JPH06102644A - Heat developable color photosensitive material - Google Patents

Abstract

PURPOSE:To obtain a heat developable color photosensitive material having excellent preservable property and superior adaptability for the fabrication by adding at least one water soluble high polymer compound which has sulfonic acid, sulfate or carboxyl groups in its side chains and a limiting viscosity number of a specified value, to a layer hardened with a specific compound and/or a layer to be coated adjacently to the former layer. CONSTITUTION:The heat developable color photosensitive material has on a substrate at least a photosensitive silver halide, a binder and a dyestuff donative compound. The photosensitive material also has a layer hardened with the compound represented by the formula. The photosensitive material further contains in the above layer and/or a layer to be coated adjacently to the former layer, at least one water soluble high polymer compound which has sulfonic acid, sulfate and carboxyl groups in its side chains and a 0.4 to 1.5 limiting viscosity number (0.1N Nail, 30 deg.C). In the formula, R is a hydrogen atom or an alkyl, aralkyl, aryl or heterocyclic group, and (n) is 0 or 1.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a heat-developable color light-sensitive material, and more particularly to a heat-developable color light-sensitive material having excellent storage stability and manufacturability.

[0002]

2. Description of the Related Art Recent advances in office automation have led to advances in commercial imaging equipment, the advent of electronic still cameras, the spread of video and facsimile, advances in computer graphics, advances in image sensors and advances in digital processing technology for original images. Along with this, there is an increasing demand for obtaining a color hard copy from image information that has been converted into an electric signal. Various methods such as electrophotography, ink jet, thermal transfer, and silver salt photography are known as methods for obtaining a color hard copy. However, the inkjet and thermal transfer methods are still insufficient in terms of image quality, and the development of a system capable of high image quality and simple and quick processing has been awaited.

On the other hand, the photographic method using silver halide is excellent in photographic characteristics such as sensitivity and gradation control as compared with other photographic methods such as electrophotography and diazo photographic method. Therefore, it has been widely used. It was In recent years, a technique has been developed that can easily and quickly obtain an image by changing the image forming processing method of a light-sensitive material using silver halide from the conventional wet processing using a developing solution or the like to dry processing such as heating. Came.

Photothermographic materials are known in the art, and regarding the photothermographic material and its process, for example, 553 of the foundation of photographic engineering (published by Corona Publishing Co. in 1979).
~ 555 pages, 40 pages of video information issued in April 1978, Nebuletts, Handbook of Photography and Reprography, 7th Edition (Nebletts, Handbook of Photographyan
d Reprography 7th Ed.) Van. Nostrand. Line hold. Company (Van Nostrand Reinhold Comp
32-33, U.S. Pat. No. 3,152,904
No. 3,301,678, 3,392,020
No. 3,457,075, British Patent No. 1,131,
No. 108, No. 1,167,777 and Research
Disclosure, June 1978, pages 9-15,
(RD-17029).

All of these generate or release a dye by heating to form an image-like distribution of the dye, and are characterized in that the image-like distribution of the dye can be obtained in a short time. On the other hand, with the recent advances in office automation, advances in business-use image equipment, the advent of electronic still cameras, the spread of video and facsimile, the advances in computer graphics, the advances in image sensors and the advances in digital processing technology for original images There is an increasing demand for obtaining a color hard copy from image information converted into an electric signal. Conventional light-sensitive materials have spectral sensitivities of blue, green, and red. Color CRT (cathode ray tube) is used to obtain an image by using image information converted into an electric signal in such a light-sensitive material. Is generally used as an exposure light source, but a CRT is not suitable for obtaining a large size print. Further, a light emitting diode (LED) or a semiconductor laser has been developed as a writing head capable of obtaining a large size print. However, none of these optical writing heads that efficiently emit blue light has been developed.

