JPH0222649A - Color photosensitive material - Google Patents

Abstract

PURPOSE:To enhance raw storage stability by dispersing a dye producing compound and/or a dispersion resistant reducing agent into an organic solvent specified in viscosity and dielectric constant and high in boiling point. CONSTITUTION:The dye producing compound and/or the dispersion resistant reducing agent are dispersed into the organic solvent having a viscosity at 25 deg.C of >=50cp and a dielectric constant of <=10, and it is preferred to select the compound having a melting point of >=10 deg.C and up to a temperature of 20 deg.C higher than a developing temperature and a dielectric constant of 9-1 in order that said reducible dye-producing compound sufficiently reacts with said dispersion resistant agent in said solvent at the time of development, and said dispersion has excellent raw storage stability.

Description

Detailed Description of the Invention (Industrial Application Field) The present invention relates to a color photosensitive material, and in particular to a color photosensitive material that can provide a positive color image with high density and good color reproducibility, and has a long shelf life. This paper relates to excellent color photosensitive materials.

(Prior Art and its Problems) Many methods have been proposed for obtaining positive color images by diffusion transfer.

For example, US Pat. No. 4,559,290, US Pat. No. 4,356.2
No. 49, No. 4,358.525, JP-A-53-355
No. 33, No. 53-110827, No. 54-13092
No. 7, No. 56-164342, No. 59-154445
No. 1, Japanese Patent Application No. 61-88625, etc., an oxidized dye-donating compound without dye-releasing ability is allowed to coexist with a reducing agent or its precursor, and wet development or thermal development is performed to adjust the amount of exposure of silver halide. A method has been proposed in which the reducing agent is oxidized and the remaining unoxidized reducing agent is used for reduction to release a diffusible dye. Also, European Patent Publication 220746
No. 87-6199 (No. 12S22),
N-
Color light-sensitive materials have been described that use non-diffusible compounds that release diffusible dyes upon reductive cleavage of an X bond (X represents an oxygen, nitrogen, or sulfur atom).

However, when the above-mentioned reducible dye-providing compound is used in combination with a silver halide emulsion together with a reducing agent or its precursor, there are problems in that color images are highly stained and storage stability is poor. I understand.

In order to suppress staining and increase image density in color light-sensitive materials for positive image formation using such reducible dye-donating compounds, in addition to a diffusion-resistant reducing agent (electron donor) as a reducing agent, It is particularly desirable to mix and dissolve the electron donor and the reducible dye-donating compound in a high-boiling organic solvent using a diffusible electron transfer agent, and then disperse the mixture in a binder. In this case, the electron donor and the reducible dye-donating compound undergo an oxidation-reduction reaction, and as a result, the dye is separated by 'ti', which tends to increase staining in the image.Therefore, further improvement is desired.

(Objective of the Invention) The first object of the present invention is to improve the shelf life of a color light-sensitive material using a reducible dye-providing compound. The second object is to provide a color photosensitive material with high density and low stain.

(Structure of the Invention) An object of the present invention is to provide a color photosensitive material containing at least a photosensitive silver halide, a binder, a reducible dye-providing compound, and a diffusion-resistant reducing agent on a support. Compound and/or diffusion-resistant reducing agent at 25°C
The viscosity is 50 centipoise or more and the dielectric constant is l
This was achieved using a color photosensitive material characterized by being dispersed in an organic solvent with a high boiling point of O or less.

In the present invention, in order for the reducible dye-providing compound and the diffusion-resistant reducing agent to react sufficiently during development in a high-boiling organic solvent having the above-mentioned physical properties, and to have excellent raw storage stability, Compounds with a melting point of 10°C or higher and a development temperature plus 20°C or lower are particularly desirable, and have a dielectric constant of 9 or lower! The above compounds are particularly desirable.

The reducible dye-providing compound and the diffusion-resistant reducing agent can be dissolved and dispersed together in the high-boiling organic solvent of the present invention, or they can be prepared as separate dispersions. In the latter case, at least one is dispersed using the high boiling point organic solvent of the present invention, while the other is dispersed using a known high boiling point organic solvent and/or a low boiling point organic solvent described below or Japanese Patent Publication No. 51-3.
9853, JP-A No. 51-59943, etc., may be used for dispersion.

Examples of high-boiling organic solvents used in the present invention are shown below, but the present invention is not limited to these compounds.

Viscosity permittivity (11(i 5o-C, HtqOhP=080.6cp 3.95 f21 (n C+aHi*0tvP=04, O
1 1h CHs tHs CyoHs CHg C00C1ffHty(iso) CH2C00
C+3Hzq(iso) ■ C00CIllHzqOsO) CH2 HOH COOC+sHx, (iso) In the present invention, a dye-donating compound and/or a diffusion-resistant reducing agent (electron donor) are dissolved and dispersed in the high-boiling organic solvent. In this case, the boiling point is 50°C to 160°C as necessary.
It can be used in combination with a low boiling point organic solvent at .degree.

Also, Japanese Patent Publication No. 51-39853, Japanese Patent Publication No. 51-5994
Polymers described in No. 3 etc. may be used in combination.

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 compound or diffusion-resistant reducing agent (or their sum, if used together). Further, it is suitable that the amount is 1 cc or less, more preferably 0.5 cc or less, particularly 0.3 cc or less per 1 g of binder.

Various surfactants known for use in dispersing hydrophobic compounds in hydrophilic colloids can also be used here. For example, those listed as surfactants on pages (37) to (38) of JP-A-59-157636 can be used.

Next, the reducible dye-providing compound used in the present invention will be explained.

The reducible dye-providing compound used in the present invention is preferably a compound represented by the following general formula (C-I).

pwR-(Time)t-Dye General formula (
Cl), where PWR is reduced to (Tim
e) Represents a group that releases t-D y e.

Time is from PWR -(Time)t -D y e
represents a group that releases Dye through a subsequent reaction after being released as Dye.

t represents an integer of 0 or 1.

[)ye represents a dye or its precursor.

First, PWR will be explained in detail.

