the above intermediate (B) was dissolved in ethanol 560 and heated to reflux in a nitrogen atmosphere. To this was added a mixture of 67 g of stannous chloride and 140,119 g of concentrated hydrochloric acid, 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. After washing the extract with water and drying over anhydrous magnesium sulfate, the solvent was distilled off under reduced pressure to obtain the intermediate (
C) 7.2g was obtained.

(3) For the synthesis of dye-donating substance (2), 5.5 g of the intermediate ([:) described above was added to a mixture of dimethylacetamide 40 and pyridine 1011, and then magenta dye sulfonyl chloride (D) 4 was cooled with water. .4g
was added little by little.

After stirring for 1 hour at 10-15°C, the reaction solution was poured into cold water containing a small amount of hydrochloric acid and extracted with ethyl acetate. After washing the extract with water and drying (the ethyl acetate was distilled off under reduced pressure, the residue was loaded by silica gel chromatography (eluent: hexane/ethyl acetate: 1/l) to obtain a dye-donating substance (2
5.1 g of orange-brown crystals of ) were obtained. Melting point 163-167
C. Other dye-donating substances (d) were also 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 to the wrinkles.

The amount to be contained is usually 0.01 per mole of silver halide.
The amount is from 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. Patent No. 2.322,0.
It can be introduced into the layer of the photosensitive material by a known method such as the method described in No. 27. In this case,
No. 9-83154, No. 59-178451, No. 59-
No. 178452, No. 59-178453, No. 59-1
No. 78454, No. 59-178455, No. 59-17
A high boiling point organic solvent such as that described in No. 8457 can be used in combination with a low boiling point organic solvent having a boiling point of 50° C. to 160° C., if necessary. 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.

Also, Japanese Patent Publication No. 51-39853, Japanese Patent Publication No. 51-5994
The dispersion method using a polymer described in No. 3 can also be used.

In the case of a compound that is substantially insoluble in water, it can be dispersed and contained in the binder in the form of fine particles in addition to the method described above.

Various surfactants can be used when dispersing in hydrophilic colloids. For example, JP-A-59-15763
The surfactants listed in No. 6, pages (37) to (38) can be used.

These methods can also be applied to hydrophobic additives such as image formation accelerators described below.

The color photographic light-sensitive material of the present invention is particularly advantageously used in the color image forming method in which a diffusible dye is released into an image, diffused, and then fixed.

The above 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. 757°959);
A method that performs heat development in a substantially moisture-free state [thermal development method] (for example, European Patent No. 76492A2 and JP-A-5B-
No. 79247, No. 59-218443, patent application 1986-
There are various forms such as those described in No. 79709, etc., but 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 gelatin and gelatin! These include proteins such as S-forms, natural substances such as cellulose derivatives, starch, polysaccharides such as gum arabic, and synthetic polymers such as polyvinyl alcohol, 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 binder and the coating amount of the polymer mordant can be easily determined by those skilled in the art depending on the star of the dye to be mordant, the type and composition of the polymer mordant, and the image forming method to be applied. Is it possible? The mordant/binter ratio is 20/80 to 80/20 (weight ratio)
The applied amount of the mordant is approximately 0.2 to approximately 15 g/ml, and preferably 0.5 to 8 g/rn2.

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.

Gelatin hardeners that can be used in the present invention include:
For example, aldehydes (formaldehyde, glyoxal, geltaraldehyde, etc.), N-methylol compounds (dimethylolurea, methylolsimethylhytantoin, etc.), dioxane derivatives (2,3-dihydroxydioxane, etc.), activated vinyl compounds [1°3 .5-1-
Liacryloyl-hexahydro-S-triazine, bis(vinylsulfonyl)methyl ether, N,N'-ethylene-bis(vinylsulfonylacetamide), N,N'
-trimethylene-bis(vinylsulfonylacetamide)
etc.], active halogen compounds (2,4-dichloro-6-
Hydroxy-5-triazine, etc.), mucohalogen acids (mucochloric acid, mucophenoxychloroic acid, etc.), epoxy compounds, isoxazoles, dialdehyde starch, 1-chloro-6-hydroxytriazinylated gelatin, etc. I can do it. Specific examples include U.S. Patent Nos. 1,870,354, 2,080,019, 2,726°162, and 2,870,013
No. 2,983,611, No. 2,992,10
No. 9, No. 3.047,394, No. 3,057.7
No. 23, No. 3,103,437, No. 3,321,
No. 313, No. 3.325゜287, No. 3.362
, No. 827, No. 3,490,911, No. 3,53
British Patent No. 9,644, British Patent No. 3,543,292, British Patent No. 676.628, British Patent No. 825,544, British Patent No. 1, 2
70,578, German Patent No. 872.153, German Patent No. 1,090,427, German Patent No. 2,749,260, Japanese Patent Publication No. 34-7133, German Patent No. 46-1872, etc. Of the gelatin hardeners, especially aldehydes,
Active vinyl compounds, active halogen compounds, patent application 1980-
Epoxy compounds described in No. 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 can be arbitrarily selected depending on the purpose.