Thus, for example, a light emitting diode (LED)
When using, near infrared (800nm), red (670n
It is necessary to expose a color light-sensitive material having three layers spectrally sensitized to near infrared, red and yellow by a light source combining three light emitting diodes of m) and yellow (570 nm). Image recording system is "Nikkei New Material" September 14, 1987 issue 47-5
It is described on page 7 and is partly in practical use. Also, 8
Japanese Patent Application Laid-Open No. 61-137149 discloses a system for recording on a color light-sensitive material having three light-sensitive layers having spectral sensitivity at each wavelength with a light source combining three semiconductor lasers emitting light of 80 nm, 820 nm and 760 nm. Has been done.

By the way, in such a heat-developable color light-sensitive material, the physical properties of the film largely control the photographic property. In particular, in a system in which heat development and dye transfer are performed in the presence of a small amount of water, the development speed and the transfer speed change depending on the hardness of the film, which directly affects the water absorption speed and the amount of water. Therefore, in order to keep the photographic properties of the heat-developable color light-sensitive material stable during raw storage, it is necessary to prevent the hardness of the film from changing during storage. Factors that govern the degree of hardening include the water content of the film, the pH, and the temperature during storage, but the reactivity of the hardening agent is the most important factor. Depending on the type of hardener, the hardening reaction may gradually progress over several days to several months, and it may be very difficult to keep the photographic properties of the product stable. In order to solve these problems, Japanese Patent Application No. 3-73684 describes a photothermographic material containing a fast-acting hardener, that is, a photothermographic material containing a fast-acting hardener. When a fast hardening agent is added to the coating solution, the reaction may occur quickly, causing the coating solution to gel.As a countermeasure against this, the hardening agent may be mixed immediately before coating or the coating solution may be slowed down. A method of lowering the pH of the is proposed.

On the other hand, when a coating solution containing a fast-acting hardening agent was examined, gelation of the coating solution could be suppressed considerably by eliminating binders, such as gelatin, that interact with the hardening agent. I found out. However, some of the compounds having these interactions cannot be excluded in terms of coating suitability, and a typical compound thereof is a water-soluble polymer compound thickening agent for ensuring a coating suitability viscosity of the coating liquid. Can be given. Therefore, in order to stably manufacture the heat-developable color light-sensitive material, there arises a problem that it is necessary to maintain the coating suitability of the coating liquid and prevent foreign matter from being broken due to gelation of the coating liquid.

[0009]

SUMMARY OF THE INVENTION An object of the present invention is to obtain a heat-developable color light-sensitive material having excellent storage stability and manufacturability.

[0010]

The above object is achieved by the present invention described below. A heat-developable color light-sensitive material having at least a light-sensitive silver halide emulsion, a binder and a dye-donor compound on a support, and having a layer hardened with a compound represented by the following general formula (I), and The layer hardened with the compound represented by the general formula (I) and / or the layer applied adjacent to the layer has a sulfonic acid group, a sulfuric ester group or a carboxyl group in the side chain, A heat-developable color photosensitive material comprising at least one water-soluble polymer compound having an intrinsic viscosity [η] (0.1N NaCl, 30 ° C) of 0.4 to 1.5.

[0011]

[Chemical 2]

In the formula, R represents a hydrogen atom, an alkyl group, an aralkyl group, an aryl group or a heterocyclic group. n represents 0 or 1.

(Specific Structure) The hardener and water-soluble polymer compound used in the heat-developable color light-sensitive material of the present invention will be described in more detail. First, the hardener compound represented by the general formula (I) used in the present invention will be described. In general formula (I), R represents a hydrogen atom, an alkyl group, an aralkyl group,
It represents an aryl group or a heterocyclic group. n represents 0 or 1. More specifically, R is a hydrogen atom and has 1 to 1 carbon atoms.
20 alkyl groups (including substituted ones such as methyl and ethyl), C7 to C20 aralkyl groups (including substituted ones such as benzyl and phenethyl), and C6 to C20 aryl groups (Including those which are substituted, for example, phenyl, naphthyl) or a 5- or 6-membered nitrogen-containing heterocyclic group (for example, pyridyl). Examples of the substituent include a sulfonic acid group, a hydroxyl group and a carboxyl group. Particularly preferred as R is a hydrogen atom. n represents 0 or 1. Specific examples of the compound represented by formula (I) of the present invention are shown below, but the present invention is not limited thereto.