For PWR, US Patent No. 4,139,389, or US Patent No. 4,139,379, US Patent No. 4,564.577,
Electron-accepting center and intramolecular nucleophilic substitution reaction in a compound that releases a photographic reagent by an intramolecular nucleophilic substitution reaction after being reduced as disclosed in JP-A-59-185333 and JP-A-57-84453 It may correspond to the part including the center, or it may correspond to the part including the center, or as described in U.S. Pat. No. 4,232,107.
As disclosed in JP-A No. 59-101649, Research Disclosure (1984) IV, No. 24025, or JP-A No. 61-88257, the photographic reagent is eliminated by an electron transfer reaction within the molecule after being reduced. It may correspond to the electron-accepting quinonoid center in the compound and the carbon atom-containing moiety that connects it to the photographic reagent.
No. 30, U.S. Patent No. 4,343.893, U.S. Patent No. 4,619
．． No. 884, the single bond is cleaved to release the photographic reagent after reduction, and the atom (sulfur atom or It may correspond to a moiety containing a carbon atom or a nitrogen atom). Also, U.S. Patent 4,45
It may correspond to a moiety containing a nitro group in a nitro compound that releases a photographic reagent after electron acceptance and a carbon atom that connects the photographic reagent with the nitro group as disclosed in No. 0.223. , corresponds to the geminal dinitro moiety in the dinitro compound that beta-desorbs the photographic reagent after electron acceptance and the moiety containing the carbon atom linking it to the photographic reagent described in U.S. Pat. No. 4,609,510. It may be.

In addition, a compound containing So, -X (X represents oxygen, sulfur, or nitrogen) and an electron-withdrawing group in one molecule as described in Japanese Patent Application No. 106885/1982;
Compound containing a po-x bond (X has the same meaning as above) and an electron-withdrawing group in one molecule described in No. 06895, patent application No. 6
Examples include compounds having a c-x' bond (X' is synonymous with X or represents -302-) and an electron-withdrawing group in one molecule as described in No. 2-106887.

In order to more fully achieve the object of the present invention, N-X A compound having a bond (X represents an oxygen, sulfur or nitrogen atom) and an electron-withdrawing group, that is, a compound represented by the following general formula (CI+) is preferred.

The general formula (CI[] EAG (Time)-t Dye is bonded to at least one of R'O' % R"" or EAG.

The portion corresponding to PWR in general formula (CI+) will be explained.

X represents a group (-NCR'')-) containing an oxygen atom (-0-), a sulfur atom (-3-), or a nitrogen atom.

R"', R"" and Rloff represent a group other than a hydrogen atom or a simple bond.

RIOI, R1o! Groups other than hydrogen atoms represented by You may do so.

R"' and R103 are preferably substituted or unsubstituted alkyl groups, alkenyl groups, alkynyl groups, aryl groups, heterocyclic groups, acyl groups, sulfonyl groups, etc. RI
The number of carbon atoms in OI and R10'' is preferably 1 to 40.

Preferable examples of RIOf include substituted or unsubstituted acyl groups and sulfonyl groups, which are the same as the acyl groups and sulfonyl groups described for RIOI and RI03. The number of carbon atoms is preferably 1 to 40.

R1+II, R+O2 and R103 may be bonded to each other to form a 5- to 6-membered ring.

As X, oxygen is particularly preferred.

EAG will be described later.

Furthermore, in order to achieve the object of the present invention, the general formula (CII
) Among the compounds represented by the formula (CI[I), those represented by the general formula (CI[I) are preferred.

The general formula (CI[l) BAG (Time-)-71)ye binds to at least one of R1"' and EAG.

X has the same meaning as above.

R104 represents an atomic group that is bonded to X and a nitrogen atom to form a five- or six-membered monocyclic or condensed heterocycle including the nitrogen atom.

EAG represents a group that accepts or takes electrons from a reducing substance, and is bonded to a nitrogen atom. EAG is preferably a group represented by the following general formula (A).

General formula (A) In general formula (A), Zt represents -C-3ub or -N-.

v and l represent an atomic group forming a three- to six-membered aromatic group together with Zt and Zt, and n represents an integer from 3 to 3.

VaiZz-1v, 1-Zs-Z, -1■.

i Zs Za Zs-1Vb ;-Z3
Za -Za-z, -1Vt; Zs Za
Zs ZhZ, -1V8; Z3 Za Zs -Zb Zt''-Z
It is m-.

Each Sub 5ub Z z Z s is -C--Nub S-2 or -3O! -, each Sub represents a simple bond (pi bond), a hydrogen atom, or a substituent described below, even if each Sub is the same,
Each of them may be different, or each may be bonded to each other to form a king to six-membered saturated or unsaturated carbocycle or heterocycle.

In general formula (A), the sum of the Hammett substituent constant sigma variations of the substituents is +0.50 or more, more preferably +0.
Select Sub so that it is 70 or more, most preferably +0°85 or more.

EAG is preferably an aryl group or a heterocyclic group substituted with at least one electron-withdrawing group. The substituents bonded to the aryl group or 〇-heterocyclic group of BAG can be used to adjust the physical properties of the entire chemical compound. Examples of the physical properties of the entire compound include ease of accepting electrons, water solubility, oil solubility, diffusibility, sublimation, melting point, dispersibility with binders such as gelatin, and reactivity with nucleophilic groups. , can be used to adjust reactivity to electrophilic groups, etc.

A specific example of an EAG is described in European Patent Publication No. 220746A2, pages 6-7.

Time may lead to the cleavage of nitrogen-oxygen, nitrogen-nitrogen or nitrogen-sulfur bonds, resulting in D
Represents a group that releases ye.

Various groups represented by Time are known, for example, JP-A-61-147244, pages (5)-(6), JP-A-61-147244, pages 61-
No. 236549 (8) page-page, patent application No. 6l-88625
Examples include the groups described on page (36) = page (44).

Dyes include azo dyes, azomethine dyes, anthraquinone dyes, naphthoquinone dyes, styryl dyes,
These include nitro dyes, quinoline dyes, carbonyl dyes, and phthalocyanine dyes. Note that these dyes can also be used in the form of a temporarily shortened wavelength that can be multicolored during development.

Specifically, BP76.492A, JP 59-165
Dye disclosed in No. 054 can be used.

The compound represented by the above-mentioned catalytic formula (Cn) or (C1ff) must itself be immobile in the photographic layer,
For that purpose, EA G, R1111, R1etR11
It is desirable to have a ballast group having 8 or more carbon atoms at the 14 or X position (particularly at the BAG position).

Typical specific examples of the reducible dye-providing compound used in the present invention are listed below, but the present invention is not limited thereto, and is described in European Patent Publication No. 220746A2, Publication Branch Axis No. 87-6199, etc. Dye-providing compounds that have been described can also be used.

(lO) C+61133 CIffHtt Each of these compounds can be synthesized by the methods described in the patent specifications cited above.

The amount of the dye-donating compound used depends on the extinction coefficient of the dye, but is 0.05 to 5 mmol/rd, preferably 0.1 to 5 mmol/rd.
The dye-donating substances having a concentration of 3 mmol/rd can be used alone or in combination of two or more. In addition, in order to obtain images of black or different hues,
As described in No. 2251, mobile dyes having different hues, for example, at least one of cyan, magenta, and yellow dye-providing substances are mixed and contained in a layer containing silver halide or in an adjacent layer. It is also possible to use a mixture of two or more types of dye-providing substances that emit .