Typically, 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 forms a mordant layer containing a mordant,
Alternatively, it can be added to a layer adjacent thereto (either near or far from the support carrying the mordant layer etc.). The metal ions used here are colorless and heat-resistant.
It is desirable that it be stable to light. That is, Cu
", Zn", N i ", pt", P d ", C03
Polyvalent ions of transition metals such as 1 ion are preferable,
Particularly preferred is Zn''. This metal ion is usually added in the form of a water-soluble compound, for example, ZnSO4, Zn(CH3CO2)2, and the amount of addition is suitably about 0.01 to about 5 g/rn''. , preferably 0.1 to 1. It is 5g/d.

A hydrophilic polymer can be used as a binder in the layer to which these metal ions are added. As the wood-philic binder, transparent or translucent hydrophilic colloids such as those specifically listed above with respect to the mordant layer are useful.

Since the compounds of the present invention have reducing properties themselves, it is not necessarily necessary to use a separate reducing agent, but by increasing the reactivity,
It is desirable to use a reducing agent in combination for the purpose of improving image distinguishability.

Examples of reducing agents used in this invention include inorganic reducing agents such as sodium sulfite and sodium bisulfite, benzenesulfinic acids, hydroxyamines, hydrazines,
In addition to hydrazides, borane-amine complexes, hydroquinones, aminophenols, catechols, p-phenylenediamines, 3-pyrazolidinones, hydroxytetronic acid, ascorbic acid, 4-amino-5-pyrazolones, etc. T, tl, james, “
The theory of thephoto
“graphic process” 4th, Ed
, , pages 291-334 can also be used.

Also, JP-A-56-138,736, U.S. Patent No. 4,3
Reducing agent precursors such as those described in No. 30,617 can also be used.

Examples of more preferable reducing agents include those listed below.

3-pyrazolidones and their precursors [e.g.
-Phenyl-3-pyrazolidone, 1-phenyl-4,4
-dimethyl-3-pyrazolidone, 4-hydroxymethyl-4-methyl-1-phenyl-3-pyrazolidone, 1-
m-) Zyl-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(2)-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-)lifluoroethyl)-
4,4-dimethyl-3-pyrazolidone, 5-methyl-3
-pyrazolidone, 1,5-diphenyl-3-pyrazolidone, 1-phenyl-4-methyl-4-stearoyloxymethyl-3-birasilitone, 1-phenyl-4-methyl-4-lauroyloxymethyl-3-pyrazolidone,
■-Phenyl-4,4-bis=(lauroyloxymethyl)-3-pyrazolidone, 1-phenyl-2-acetyl-3-bilasiliton, 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-7-octylhydroquinone, pentadecylhydroquinone, Sodium 5-pentadecylhydroquinone-2-sulfonate, p-benzoyloxyphenol, 2-methyl-4-benzoyloxyphenol, 2-t-butyl-4-(4-chlorobenzoyloxy)phenol]; Sulfonamidophenol or Naphthols [e.g., Nh:5 (J2-C12H2S, etc.)]: Paraphenylenediamines [e.g., N,N-diethylparaphenylenediamine, N,N-ethyl-3-methyl-p-phenylenediamine, ShiI' 13 Aminephenols [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 may 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 reducing agent added is 0.00% per mole of silver.
01 to 20 mol, particularly preferably 0.1 to 10 mol.

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. Patent No. 4,500,626, column 50, Research Disclosure, June 1978 issue 9.
Pages - 10 (RD17029), Patent Application 1986-2285
No. 51, No. 60-225176, No. 60-22826
Any of the silver halide emulsions described in No. 7 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 nitrogen-containing heterocyclic compounds (JP-A-58-126526, JP-A-58-215644).
issue).