[0014]

[Chemical 3]

[0015]

[Chemical 4]

The addition amount of the compound represented by the general formula (I) is preferably selected in accordance with the kind of compound example, the kind of gelatin, etc., and is preferably 6 × 10-6 × 10 mol per 100 g of gelatin. , And more preferably 3
It is x10 to 12x10 mol.

Next, the soluble polymer compound used in the present invention is
explain. In the present invention, at least one sulfone is included in the side chain.
Compounds containing phosphonic acid groups, sulfuric acid ester groups, carboxylic acid groups
Such as vinylbenzene sulfonic acid, 2-acryl
Amido-2-methylpropanesulfonic acid, acrylic acid,
Methacrylic acid, maleic acid, maleic acid half ester
-SO on the side chain like vinyl benzene carboxylic acid ₃ 
M, -OSO₃ M, -COOM (M is H, metal ion
A polymer of a monomer having a group such as
Means a copolymer containing at least one of these monomers
To do.

Particularly preferred monomers are those having a sulfonic acid group, a sulfuric ester group or a carboxyl group in the side chain of the present invention. For example, vinylbenzenesulfonic acid (Na salt) -acrylic acid (Na salt). ) And 2-acrylamido-2-methylpropanesulfonic acid (Na salt) -methacrylic acid (Na salt). The copolymerization ratio in this case is not particularly limited. Other examples include, for example, butyl acrylate, butyl methacrylate, styrene, acryloamide, N-vinylpyrrolidone, etc. The copolymerization ratio in these cases is not particularly limited, but the side chain is preferred. The amount of the monomer having a sulfonic acid group, a sulfuric acid ester group, and a carboxyl group is 50 mol% or more. Among these polymers or copolymers, particularly preferable are polybenzene sulfonate, poly (2-acrylamido-2-methylpropane) sulfonate, and polyacrylate.

These polymers or copolymers (hereinafter referred to as "polymers") used in the present invention are not different in structure from the conventionally known polymers, but their characteristic features are as follows. The polymer has an average molecular weight and its intrinsic viscosity [η] is 0.4 to 1.5 (0.1N NaCl, 30
℃). Particularly preferably [η] = 0.5
~ 1.2. In general, when a water-soluble polymer is added to a photographic coating liquid for the purpose of thickening, a polymer having a higher average molecular weight, which has a stronger thickening action and can achieve a target viscosity with a small amount used, is used. Therefore, the average molecular weight is usually 7
Often exceeds 0 to 1 million. That is, [η] = 2.
0-10.0 (0.1N NaCl, 30 ° C).

However, as a result of repeated studies on the coating solution containing the above-mentioned quick-acting hardener, it was found that the degree of gelation of the solution decreases as the average molecular weight of the water-soluble thickening polymer decreases. It was This phenomenon remarkably appears when the intrinsic viscosity [η] of the polymer is 1.5 (0.1 N NaCl, 30 ° C.) or less, and it was found that the degree of gelation can be suppressed as the molecular weight decreases. However, an extremely low molecular weight polymer, that is, [η] = 0.4 (0.1N Na
If the temperature is lower than Cl, 30 ° C.), the target viscosity cannot be obtained because the thickening effect of the polymer is significantly reduced.

An example of the method for measuring the intrinsic viscosity number in the present invention is shown below. Viscometer; Utsuberode viscometer (Automatic viscometer Ty manufactured by Fusion Co., Ltd.
pe VMC-052) Temperature: 30 ° C Solvent: 0.1N NaCl Concentration: 1%, 0.75%, 0.6%, 0.5% (wt /
vol) Obtain the relative viscosity, specific viscosity, and reduced viscosity of the polymer solution at each of the above concentrations, and obtain the intrinsic viscosity number from the reduced viscosity and the intercept when extrapolating from 0 to 0.