In the present invention, a diffusion-resistant reducing agent is used, and details of this compound are described in European Patent Publication No. 220746A2, Published Technical Publication No. 87-6199, and the like. Particularly preferred diffusion-resistant reducing agents include the following general formula (C) or (
This is a compound represented by D).

General formula (C) General formula CD) In the formula, A1° and A+OZ each represent a hydrogen atom or a protecting group for a phenolic hydroxyl group that can be deprotected with a nucleophilic reagent.

Here, examples of nucleophilic reagents include OHe, Roe (R; alkyl group, oryl group, etc.), hydroxamic acid anions, etc. ! Examples include anionic reagents such as e, and compounds having lone pairs of electrons such as primary or secondary amines, hydrazine, hydroxylamines, alcohols, and thiols.

A1゜1. A. Preferred examples of 2 include a hydrogen atom, an acyl group, an alkylsulfonyl group, an arylsulfonyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a dialkylphosphoryl group, a dialkylphosphoryl group, or JP-A-59-197037, JP-A-59-20.
It may be a protecting group disclosed in No. 105, and A1
゜1, A1゜2 is Niha R201, RZ OZ if possible
, RZ' 2 and R204 may be combined with each other to form a ring. A again. I and A+oz may both be the same or different.

R201, Rlot, Rzo3 and R204 are each a hydrogen atom, an alkyl group, an aryl group, an alkylthio group, a ruthio group, a sulfonyl group, a sulfo group, a halogen atom, a cyano group, a carbamoyl group, a sulfamoyl group, an amide group, an imido group , carboxyl group, sulfonamide group, etc. These groups may have a substituent if possible.

However, the total number of carbon atoms in R"'%R"' is 8 or more. In addition, in -a formula (C), R2111 and R"" and/or R11 and R204 are combined with each other to form a saturated or unsaturated ring. may be formed.

Among the electron donors represented by the general formula (C) or CD), those in which at least two of Rt·1 to R204 are substituents other than hydrogen atoms are preferable. Particularly preferable compounds include R211+ and Rzox. Few (on the other hand,
and at least one of Rt62 and Rzoa is a substituent other than a hydrogen atom.

A plurality of diffusion-resistant reducing agents may be used in combination, or a diffusion-resistant reducing agent and its precursor may be used in combination.

Specific examples of the diffusion-resistant reducing agent are listed below, but the present invention is not limited to these compounds.

CH3 (ED (ED-9) (ED CH.

(ED-13) The amount of the diffusion-resistant reducing agent of the present invention added is 0.001 to 20 mol, particularly preferably 0.01 to 10 mol, per 1 mol of silver.
It is a mole. Further, the amount is 0.05 to 10 mol, particularly preferably 0.1 to 5 mol, per 1 mol of the reducible dye-donating substance.

It is also possible to use a combination of the diffusion-resistant reducing agent of the present invention and a known reducing agent.

Examples of known reducing agents include U.S. Pat.
Columns 49-50 of No. 26, Columns 30-31 of No. 4.483.914, No. 4,330°617, No. 4.
No. 590.152, No. Q of JP-A-60-140335
? l~as pages, No. 57-40245, No. 56-13
No. 8736, No. 59-178458, No. 59-538
No. 31, No. 59182449, No. 59-182450
No. 60-119555, No. 60-128436 to No. 60-128439, No. 60-19854
No. 0, No. 60-181742, No. 61-259253
No. 62-244044, No. 62131253 to No. 62-131256, European Patent No. 220,7
There are reducing agents and reducing agent precursors described in pages 78 to 96 of No. 46A2.

Since the reducing agent of the present invention has low diffusivity, the reducing agent of the present invention (
It is preferred to use a combination of electron transfer agents and/or electron transfer agent precursors to facilitate electron transfer between the electron donor (electron donor) and the developable silver halide.

The electron transfer agent or its precursor can be selected from the aforementioned reducing agents or its precursors. It is desirable that the mobility of the electron transfer agent or its precursor is greater than that of the diffusion-resistant reducing agent (electron donor).

Particularly useful electron transfer agents are 1-phenyl-3-pyrazolidones or aminophenols.

The combination of electron donor and electron transfer agent of the present invention is preferably incorporated into a color photosensitive material.

Electron donors, electron transfer agents, or their precursors can be used in combination of two or more, and can be used in combinations of two or more types of electron donors, electron transfer agents, or their precursors. etc.), it can be added only to some emulsion layers, it can be added to layers adjacent to the emulsion (antihalation layer, undercoat layer, intermediate layer, protective layer, etc.), or it can be added to all emulsion layers. It can also be added to the layer. The electron donor and the electron transfer agent can be added to the same layer or to separate layers. In addition, these reducing agents can be added to the same layer as the dye-donating compound or to a separate layer, but
The diffusion-resistant reducing agent (electron donor) is preferably present in the same layer as the dye-donating compound, particularly preferably in the phase of the high-boiling R solvent of the present invention together with the dye-donating compound.

The electron transfer agent can be incorporated into the dye-fixing material, or
When a solvent is present during development, it may be dissolved in this solvent.

The light-sensitive material of the present invention basically contains a photosensitive silver halide, a binder, a reducing agent, a reducible dye-providing compound, and a high-boiling organic solvent on a support. These components are often added to the same layer, but if they are in a reactable state, they can be added separately to separate layers.
For example, if a colored dye-providing compound is present in the lower layer of the silver halide emulsion, deterioration in color can be prevented. When the reducing agent is added not only to the emulsion layer but also to the intermediate layer, color reproducibility is improved.

In order to obtain a wide range of colors in the chromaticity diagram using the three primary colors yellow, magenta, and cyan, at least three silver halide emulsion layers each sensitive to a different spectral region are used in combination.

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 photosensitive layer can be arranged in various arrangements known for conventional color photosensitive materials.

Further, each of these photosensitive layers may be divided into two or more layers as necessary.

The light-sensitive material of the present invention can be provided with various auxiliary layers such as a protective layer, an undercoat layer, an intermediate layer, a yellow filter layer, an antihalation layer, and a back layer.

Silver halides that can be used in the present invention include silver chloride, silver bromide,
Any of silver iodobromide, silver chlorobromide, silver chloroiodide, and silver chloroiodobromide may be used.

The silver halide emulsion used in the present invention may be a surface latent image type emulsion or an internal latent image type emulsion. The internal latent image type emulsion is used as a direct reversal emulsion in combination with a nucleating agent and an optical coupler. 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.
Silver halide emulsions may be monodisperse or polydisperse, and monodisperse emulsions may be mixed and used. Grain size is 0.1 to 2.
μ, particularly preferably 0.2 to 1.5 μ. The crystal habit of the silver halide grains may be cubic, octahedral, tetradecahedral, tabular with a high aspect ratio, or any other form.