The coating amount of the photosensitive silver halide used in the present invention is in the range of 1 mg to 10 g/rn'' 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, Japanese Patent Publication Nos. 59-180550 and 60-1
No. 40335, Research Disclosure Magazine 197
The sensitizing dyes described in June 1988 issue, pages 12-13 (RD17029), JP-A-60-111239, Japanese Patent Application No. 1983
Examples include heat-decolorizable sensitizing dyes described in Japanese Patent No. 172,967 and the like.

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, it is a dye that itself does not have a spectral sensitizing effect or a substance that does not substantially absorb visible light,
Substances exhibiting supersensitization may also be included in the emulsion (e.g., U.S. Pat. Nos. 2,933,390 and 3,635,72).
No. 1, No. 3,743,510, No. 3,615゜6
No. 13, No. 3,615,641, No. 3.617.
No. 2'95 and No. 3,635,721)
.

These sensitizing dyes may be added to the emulsion at or before chemical ripening, and may be added to the emulsion as described in US Pat. No. 4,183.
It may be carried out before or after nucleation of silver halide grains according to No. 756 and No. 4,225.666.

The amount added is generally about 10'' to 10 to 2 moles per mole of silver halide.

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 the film unit is a form in which the above image-receiving element and photosensitive element 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, or 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, magenta in each of the above emulsion layers. It is composed of a combination of a dye-donating substance and a cyan dye-providing substance (herein, an infrared light-sensitive emulsion layer refers to an infrared light-sensitive emulsion layer that
(This refers to an emulsion layer that is sensitive to the following types of light.)
A white reflective layer containing a solid pigment such as titanium oxide is provided between the mordant layer and the photosensitive layer or the layer containing a dye-donating substance 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 peeling layer may be provided at an appropriate position to allow all or part of the photosensitive element to be peeled off from the image receiving element. 674°082).

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. A mode in which an image receiving element, a white reflective layer, a peeling 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 U.S. Pat. No. 3,730.718. has been done. 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 separate layer type and the other a peel-free 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 mordant layer do not face each other before exposure is completed, but after the completion of exposure (for example, during development), the surface coated with the photosensitive layer is It is devised so that it turns over and overlaps the surface on which the image-receiving layer is applied. Immediately after the transfer image is completed with the mordant layer, the photosensitive element is peeled off from the image receiving element.

Further, in a preferred embodiment of the separate 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-blocking layer, The surface coated with the photosensitive layer and the surface coated with the mordant layer are stacked facing each other.

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. You can. 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 overlaid 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, the processing element preferably contains a light shielding agent (such as carbon black or a dye whose color changes with pi) and/or a white pigment (such as titanium oxide). Further, in a color diffusion transfer film unit, a neutralization timing mechanism comprising a combination of a neutralization layer and a neutralization timing layer is preferably incorporated into the cover sheet, the receiver 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. Joule heat generated when electricity is applied may be used for diffusion transfer.

Semiconductive inorganic materials (e.g. silicon carbide,
molybdenum silicide, lanthanum chloride, barium titanate ceramics, tin oxide, zinc oxide, etc.) may also be used.

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, a metal salt can be used together with silver halide as an oxidizing agent. In this case, the photosensitive silver halide and the metal salt must be in contact with each other or at a close distance.

Among such 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, page 37-
There are compounds described on page 39, columns 52 to 53 of US Pat. No. 4,500.626. Also, special application 1986-1
Silver salts of carboxylic acids having an alkynyl group such as silver phenylpropiolate described in No. 13235, and
Acetylene silver described in 90089 is also useful. Two or more types of organic silver salts may be used in combination.

The above-mentioned organic silver salts contain, per mol of photosensitive silver halide,
0.01 to 10 mol, preferably 0.01 to 1
Moles can be used together. The total coating amount of photosensitive silver halide and organic silver salt is 50 mg or Log in terms of silver.
/m' is appropriate.

In the present invention, a compound that activates development and simultaneously stabilizes images can be used in the photosensitive element. For specific compounds preferably used, see U.S. Patent Nos. 4 and 5.
No. 00,626, columns 51-52.