These polymers used in the present invention can be easily synthesized by a conventional method. The molecular weight can be freely controlled by the amount of the initiator, the monomer concentration, the solvent type, the temperature and the like. For example, as the amount of the polymerization initiator is increased, the intrinsic viscosity number tends to be decreased, as the monomer concentration is increased, the intrinsic viscosity number tends to be increased, and as the reaction temperature is increased, the intrinsic viscosity number is increased. Tends to be smaller. Therefore, a polymer having a desired intrinsic viscosity number can be obtained by appropriately controlling these factors.

In the present invention, these polymers can be used in a wide range. Specifically, it varies depending on the gelatin coating amount and concentration of the layer used and the amount of the hardener used, but is usually 1 mg / m ^{2 to} 100 mg / m ² , preferably 5 per layer to be added.
a ^{mg / m 2 ~50mg / m 2} .

The light-sensitive material used in the present invention is basically a support having a light-sensitive silver halide, a binder and a dye-donating compound (which may also serve as a reducing agent as described later).
In addition, an organic metal salt oxidizing agent and the like can be added as necessary. These components are often added to the same layer, but if they are in a reactive state, they can be divided and added to separate layers. For example, when a colored dye-donor compound is present in the lower layer of the silver halide emulsion, the reduction in sensitivity can be prevented. The reducing agent is preferably incorporated in the photothermographic material, but it may be supplied from the outside by, for example, a method of diffusing from a dye fixing material described later.

In order to obtain a wide range of colors in the chromaticity diagram by using the three primary colors of yellow, magenta and cyan, a combination of at least three silver halide emulsion layers sensitive to different spectral regions is used. . For example, a combination of three layers of blue-sensitive layer, green-sensitive layer and red-sensitive layer, green-sensitive layer, red-sensitive layer,
There are combinations of infrared photosensitive layers. Each of the light-sensitive layers can take various arrangement orders known in a conventional type color light-sensitive material. Further, each of these photosensitive layers may be divided into two or more layers if necessary. Further, in the present invention, a black and white photosensitive material or a monochromatic color photosensitive material can be used. The black-and-white light-sensitive material may be any of a case where the dye-donating compound releases a black-and-white dye, a case where the dye-donating compound contains a mixture of yellow, magenta, and cyan dye-donating compounds. For the photothermographic material, a protective layer, an undercoat layer, an intermediate layer,
Various auxiliary layers such as a yellow filter layer, an antihalation layer and a back layer can be provided.

The silver halide usable in the present invention may be any of silver chloride, silver bromide, silver iodobromide, silver chlorobromide, silver iodochloride and silver chloroiodobromide. The silver halide emulsion used in the present invention may be either 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 or an optical fogging. Further, it may be a so-called core-shell emulsion in which the inside of the grain and the surface layer of the grain have different phases. The silver halide emulsion may be monodisperse or polydisperse, and monodisperse emulsions may be mixed and used.
Particle size is from 0.1 μm to 2 μm, especially 0.2 μm
˜1.5 μm is preferable. The crystal habit of silver halide grains is
Cube, octahedron, tetradecahedron, flat plate with high aspect ratio,
Any other may be used. Specifically, US Patent No. 45
No. 00626, 50th column, No. 4628021, Research Disclosure (hereinafter abbreviated as RD) 170
29 (1978), and any of the silver halide emulsions described in JP-A No. 62-253159 and the like can be used.

The silver halide emulsion may be used in an unripened state, but it is usually chemically sensitized before use. The known sulfur sensitizing method, reduction sensitizing method, noble metal sensitizing method, selenium sensitizing method and the like can be used alone or in combination for the emulsion for a conventional type light-sensitive material. These chemical sensitizations can be carried out in the presence of a nitrogen-containing heterocyclic compound (JP-A-62-2531).
59). The coating amount of the photosensitive silver halide used in the present invention is in the range of 1 mg / m ² to 10 g / m ^{2 in} terms of silver.