Specifically, U.S. Pat. No. 4,500,626, column 50, U.S. Pat.
Any of the silver halide emulsions described in JP-A-62-253159 and the like can be used.

Although silver halide emulsions may be used unripe, they are usually used after being chemically sensitized.8 Emulsions for conventional light-sensitive materials include well-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 (JP-A-62-253159).

The coating amount of the photosensitive silver halide used in the present invention is in the range of 1 to 10 g/m in terms of silver.

In the present invention, an organic metal salt can also be used as an oxidizing agent together with photosensitive silver halide.

Among such organic metal salts, organic silver salts are particularly preferably used.

Organic compounds that can be used to form the above-mentioned organic silver salt oxidizing agents include U.S. Pat.
There are benzotriazoles, fatty acids, and other compounds described in column 53, etc. Also useful are silver salts of carboxylic acids having an alkynyl group, such as silver phenylpropiolate described in JP-A-60-113235, and acetylene silver as described in JP-A-61-249044. Two or more types of organic silver salts may be used in combination.

The above organic silver salts can be used in combination in an amount of 0.01 to 10 mol, preferably 0°Ol to 1 mol, per 1 mol of photosensitive halide tM. The total coating amount of photosensitive silver halide and organic silver salt is 50 to 10 cm in terms of silver.
g/rd is appropriate.

Various antifoggants or photographic stabilizers can be used in the present invention. An example is RD176
43 (1978) pages 24-25, nitrogen-containing carboxylic acids and phosphoric acids described in JP-A-59-168442, or mercapto compounds and their Metal salts, acetylene compounds described in JP-A No. 62-87957, and the like are used.

The silver halide used in the present invention may be spectrally sensitized with methine dyes and others. The pigments used include cyanine pigments, merocyanine pigments, composite cyanine pigments, composite merocyanine pigments, holopolar cyanine pigments,
Included are hemicyanine dyes, styryl dyes and hemioxonol dyes.

Specifically, U.S. Pat.
17029 (1978) 12-13 Shin et al.

These sensitizing dyes may be used alone or in combination (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 does not itself have a spectral sensitizing effect or a compound that does not substantially absorb visible light and exhibits supersensitization (for example, as described in U.S. Pat. , No. 615゜641, patent application No. 61-22
6294 etc.).

These sensitizing dyes may be added to the emulsion during or before or after chemical ripening.
It may be added before or after nucleation of silver halide grains according to No. 756 and No. 4,225,666, and the amount added is generally about lo-8 to 10-2 moles per mole of silver halide.

A hydrophilic binder is preferably used for the constituent layers of the photosensitive material or dye fixing material. Examples include those described on pages (26) to (2) of JP-A-62-253159.

Specifically, transparent or translucent hydrophilic binders are preferred, and include natural compounds such as proteins or cellulose derivatives such as gelatin and gelatin MR, and polysaccharides such as starch, gum arabic, dextran, and pullulan.
Examples include polyvinyl alcohol, polyvinylpyrrolidone, acrylamide polymer, and other synthetic polymer compounds. In addition, super absorbent polymers described in JP-A-62-245260 etc., namely -COOM or -3O,M(
M is a hydrogen atom or an alkali metal), or a copolymer of these vinyl monomers with each other or with other vinyl monomers (e.g., sodium methacrylate, ammonium methacrylate, Sumitomo Chemical (
Sumikagel L-5H) manufactured by Co., Ltd. is also used. Two or more of these binders can also be used in combination.

When employing a system that performs thermal development by supplying Hl water, the use of the above-mentioned super absorbent polymer allows rapid absorption of water. Further, when a highly water-absorbing polymer is used in the dye fixing layer or its protective layer, it is possible to prevent the dye from being retransferred from the dye fixing material to another material after transfer.

In the present invention, the amount of binder applied is 20% per 1%.
The amount is preferably 10 g or less, more preferably 7 g or less.

Constituent layers (including back layers) of photosensitive materials or dye-fixing materials contain various polymers for the purpose of improving film properties such as dimensional stabilization, prevention of curling, prevention of adhesion, prevention of film cracking, and prevention of pressure sensitivity. It can contain latex. Specifically, Japanese Patent Publication Nos. 62245258 and 62-1366
Any of the polymer latexes described in No. 48, No. 62-110066, etc. can be used. In particular, using a polymer latex with a low glass transition point (below 40°C) for the mordant layer can prevent cracking of the mordant layer, and using a polymer latex with a high glass transition point for the back layer can prevent curling. can get.

In the present invention, a compound that activates development and stabilizes images can be used in the light-sensitive material. For specific compounds preferably used, see U.S. Patent No. 4,50.
No. 0,626, 51-52 WI.

In systems that form images by diffusion transfer of dyes, a dye-fixing material is used together with a light-sensitive material. Even if the dye-fixing material is coated separately on a support separate from the light-sensitive material, It may also be coated on the same support. Regarding the relationship between the light-sensitive material and the dye-fixing material, the relationship with the support, and the relationship with the white reflective layer, the relationships described in column 57 of US Pat. No. 4,500.626 can also be applied to the present application.

The dye fixing material preferably used in the present invention has at least one layer containing a mordant and a binder. As the mordant, those known in the photographic field can be used, and specific examples thereof include U.S. Pat. The mordant described in JP-A No. 62-244043, No. 62-
Examples include those described in No. 244036 and the like.

Also, dye-receiving polymeric compounds such as those described in US Pat. No. 4,463,079 may be used.

The dye fixing material 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.

A high boiling point organic solvent can be used in the constituent layers of the light-sensitive material and the dye-fixing material as a plasticizer, a slippery agent, or a peelability improver between the light-sensitive material and the dye-fixing material. Specifically, pages (25) and 62 of JP-A-62-253159.
-245253, etc.

Furthermore, for the above purpose, various silicone oils (all silicone oils from dimethyl silicone oil to modified silicone oil in which various organic groups are introduced into dimethylsiloxane) can be used. Examples include various modified silicone oils, especially carboxy-modified silicone (trade name: X-22
3710) etc. are effective.

Also, Japanese Patent Application Laid-Open No. 62-215953, Japanese Patent Application No. 62-236
The silicone oil described in No. 87 is also effective.

Antifading agents may be used in the photosensitive materials and dye fixing materials. Antifading agents include, for example, antioxidants, ultraviolet absorbers, or certain metal complexes.