Various antifoggants or photographic stabilizers can be used in the present invention. Examples include Research Disclosure magazine, December 1978 issue 24-2.
Athols and azaindenes described on page 5, JP-A-59
Nitrogen-containing carboxylic acids and phosphoric acids described in Japanese Patent Application No. 168442, or mercapto compounds and metal salts thereof described in JP-A-59-111636, Japanese Patent Application No. 60-22
Acetylene compounds described in No. 8267 are 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 on the chromaticity diagram using the three primary colors yellow, magenta, and cyan, a light-sensitive element having at least three silver halide emulsion layers each sensitive to a different spectral region is used. good. For example, there are combinations of three layers such as a blue-sensitive layer, a green-sensitive layer, and a red-sensitive layer, and a combination of a green-sensitive layer, a red-sensitive layer, and an infrared-sensitive layer. 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 use in 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. It can have a release layer, a matte layer, etc. to facilitate peeling off from the element. Various additives are listed in Research Disclosure Magazine, 1978, 6.
Plasticizers, matting agents, dyes for improving sharpness, which are described in pages 9 to 15 of the Japanese issue, Japanese Patent Application No. 59-209563, etc.
Additives include antihalation dyes, surfactants, optical brighteners, antislip agents, antioxidants, and antifading agents.

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 release 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 nail layer include a hydrophilic thermal solvent;
Plasticizers, anti-fading agents, UV absorbers, shearing agents, matting agents, antioxidants, dispersed vinyl compounds to increase dimensional stability, surfactants, optical brighteners, etc. may be included. . In addition, especially in a system in which thermal development and dye transfer are carried out 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 promoters include promoting redox reactions between silver salt oxidizing agents and reducing agents;
It has functions such as promoting reactions such as generation of dye from dye-donating substance, decomposition of dye, and release of diffusible dye, and promotion of movement of dye from the light-sensitive material layer to the dye fixing layer. The functions include bases or base precursors, nucleophilic compounds, high-boiling organic solvents (oils), thermal solvents,
It is classified as a surfactant, a compound that interacts with silver or silver ions, etc. 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 the patent application in 1983.
-213978, pages 67-71.

There are various other methods of generating bases, and the compounds used in these methods are all useful as base precursors. For example, a method of generating a base by mixing a sparingly soluble metal compound and a compound (referred to as a complex-forming compound) that can undergo a complex-forming reaction with the metal ions constituting the sparingly soluble metal compound, as described in Japanese Patent Application No. 169585/1985. There is also a method of generating a base by electrolysis as described in Japanese Patent Application No. 74702/1983.

The former method is particularly effective. Examples of poorly soluble metal compounds include carbonates, hydroxides, and oxides of zinc, aluminum, calcium, barium, and the like. Also,
Regarding complex-forming compounds, see, for example, N. E. Martell, R. M. Smith (8, E., Martell, R.
,M.

Sm1th) co-author, 1 critical stability constant
yCans tants) J, Volumes 4 and 5, Plenum Press.

Specifically, aminocarboxylic acids, imidinoacetic acids, pyridylcarboxylic acids, amine phosphoric acids, carboxylic acids (mono, di, tri, and tetracarboxylic acids, as well as phosphono, hydroxy, oxo, ester, amide, alkoxy, mercapto, alkylthio, and phosphino) Examples include salts of alkali metals, guanidines, amidines, or quaternary ammonium salts with hydroxamic acids, polyacrylates, polyphosphoric acids, etc.

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 Specifically, examples include acid precursors that release acids when heated, electrophilic compounds that cause a substitution reaction with coexisting bases when heated, nitrogen-containing heterocyclic compounds, mercapto compounds, and their precursors (for example, Application No. 58-216928, No. 59-
No. 48305, No. 59-85834 or No. 59-8
Compounds described in No. 5836, etc. ) Compounds that release mercapto compounds upon heating are also useful; for example, Japanese Patent Application No. 190173/1982
-268926, 59-246468, 60-
No. 26038, No. 60-22602, No. 60-260
There are compounds described in No. 39, No. 60-24665, 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 %R' such as tempura and gum arabic. Includes synthetic polymeric materials such as polyvinylpyrrolidone, 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 lrn'', 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 g of binder to 1 g of solvent or less, preferably 0.
A suitable amount is 5 cc or less, more preferably 0.3 cc or less.