In the present invention, an organic metal salt may be used as an oxidizing agent together with the 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 organic silver salt oxidizing agents include US Pat.
There are benzotriazoles, fatty acids and other compounds described in No. 26, columns 52 to 53. In addition, JP-A-60-1
Silver salts of carboxylic acids having an alkynyl group such as silver phenylpropiolate described in 13235, and JP-A-61-161
The acetylene silver described in No. 249044 is also useful. Two or more kinds of organic silver salts may be used in combination. The above organic silver salts are
0.01 to 10 per mol of photosensitive silver halide
Moles, preferably 0.01 to 1 mol can be used in combination. The total coating amount of the photosensitive silver halide and the organic silver salt is preferably 50 mg / m ² to 10 g / m ² in terms of silver.

Various antifoggants or photographic stabilizers can be used in the present invention. Examples thereof include azoles and azaindenes described in RD17643 (1978), pages 24 to 25, JP-A-59-1684.
42-containing nitrogen-containing carboxylic acids and phosphoric acids,
Alternatively, the mercapto compound and its metal salt described in JP-A-59-111636, the acetylene compounds described in JP-A-62-87957, etc. may be used.

The silver halide used in the present invention may be spectrally sensitized with methine dyes and the like. 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, US Pat. No. 4,617,257, JP-A-59-180550,
No. 60-140335, RD17029 (1978)
Years) sensitizing dyes described on pages 12 to 13 and the like. These sensitizing dyes may be used alone or in combination, and the combination of sensitizing dyes is often used especially for the purpose of supersensitization. Along with the sensitizing dye, a dye having no spectral sensitizing effect itself or a compound which does not substantially absorb visible light and exhibits supersensitization may be contained in the emulsion (for example, US Pat. No. 361564).
1 and those described in JP-A-63-23145). These sensitizing dyes may be added to the emulsion during the chemical ripening or before or after the chemical ripening. US Pat. No. 4,183,756
No. 4,225,666, before or after nucleation of silver halide grains. The addition amount is generally about 10 ^-8 to 10 ^-2 mol per mol of silver halide.

A hydrophilic binder is preferably used as the binder of the constituent layers of the light-sensitive material and the dye-fixing material. As an example thereof, pages (26) to (2) of JP-A No. 62-253159.
8) The thing described in page is mentioned. Specifically, a transparent or translucent hydrophilic binder is preferable, and for example, gelatin, proteins such as gelatin derivatives or cellulose derivatives, starch, gum arabic, dextran, natural compounds such as polysaccharides such as pullulan, and polyvinyl alcohol, Examples thereof include polyvinylpyrrolidone, acrylamide polymer, and other synthetic polymer compounds. Furthermore, superabsorbent polymers described in JP-A-62-245260, i.e. -COOM or -SO ₃ M (M is a hydrogen atom or an alkali metal) homopolymer or a vinyl monomer together or with other vinyl monomers with A copolymer with a vinyl monomer (for example, sodium methacrylate, ammonium methacrylate, Sumika Gel L-5H manufactured by Sumitomo Chemical Co., Ltd.) is also used. These binders can be used in combination of two or more. The acid-processed gelatin used in the present invention may be arbitrarily selected from "950 gelatin" manufactured by Nitta Gelatin, "ABA gelatin" manufactured by Nippi Gelatin, "Croda-A148" manufactured by Kuroda Gelatin, and used. You can

When a system in which a small amount of water is supplied for thermal development is adopted, it becomes possible to quickly absorb water by using the above superabsorbent polymer. Further, when the super absorbent polymer is used in the dye fixing layer or its protective layer, the dye can be prevented from being retransferred from the dye fixing material to another after the transfer. In the present invention,
The coating amount of the binder is preferably 200 g or less per 1 m ² , particularly 10 g or less, more preferably 7 g or less.