Examples of antioxidants include chroman compounds, coumaran compounds, phenol compounds (for example, hindered phenols), hydroquinone derivatives, hindered amine derivatives, and spiroindane compounds. Compounds described in JP-A-61-159644 are also effective.

Benzotriazole compounds (
U.S. Patent No. 3,533,794, etc.), 4-thiazolidone compounds (U.S. Patent No. 3,352,681, etc.)
, benzophenone compounds (JP-A-46-2784, etc.), and other JP-A-54-48535, JP-A-62-13
In addition to the compounds described in JP-A-6641 and JP-A-61-88256, ultraviolet absorbing polymers described in JP-A-62-260152 are also effective.

As metal complexes, US Patent No. 4. 241. 155
No. 4,245,018, columns 3 to 36, No. 4,
No. 254,195, columns 3 to 8, JP-A-62-17474
There are compounds described in Japanese Patent Application No. 1, No. 61-88256, pages (27) to (29), Japanese Patent Application No. 62-234103, Japanese Patent Application No. 62-31096, and Japanese Patent Application No. 62-230596.

Examples of useful anti-fading agents are disclosed in JP-A No. 62-215272 (
125) to (137).

The anti-fading agent for preventing fading of the dye transferred to the dye-fixing material may be included in the dye-fixing material in advance, or may be supplied to the dye-fixing material from outside the photosensitive material. .

The above antioxidants, ultraviolet absorbers, and metal complexes may be used in combination.

A fluorescent whitening agent may be used in the photosensitive material or dye fixing material. In particular, it is preferable to incorporate a fluorescent whitening agent into the dye-fixing material or to supply it from outside the photosensitive material. An example is K.

Veenkataraman W rThe Chem
istry of 5ynLheticDyesJ Chapter V
Examples include compounds described in Vol. 8, Chapter 8, JP-A-61-143752, and the like. More specifically,
Examples include stilbene compounds, coumarin compounds, biphenyl compounds, benzoxacylyl compounds, naphthalimide compounds, pyrazoline compounds, and carbostyryl compounds.

Optical brighteners can be used in combination with antifade agents.

Hardeners used in constituent layers of photosensitive materials and dye-fixing materials include U.S. Pat.
Examples include hardeners described in No. 18942 and the like. More specifically, aldehyde hardeners (formaldehyde, etc.), aziridine hardeners, epoxy hardeners, vinylsulfone hardeners (N,N'-ethylenebis(vinylsulfonylacetamide)ethane, etc.) ), N-methylol hardeners (such as dimethylol urea), and polymer hardeners (compounds described in JP-A No. 62-234157, etc.).

Various surfactants can be used in constituent layers of photosensitive materials and dye fixing materials for purposes such as coating aids, improving peelability, improving slipperiness, preventing static electricity, and promoting development. Specific examples of surfactants are given in JP-A-62-173463 and JP-A-62-18.
It is described in No. 3457, etc.

The constituent layers of photosensitive materials and dye-fixing materials include improved slipperiness,
An organic fluoro compound may be included for the purpose of preventing static electricity and improving peelability. Representative examples of organic fluoro compounds include Japanese Patent Publication No. 57-9053, columns 8 to 17,
20944, 62-135826, etc., or hydrophobic agents such as oily fluorine compounds such as fluorine oil or solid fluorine compound resins such as tetrafluoroethylene resin. Examples include fluorine compounds.

A matting agent can be used in the photosensitive material and the dye fixing material. As a matting agent, silicon dioxide, polyolefin or polymethacrylate may be used.
In addition to the compounds described in No. 6 (page 29), benzoguanamine resin beads, polycarbonate resin beads, AS resin beads, etc.
There is a compound described in No. 0065.

In addition, the constituent layers of the light-sensitive material and the dye-fixing material may contain a thermal solvent, an antifoaming agent, an antibacterial agent, colloidal silica, and the like. Specific examples of these additives are given in JP-A-61-
No. 88256, pages (26) to (32).

In the present invention, an image formation accelerator can be used in the light-sensitive material and/or the dye-fixing material. 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. Physicochemical functions include bases or base precursors, nucleophilic compounds, high-boiling solvents (oils), thermal solvents, surfactants, It is classified as a compound that interacts with silver or silver ions. However, these substance groups generally have multiple functions and usually have some of the above-mentioned promoting effects. These details are available in U.S. Patent 4,678.
, No. 739, columns 38-40.

Examples of base precursors include salts of organic acids and bases that are decarboxylated by heat, compounds that release amines by intramolecular nucleophilic substitution reaction, Rossen rearrangement, or Beckmann rearrangement. Specific examples thereof are described in U.S. Pat.

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 to include a base and/or a base precursor in the dye fixing material in order to improve the storage stability of the photosensitive material.

In addition to the above, combinations of poorly soluble metal compounds and compounds that can undergo complex formation reactions with metal ions constituting the poorly soluble metal compounds (referred to as complex-forming compounds), as described in European Patent Publication 210.660, and special Kaisho 61-232451
Compounds that generate bases by electrolysis, such as those described in this issue, can also be used as base precursors. The former method is particularly effective. It is advantageous to add the poorly soluble metal compound and the oa-forming compound to the light-sensitive material and the dye-fixing material separately.

Various development stoppers can be used in the light-sensitive material and/or dye-fixing material 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, an acid precursor that releases acid upon heating;
Examples include electrophilic compounds that undergo a W exchange reaction with a coexisting base upon heating, nitrogen-containing heterocyclic compounds, mercapto compounds, and precursors thereof.

For more details, see JP-A No. 62-253159 (31) - (
It is described on page 32).

As a support for the light-sensitive material or dye-fixing material of the present invention, one that can withstand processing temperatures is used. - For boat fishing, examples include gin and synthetic polymers (films). Specifically, materials made from polyethylene terephthalate, polycarbonate, polyvinyl chloride, polystyrene, polypropylene, polyimide, celluloses (for example, triacetyl cellulose), films containing pigments such as titanium oxide, and polypropylene, etc. film method synthetic paper, mixed paper made from synthetic resin pulp such as polyethylene and natural pulp, Yankee paper,
Baryta paper, coachite paper (especially cast coated paper), metal, cloth, glass, etc. are used.

These can be used alone, or can be used as a support laminated on one or both sides with a synthetic polymer such as polyethylene.

In addition, JP-A-62-253159 (29) to (3)
The supports described on page 1) can be used.

A hydrophilic binder, alumina sol, a semiconductive metal oxide such as tin oxide, carbon black or other antistatic agent may be applied to the surface of these supports.