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 hardening agents can be found in Japanese Patent Application No. 59-268926, pages 94 to 95, and Japanese Patent Application Laid-open No. 59-157636 (
Examples include those described on page 38), 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 any of an emulsion layer, an intermediate layer, a protective layer, and a dye fixing layer, but it is preferably incorporated in the dye fixing layer and/or a layer adjacent thereto. Examples of hydrophilic thermal solvents include:
These include ureas, pyridines, amides, sulfonamides, imides, 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 photosensitive element and/or dye fixing element of the present invention is one that can withstand processing temperatures. As general supports, glass, paper, polymer films, metals and their analogs are used, as well as Japanese Patent Application No. 59-268926, pages 95-96.
Anything listed as a support can be used.

The photosensitive element and/or the dye fixing element may be of any shape having an electrically conductive heating layer as a heating means for thermal development or diffusion transfer of the dye.

The transparent or translucent 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 of using a thin film of a non-conductive material that exhibits conductivity, and a method of using a thin film of an organic material in which conductive particles are dispersed in a binder. Materials that can be used in these methods include those described in Japanese Patent Application No. 151,815/1984.

In the present invention, the method of coating the heat-developable photosensitive layer, protective layer, intermediate layer, undercoat layer, back layer, dye fixing layer, and other layers is described in columns 55 to 56 of U.S. Pat. No. 4,500,626. method can be applied.

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.
926, p. 100 and U.S. Pat. No. 4,500,626, p. 56 pJJ can be used.

In the present invention, the steps of heat 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) after imagewise exposing and heating the photosensitive element,
There are two methods: (2) a method in which the dye-fixing elements are stacked and heated if necessary to transfer the mobile dye to the dye-fixing element; and (2) a photosensitive element is imagewise exposed, and the dye-fixing elements are stacked and heated.

The methods (1) and (2) above can be carried out in the substantial absence of water or in the presence of a trace amount of water.

The heating temperature in the heat development step is about 0°C to about 250°C, and is particularly useful to be about 0°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, it 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 fixed layer also proceeds quickly.
High-density color images can be obtained in a short time.

The amount of water used in this embodiment is at least 0.1 times, preferably 0.1 times or more, the weight of the total coated film of the light-sensitive element and the dye-fixing element, and the amount of the solvent corresponds to the maximum swelling volume of the total coated film. (Especially less than the weight of the solvent corresponding to the maximum swelling volume of the entire coating film minus the weight of the entire coating film)
A small amount is enough.

The state of the film at the time of swelling D is unstable, and depending on the conditions, local bleeding may occur.To avoid this, the total coating film thickness of the photosensitive element and dye fixing element should be equivalent to the volume at maximum swelling. It is preferable that the amount of water is less than that. Specifically, 1 per square meter of the total area of the photosensitive element and dye fixing element.
A range of g to 50 g, particularly 2 g to 35 g, more preferably 3 g to 25 g is preferable.

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 undergoes a complex formation reaction with a metal ion constituting the sparingly soluble metal compound using water as a medium; Preferably, the pH of the yarn is increased by the reaction of the two stiffening compounds during 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.

The poorly soluble metal compound and the complex forming compound need to be added at least in separate layers in order to prevent them from reacting before the development process. For example, in a so-called mono-sheet 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, and one or more layers are 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. Hardly soluble metal compounds are disclosed in Japanese Patent Application Publication No. 5
6-174830, 53-102733, etc., and the average particle size thereof is 50 microns or less.
Particularly preferred is 5 microns or less. The releasable metal compound may be added to any layer of the photosensitive element, such as the photosensitive layer, intermediate layer, or protective layer, or may be added divided into two or more layers.

The amount of a poorly soluble metal compound or complex-forming compound to be added to the layer on the support depends on the type of compound, the particle size of the poorly soluble metal compound, the rate of complex formation reaction, etc. It is appropriate to use it in an amount of 50 weight percent or less, and more preferably a range of 0.01 weight percent to 40 ffi ffl percent. In addition, when the complex-forming compound is dissolved in water and supplied, 0.005 mo1 to 5 mo1 per liter. A concentration of 0.05 mol to 2 mol is particularly preferred. Furthermore, in the present invention, the content of the complex-forming compound in the reaction system is 1/100 to 100 times, particularly 1/10 to 2 times, in molar ratio relative to the content of the poorly soluble metal compound.
0 times is preferable.

The method for adding water to the photosensitive layer or dye fixing layer is as follows:
For example, page 101, line 9 of Japanese Patent Application No. 59-268926.
There is a method described on page 102, line 4.