Methods of exposing and recording images on photosensitive materials include, for example, directly photographing landscapes and people using a camera, exposing through reversal film or negative film using a printer or enlarger, and using a copying machine. A method in which the original image is scanned and exposed through a slit using an exposure device, etc. A method in which image information is transmitted via an electric signal to a light emitting diode, various lasers, etc. for exposure; There are methods of outputting the image to an image display device such as a spray display or a plasma display, and exposing the light directly or through an optical system.

As mentioned above, light sources for recording images on photosensitive materials include natural light, tungsten lamps, light emitting diodes, laser light sources, CRT light sources, etc., such as U.S. Pat.
The light source described in No. 26, column 56 can be used.

Further, image exposure can also be performed using a wavelength conversion element that is a combination of a nonlinear optical material and a coherent light source such as a laser beam. Here, nonlinear optical materials are materials that can exhibit nonlinearity between the polarization and electric field that appear when a strong optical electric field such as a laser beam is applied, and include lithium niobate, potassium dihydrogen phosphate (KDP) ), lithium iodate, inorganic compounds such as BaBzOa,
Urea m4, nitroaniline derivatives, e.g. nitropyridine-N-oxide derivatives such as 3-methyl-4-nitropyridine-N-oxide (POM), JP-A-61-
Compounds described in No. 53462 and No. 62-210432 are preferably used.

As the form of the wavelength conversion element, single crystal guided waveguide type, fiber type, etc. are known, and either of them is useful.

In addition, the above-mentioned image information includes image signals obtained from a video camera, electronic still camera, etc., a television signal represented by the Nippon Television Signal Standard (NTSC), and an image obtained by dividing an original image into a large number of pixels using a scanner. signal, CG,
Image signals created using a computer such as CAD can be used.

The photosensitive material and/or the dye-fixing material may have a conductive heating layer as a heating means for heat development or diffusion transfer of the dye.

In this case, the transparent or opaque heating element is
1-145544 can be used. Note that these conductive layers also function as antistatic layers.

The temperature of the development (and/or transfer) process can be arbitrarily set at about 10°C or higher, so especially when thermal development is used, development can be done at a heating temperature of about 0°C to about 250°C.
A temperature of about 0°C to about 180°C is particularly useful. The dye diffusion transfer step may be performed simultaneously with the heat development, or may be performed after the heat development step is completed. In the latter case, the heating temperature in the transfer step can be in the range from the temperature in the heat development step to room temperature, but is particularly preferably 50° C. or higher and up to about 10° C. lower than the temperature in the heat development step.

Dye migration can also be caused by heat alone, but a solvent may be used to promote dye migration.

Also, JP-A-59-218443, JP-A No. 61-2380
56, etc., a method in which development and transfer are performed simultaneously or continuously by heating in the presence of a small amount of solvent (particularly water) is also useful. In this method, the heating temperature is 5
The temperature is preferably 0°C or higher and the boiling point of the solvent or lower. For example, when the solvent is water, the temperature is preferably 50°C or higher and 100°C or lower.

Examples of solvents used to accelerate development and/or transfer the diffusible dye to the dye fixing layer include water or basic aqueous solutions containing inorganic alkali metal salts or organic bases (these bases may Those described in the section on formation promoters can be used. Furthermore, a low boiling point solvent or a mixed solution of a low boiling point solvent and water or a basic aqueous solution can also be used. Further, a surfactant, an antifoggant, a complex-forming compound with a sparingly soluble metal salt, etc. may be included in the solvent.

These solvents can be used in a method of applying them to dye fixing materials, photosensitive materials, or both.

The amount used may be as small as the weight of the solvent corresponding to the maximum swelling volume of the entire coating film (particularly in mass sales, which is calculated by subtracting the weight of the entire coating film from the weight of the solvent corresponding to the maximum swelling volume of the entire coating film).

As a method for applying a solvent to the photosensitive layer or the dye fixing layer, there is, for example, the method described in JP-A-61-147244, page (26). Further, the solvent can be incorporated in advance into the photosensitive material, the dye fixing material, or both, such as by encapsulating the solvent in microcapsules.

Furthermore, in order to promote dye transfer, a method may be adopted in which a hydrophilic thermal solvent that is solid at room temperature and dissolves at high temperature is incorporated into the light-sensitive material or dye fixing material. The hydrophilic thermal solvent may be incorporated into either the photosensitive material or the dye-fixing material (or may be incorporated into both.Also, the layer in which it is incorporated may be an emulsion layer, an intermediate layer, a protective layer, or a dye-fixing layer. , it is preferable to incorporate it into the dye fixing layer and/or its adjacent layer.

Examples of hydrophilic heat solvents 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 included in the light-sensitive material and/or the dye fixing material.

Heating methods in the development and/or transfer process include contact with a heated block or plate, contact with a hot plate, hot breather, heat roller - halogen lamp heater, infrared and far infrared lamp heater, etc. For example, it may be passed through an atmosphere of

The pressure conditions and method of applying pressure when overlapping the photosensitive material and the dye-fixing material and bringing them into close contact are described in Japanese Patent Application Laid-Open No. 1472-1983.
The method described in No. 44, page 27 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 No. 5975247, No. 59-177547, No. 59181353, No. 60
Apparatuses such as those described in Japanese Utility Model Application Publication No. 18951, Japanese Utility Model Application Publication No. 62-25944, etc. are preferably used.

The color photosensitive material of the present invention may be designed to be processed by a so-called normal wet color diffusion transfer method. In this case, the above-mentioned photosensitive material and dye fixing material can be used, except for additives specific to heat development (eg, organic silver salt).

The base and electron transfer agent may be supplied from the processing solution in a breakable container, to which viscosity-imparting agents and the like can be added as is well known. Color diffusion transfer methods are well known in the art, and the present invention is applicable to any of these known means.

Example 1 The method for preparing the emulsion (T) for the first layer will be described.

600ml+ of an aqueous solution containing sodium chloride and potassium bromide in a well-stirred aqueous gelatin solution (20g of gelatin and 3g of sodium chloride in 10100O water kept at 75°C)! and silver nitrate aqueous solution (water 600
0.59 mol of silver nitrate dissolved in rr+jl) was simultaneously added at an equal flow rate 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, sodium thiosulfate 5■ and 4-hydroxy-6-methyl-1,3,3a,7-titrazaindene 2
Chemical sensitization was carried out at 60° C. by adding 0.0 μm. The yield of emulsion was 600 g.

Next, a method for preparing the 3rd N emulsion (I+) will be described.

A well-stirred aqueous gelatin solution (20 g of gelatin and 3 g of sodium chloride in 10,100 O of water kept at 75°C), 600 ml of an aqueous solution containing sodium chloride and potassium bromide, and an aqueous silver nitrate solution (600 ml of water)
j! (in which 0.59 mol of silver nitrate was dissolved) and the following dye solution (1) were simultaneously added at equal flow rates over 40 minutes.