As heating means in the development and/or transfer process, heat plates, irons, heat rollers, etc.
There is a means described in No. 8926, page 102, line 14 to page 103, line 11. Alternatively, the photosensitive element and/or the dye fixing element may be coated with a layer of conductive material such as graphite, carbon black, metal, etc., and the conductive layer may be heated directly by passing an electric current through it. 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 described in Japanese Patent Application No. 59-2689.
The method described in No. 26, pages 103 to 104 can be applied.

Any of the following thermal development equipment can be used to process the photographic elements of this invention. For example, JP-A No. 59-75247,
Apparatuses described in Japanese Patent No. 59-177547, No. 59-181353, 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 (I) that 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 provides high dye 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.

(2) 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, how to prepare a benzotriazole silver emulsion will be described.

28 g of gelatin and 13.2 g of benzotriazole were dissolved in 3000 ndl of water. This solution was kept at 40°C and stirred. Add 17g of silver nitrate to this solution.
was dissolved in 100 n+ffi of water and added over 2 minutes.

The pH of the benzotriazole silver emulsion was adjusted and allowed to settle to remove excess salt.

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 aqueous gelatin solution (20 g of seratin and 3 g of sodium chloride in 100011 λ of water kept at 75°C) was mixed with 600 mN of an aqueous solution containing sodium chloride and potassium bromide and an aqueous solution of silver nitrate (600 mN of water).
0.59 mol of silver nitrate dissolved in 1'112) was simultaneously added at an equal flow rate over a period of 40 minutes. In this way, a monodisperse cubic silver chlorobromide emulsion (80 mol % bromine) with an average grain size of 0.35 μs was prepared.

After washing with water and desalting, 5 mg of sodium thiosulfate and 4-
Chemical sensitization was carried out at 60° C. by adding 20+++ g of hydroxy-6-methyl-1,3°3a,7-chitrazaindene. The yield of emulsion was 600 g.

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, 0.5 g of sodium succinate-2-ethyl-hexyl ester sulfonate and 5 g of triiso-nonyl phosphate as surfactants, 15 g of cyclohexanone The mixture was heated to approximately 60° C. to form a homogeneous solution.

After stirring and mixing this solution and 100 g of a 10% solution of lime-treated gelatin, the mixture was heated using a homogenizer for 10 minutes at 10.0 g.
Dispersion was carried out at 00 rpm.

This dispersion is called magenta dye-providing substance dispersion A.

A method for preparing photosensitive coatings will be described.

a) Benzotriazole silver emulsion 10 gb) Photosensitive silver chlorobromide emulsion 15 gC) Dispersion A of dye-providing substance 25 gd) 5% of the following compounds
Aqueous solutionC9H+900+CH2CH20)8H5m1e) 10% methanol solution of benzenesulfonamide 5D or [)p-
5% aqueous solution of guanidine chlorphenylsulfonylacetate 25m9 or more a)
~f) were mixed and a thickener (e.g. polystyrene-P-sulfonic acid sorter) and water were added to 100 ni.

This solution was applied to a wet film thickness of 50 mm on a polyethylene terephthalate film having a thickness of 180 mm.

Next, the following protective layer coating composition was prepared.

Protective layer coating composition g) 10% Seratin 400gh) p
-Chlorphenylsulfonyl guanidine acetate 5% aqueous solution 4 30 mui)
0ml of 4% aqueous solution of hardener with the following structural formula Ct12= CHSO□Ct12CONII (e11□
) Mix OCH□502ell=C11□ with 2NH, add a thickener and water, and make 1000 nu
I made it.

This coating composition was coated on the above photosensitive coating material to a thickness of 30 mm, and then dried to form a photosensitive material No. 3. 1 was produced.

These photosensitive materials were exposed to 5,000 yen using a tungsten light bulb.
Imagewise exposure was made for 1 second at lux.

Thereafter, it was heated uniformly for 30 seconds using a heat block-L heated to 150°C.

Next, a method for forming a dye-fixing material suitable for an image-receiving layer will be described.

Dissolve 10g of poly(methyl acrylate-N,N,N-trimethyl-N-vinylbenzylammonium chloride) (the ratio of methyl acrylate and vinylbenzylammonium chloride is 1:1) in 180+nJZ water, and add 10% lime-treated ceratin. 100 g and 20 g of a 4% aqueous solution of 1,4-bis(2',3'-epoxypropoxy)butane were uniformly mixed. 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 . made.