In this way, a monodisperse cubic silver chlorobromide emulsion (bromine 80 mol %) was prepared, in which a dye having an average grain size of 0.35 μm was adsorbed.

After washing with water and desalting, sodium thiosulfate 5■ and 4-hydroxy-6-methyl-1,3,3a,7-titrazaindene 2
Chemical sensitization was carried out at 60° C. by adding 0.0 μm. The yield of emulsion was 600 g.

Dye solution (1) 160 ■ Dye with the following structure Methanol 400 m 1 Next, we will describe how to prepare the 5th N emulsion (III).

1000rr+j of an aqueous solution containing potassium iodide and potassium bromide in a well-stirred gelatin aqueous solution (20g of gelatin and ammonium dissolved in 10100Q water and kept at 50°C)! and silver nitrate aqueous solution (water 10
(1 mole of silver nitrate dissolved in 00m/) at the same time.
It was added while keeping the Ag constant. In this way, a monodisperse octahedral silver iodobromide emulsion (5 mol % of iodine) with an average grain size of 0.5 μm was prepared.

After washing with water and desalting, gold and sulfur sensitization was carried out at 60° C. by adding 5 μ of chloroauric acid (tetrahydrate) and 2 μ of sodium periosulfate. The yield of emulsion was 1 kir.

Next, we will describe how to make a gelatin dispersion of a dye-donating substance.

Weighed 18 g of the yellow dye donor W fil'', 12 g of the electron donor (1)0, and 9 g of the high boiling point organic solvent shown in Table (2), added 46 ml of ethyl acetate, and heated at about 60°C.
The mixture was heated and dissolved to form a homogeneous solution. After stirring and mixing this solution with 100 g of a 10% solution of lime-treated gelatin, 60 cc of water, and 1.5 g of sodium dodecylbenzenesulfonate, use a homogenizer for 10 minutes.
Dispersed at rpm.

This dispersion is called a yellow dye-providing substance dispersion.

The dispersion of magenta and cyan dye-providing substances is similar to the yellow dye-providing substance, magenta dye-providing substance ff+21", or cyan dye-providing substance +31".
” was made using.

Photosensitive materials 101 to 10 having the configurations shown in the table below.
9 was created.

Table 1 Layer number Layer name Additive Zn (OH) Amount (g/m) Surfactant aerosol OT Support (polyethylene telecrate: thickness 100μ)
Vinyl chloride Electron transfer agent Precursor Polymer Lid CHCHif CONHC (CHJs) Yellow dye-donating substance Magenta dye-donating substance Cyan dye-donating substance Dye fixing material Structure of R-1 Reducing agent (l Bi is a polymer (1) It was added in a dispersed manner.

15 g of reducing agent + 11" and 7.5 g of polymer (11") were dissolved in ethyl acetate 4 Qm6 at about 60°C to form a homogeneous solution. This solution and a 10% aqueous solution of lime-processed gelatin 10
After stirring and mixing 0 g and 3.8 ml of a 5% aqueous solution of surfactant (5%), the
Dispersed at 000 rpm.

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

A dye fixing material R-1 was prepared by coating on a paper support laminated with polyethylene according to the composition shown in the following table.

silicone oil′″1 Surfactant 1 Aerosol OT C.FI? SO□NCH! C00K C, H7 C.I.

CnHtscONHcHt CHt CHt N@Cf
Iz CooeHff Dextran (molecular weight 70,000) Mordant High boiling point organic solvent Luofuos 95 (manufactured by Ajinomoto Co., Inc.) Benzoguamine resin Average particle size 10μ A tungsten light bulb is used for the above multilayered color photosensitive materials 101 to 109, and the concentration changes continuously. B,G doing
, R and Gray color separation filters at 500 lux for 1 second.

The exposed photosensitive material was immersed in water for 5 seconds, passed between a pair of rubber rollers to remove excess water, and then superimposed so that the membrane surface was in contact with the dye fixing material.

The film was heated for 15 seconds using a heat roller whose temperature was adjusted so that the temperature of the water-absorbed film was 85°C.

Next, when peeled off from the dye fixing material, B,
Clear images of blue, green, red, and gray were obtained corresponding to G, R, and gray color separation filters.

Table 2 shows the results of measuring the maximum density (Dmax) and minimum density (Dmin) of each color of cyan, magenta, and yellow in the gray part.

Furthermore, Table 2 also shows the results of storing the color photosensitive materials 101 to 109 at 45 DEG C. and 70% relative humidity for a period of time and then processing them in the same manner.

The physical property values of the high boiling point organic solvent used as a comparative example in Table 2 are as follows.

Viscosity permittivity (A) (i30-Cwll+, 0)-! P=
036.3CI) 4.46 (B) (C7ICII□ ClCH2O)-s
P=011.64 (C) From the results in Table 2, it was found that the raw storage stability of the photosensitive material could be improved by using a compound with a viscosity of 50 Cp or more and a dielectric constant of 1O or less at 25° C. as a high boiling point organic solvent.

Example 2 A photosensitive material similar to that of Example 1 was prepared except that the electron donor (1) 0 in Example 1 was replaced with the following compound and equimolar amounts were added, and the raw storage stability was compared. It has been found that photosensitive materials using high boiling point organic solvents exhibit good storage stability.

Electron Donor: Example 3 A photosensitive material was prepared in the same manner as in Example 1, except that cyan dye-donating substance (3) 0 was added in equal moles instead of the following compound, and the raw storage stability was By comparison, the photosensitive material using the high boiling point organic solvent of the present invention was
It was found that even after storage for one week in %, it showed a low Dmin.

Cyan dye-donating compound: Example 4 In the photographic material 102, 103, 105, 106 of Example 1, each dye-donating compound and electron donor (I)0 were dissolved together in a high boiling point organic solvent to form gelatin. Instead of being dispersed throughout, they were separately dispersed and used as shown below.

The amounts of each dye-donating compound and electron donor (1)* added to the light-sensitive material were the same as in Example 1.

Weigh out 18 g of yellow dye-donating substance +11'' and 9 g of high boiling point 81 solvent, add 46 mA of ethyl acetate, and heat to approx. 60°C.
Heat it to dissolve it and make it uniform? It was made into 8 liquids. After stirring and mixing this solution with 80 g of a 10% solution of lime-treated gelatin, 60 cc of water, and 1.5 g of sodium dodecylbenzenesulfonate, the mixture was heated to 11,000 ml using a homogenizer for 10 minutes.
Dispersed at 0 rp. This dispersion is called a yellow dye-providing substance dispersion.

Dispersions of magenta and cyan dye-providing materials were made using magenta dye-providing material (21" or cyan dye-providing material + 31") as well as dispersions of yellow dye-providing material.

(1) 12 g of gelatin cast donor + 11” and 3 g of high boiling point organic solvent
Weighed 1 g of polymer (1) 0 and 20 ethyl acetate.
mj! was added and dissolved at about 60°C. After stirring and mixing this solution with 40 g of a 10% solution of lime-treated gelatin, 3 Qcc of water and 0.8 g of sodium dodecylbenzenesulfonate, the mixture was heated at 110,000 r for 10 minutes using a homogenizer.
It was prepared by dispersing it with p.

Photosensitive materials 202.203.20 using these dispersions
5 and 206 were created. When raw storage stability was compared in the same manner as in Example 1, it was found that the photosensitive materials 205 and 206 using the high boiling point organic solvent of the present invention were compared with the photosensitive materials 202 and 20.
It was found that it had better storage stability than No. 3.

Example 5 Color photosensitive materials 303 and 306 with multilayer structures shown in Table 3 were prepared using the same emulsions, dye-donating substances, electron donors, and electron transfer agents as in color photosensitive materials 103 and 106 of Example 1. .

Note that the same additives as in Example 1 were used unless otherwise specified.

The organic silver salt emulsion was prepared as follows.

20 g of gelatin and 5.9 g of 4-acetylaminophenylpropiolic acid were mixed with 10 g of 0.1% sodium hydroxide aqueous solution.
00mf and ethanol 200mA. This solution was kept at 40°C and stirred.

Add 4.5 g of silver nitrate to this solution and 200 mj of water! Excess salt was then removed by a sedimentation method in which a solution dissolved in water was added for 5 minutes. After that, adjust the pH to 6.3 and settle at ff1300.
g of a silver salt dispersion was obtained.

Further, anti-capri agent precursor (1) 1 having the following structure was added in 0.2 times the molar amount to the dye-donating substance, and the mixture was dispersed in oil together with the dye-donating substance and the electron donor by the method of Example 1.

O-sold l) O-sold 2) Support (polyethylene telecrate; thickness 100μ)
Anti-capri agent precursor (1) 0 Heat solvent (11") Benzene sulfonamide base precursor (1) 0 4-Chlorphenylsulfonylacetate guanidine Next, the method of preparing the dye fixing material (R-2) will be described.

Poly (methyl acrylate-N,N,N-trimethyl-N-vinylhensyl ammonium chloride) (
The ratio of methyl acrylate and vinylbenzylammonium chloride is 1:l) Log is 200mj! of water and uniformly mixed with 100 g of 10% lime-treated gelatin. A hardening agent was added to this mixed solution, and the mixture was uniformly coated to a wet film thickness of 90 μm on a paper support laminated with polyethylene in which titanium dioxide was dispersed. After drying, this sample is used as a dye fixing material (R-2) having a mordant layer.

After exposure in the same manner as in Example 1, it was heated uniformly for 30 seconds on a heat block heated to 140°C.

After supplying 20 m4 of water per IM to the film surface side of the dye fixing material (R-2), the heat-treated photosensitive materials were stacked on the fixing material so that the film surfaces were in contact with each other.

After that, it was placed in a laminator heated to 80℃ at a linear speed of 12+n/
After passing through the dye for several seconds, both materials were peeled off to obtain a positive image on the dye-fixing material.

D+i for some cyan, magenta, and yellow colors
ax was measured. Further, the photosensitive materials 303 and 30
After storing Sample No. 6 at 45° C. and 70% relative humidity for one week, it was processed in the same manner and the photographic properties were compared with those processed immediately after preparation. Photosensitive material 303 received I)+i in the forced test.
Although there was a large increase in n, photographic properties of photographic material 306 showed little variation.0 It was found that the storage stability of photographic materials could be improved by using the high boiling point organic solvent of the present invention.

Example 6 Photosensitive material 401 was prepared by sequentially coating the following layers on a transparent polyethylene terephthalate support.

Note that unless otherwise specified, the same additives as in Photosensitive Material 101 were used.

a cyan dye-donor layer containing a dye-receiving layer containing a red-sensitive layer containing an intermediate layer containing a white reflective layer (・) a magenta dye-donor layer containing a surfactant (1) (0.2 g/ m) Blue-sensitive layer (IX) containing surfactant (IX) C) Green-sensitive layer containing surfactant (1) (■ Intermediate layer (0,2 g/bon), same as n) e) Surfactant (l Bi (0,2 g) The (IV)th layer, (■)th layer, and (X)th layer of the yellow dye-donating layer photosensitive material 402 including the retaining fl1 layer containing /rrr)
The compound of the present invention (
A photosensitive material 402 having the same composition as the photosensitive material 401 was prepared except that the same amount of 6) was added.

The following layers were then sequentially coated onto a transparent polyethylene terephthalate film to prepare a cover sheet.

(°)
Acid neutralization layer (II) containing cellulose acetate (saccharification degree 54%) to a thickness of 2 microns.Timing layer (III) Copolymer latex of vinylidene chloride and acrylic acid applied to a thickness of 4 microns. A timing layer and a processing solution having the following composition were prepared.

Potassium hydroxide 48g 4-hydroxymethyl-4-methyl-1-P-tolyl 3-pyrazolidinone 10g 5-methylbenzenetriazole 1.5g Sodium sulfite 1.5g Potassium bromide
1g benzyl alcohol l,
5 m j! Carboxymethyl cellulose 6.
1g carbon black 150g water
Amount of light-sensitive material to make the total amount 11 401.40
2 is exposed through a wedge, then overlapped with the cover sheet, and using a pair of juxtaposed rollers, the processing liquid was applied between 8
It was spread uniformly to a thickness of 0μ.

The results of sensitometry performed 1 hour after the treatment are shown in the following table.

Further, the photosensitive materials 401 and 402 were heated at 45° C. relative humidity 7.
After storing it under 0% conditions for one week, it was processed in the same manner and compared with that processed immediately after creation, I)++
Although there was almost no variation in aχ, the increase in Dmin was smaller in photosensitive material 402 than in photosensitive material 401. It has been found that the storage stability of photosensitive materials can be improved by using the high boiling point organic solvent of the present invention.

Patent applicant: Fuji Photo Film Co., Ltd. Procedural Amendment

Claims (1)

[Claims] 1) In a color photosensitive material containing at least a photosensitive silver halide, a binder, a reducible dye-providing compound, and a diffusion-resistant reducing agent on a support, the dye-providing compound and/or the diffusion-resistant reducing agent is dispersed in a high boiling point organic solvent having a viscosity of 50 centipoise or more and a dielectric constant of 10 or less at 25°C.