Similarly, using 4.5 g of cyan dye-donating substance (5),
Photosensitive material No. 003 was made.

After 30 seconds, peel off the dye fixing material from the photosensitive material.
Negative magenta, yellow, and cyan dye images were obtained.

The density of the negative image was measured using a Macbeth reflection densitometer using green light, blue light, and red light, respectively. The results are shown in the table below.

It has been found that transferred dye images with sufficient distinctiveness can be obtained using the dye-providing substance of the present invention.

Example 2 Add 1 g of the following reducing agent to the dispersion of each dye-donating substance used in Example 1 (in the same manner as above, except that it was dissolved in triisononyl phosphate at the same time as the dye-donating substance).
Photosensitive material no.

I made 4.5.6. This was treated in the same manner as in Example 1, and the results obtained are shown in the following table.

It can be seen that the image distinguishability is improved by using a reducing agent in combination.

Example 3 A light-sensitive material was prepared by replacing the dye-donor 1F as shown in the table below, and processed in the same manner as in Example 1. The results are shown below.

■ *Amount used when making a dispersion of a dye-providing substance ** Same as in Example 2 Example 4 Using the emulsion of Example 1 and dispersion (2) of a dye-providing substance, the following procedure was carried out. A photosensitive coating was prepared.

a) Benzotriazole silver emulsion 10gb) Photosensitive silver chlorobromide emulsion 15gC) Dispersion A of dye-providing substance 25gd) 5% aqueous solution of the following compound C9Hl900+ CH2CH20) (IHS- or above a) to d) were mixed. , thickeners (e.g. polystyrene-p
- sulfonic acid sorter) and water were added to make up to 100 +ijl. This solution was applied to a wet film thickness of 50 mm on a 180 mm polyethylene terephthalate film.

Next, the following protective layer coating composition was prepared.

e) 10% Ceratin 400gf) Zinc hydroxide (average size 0.2 units 94g g) 50 companies 4% aqueous solution of hardener with structural formula of F (:112==CH30□(:H2C0NH(CI(
2) H2 was mixed with 2NHCOCH2So□CH=, and a thickener and water were added to make the mixture 100100O.

Apply 30p1 of this coating composition onto the above photosensitive coating.
After coating to a thickness of , it is dried to form photosensitive material No. 11
was created.

Photosensitive material No. 12 was prepared in exactly the same manner as photosensitive material No. 11 except that 1 g of a reducing agent (same as in Example 2) was added to the dispersion of the dye-donating substance (2).

Next, we will discuss how to make the dye fixing material.

63 g of gelatin, 130 g of a mordant having the following structure, and 80 g of guanidine picolinate were dissolved in 300 ml of water, uniformly coated on a paper support laminated with polyethylene to a wet film thickness of 45 mm, and then dried.

Furthermore, a solution prepared by dissolving 35 g of ceratin and 1.05 g of 1.2-bis(vinylsulfonylacetamidoethane) in water was applied to a wet film thickness of 17 mm and dried to prepare a dye fixing material. Ta.

The above photosensitive material was imagewise exposed for 1 second at 5000 lux using a tungsten bulb.

Water of 1011 N/bar was supplied to the emulsion surface of the exposed light-sensitive material using a wire bar, and the material was then 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 beat 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 macenta image was obtained on the fixing material. The results of concentration measurements are shown in the table below.

Example 5 Light-sensitive materials Nos. f3 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.

*Amount used when preparing a dispersion of the dye-providing substance **Same as that in Example 2 *Umbrella (a) Comparative compound 61+11 (L) The effects of the present invention are clear from the above examples.

Applicant: Fuji Photo Film Co., Ltd. i; Agent: Patent attorney Minoru Watanabe, ′, :・]

Claims (1)

[Scope of Claims] A support comprising at least a photosensitive silver halide, a binder, and a dye-donating substance represented by the following general formula (I) that releases a diffusible dye upon oxidation during development. color photographic material. General formula (I) ▲ Numerical formulas, chemical formulas, tables, etc.▼ (In the above general formula (I), R_1 and R_2 are hydrogen atoms, halogen atoms, cyano groups, alkyl groups, aryl groups, heterocyclic groups, 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 arylsulfonyl group, R_1 At least one of R_2 and R_2 has 10 or more carbon atoms. Dye represents a dye group or a dye precursor group. )