The constituent layers (including the back layer) of the light-sensitive material or the dye-fixing material are used for the purpose of improving physical properties of the film such as dimensional stabilization, curl prevention, adhesion prevention, film cracking prevention, and pressure increase / decrease prevention. Various polymer latices can be included. Specifically, any of the polymer latexes described in JP-A Nos. 62-245258, 62-136648, 62-110066 and the like can be used. In particular,
When a polymer latex having a low glass transition point (40 ° C. or less) is used in the mordant layer, cracking of the mordant layer can be prevented, and when a polymer latex having a high glass transition point is used in the back layer, a curl preventing effect can be obtained. .

As the reducing agent used in the present invention, those known in the field of photothermographic materials can be used. Further, a dye-donor compound having a reducing property described later is also included (in this case, other reducing agents can be used together). Further, a reducing agent precursor which has no reducing property itself but exhibits reducing property by the action of a nucleophile or heat during the development process can also be used. Examples of the reducing agent used in the present invention include U.S. Pat. No. 4,500,626, columns 49 to 50 and U.S. Pat. No. 4,483,914, columns 30 to 31.
Column, No. 4330617, No. 4590152, and JP-A No. 60-140335, pages (17) to (18), ibid.
7-40245, 56-138736, 59-
178458, 59-53831, 59-18
No. 2449, No. 59-182450, No. 60-119.
555, 60-128436 to 60-128
No. 439, No. 60-198540, No. 60-18
1742, 61-259253, 62-244
044, 62-131253 to 62-131
Up to 256, 78 of EP 220 746 A2
There are reducing agents and reducing agent precursors described on page 96 and the like. Combinations of various reducing agents such as those disclosed in US Pat. No. 3,039,869 can also be used.

When a diffusion resistant reducing agent is used, an electron transfer agent and / or an electron transfer agent may be added, if necessary, in order to promote electron transfer with the developable silver halide as the diffusion resistant reducing agent. An electron transfer agent precursor can be used in combination. The electron transfer agent or its precursor is
It can be selected from the above-mentioned reducing agents or their precursors. It is desirable that the electron transfer agent or its precursor has a mobility higher than that of the diffusion resistant reducing agent (electron donor). A particularly useful electron transfer agent is 1-phenyl-
3-pyrazolidones or aminophenols.
The diffusion-resistant reducing agent (electron donor) used in combination with the electron transfer agent may be any of those reducing agents that do not substantially move in the layer of the light-sensitive material, and preferably hydroquinones, Examples thereof include sulfonamide phenols, sulfonamide naphthols, compounds described as electron donors in JP-A No. 53-110827, and dye-donating compounds having diffusion resistance and reducing properties described later.

In the present invention, the reducing agent is added in an amount of 0.01 to 20 mol, and particularly preferably 0.1 to 1 mol of silver.
10 to 10 mol.

In the present invention, silver can be used as the image forming substance. Further, when a silver ion is reduced to silver under a high temperature condition, a compound that produces or releases a mobile dye in response to this reaction or vice versa, that is, contains a dye-donating compound. You can also

As an example of the dye-donating compound which can be used in the present invention, first, a compound (coupler) which forms a dye by an oxidative coupling reaction can be mentioned. The coupler may be a 4-equivalent coupler or a 2-equivalent coupler. A 2-equivalent coupler having a diffusion resistant group as a leaving group and forming a diffusible dye by an oxidative coupling reaction is also preferable. The diffusion resistant group may form a polymer chain. Specific examples of color developers and couplers are TH James
"The Theory of the Photographic Process" 4th edition, pages 291-334 and 354-361, JP-A-58
-123533, 58-149046, 58-
No. 149047, No. 59-111148, No. 59-1
24399, 59-174835, and 59-23.
1539, 59-231540, 60-295.
No. 0, No. 60-2951, No. 60-14242, No. 60-23474, No. 60-66249 and the like.

As another example of the dye-donor compound,
Examples thereof include compounds having a function of releasing or diffusing a diffusible dye in an image form. This type of compound can be represented by the following general formula [LI]. (Dye-Y) n-Z [LI] Dye represents a dye group, a temporarily shortened dye group or a dye precursor group, Y represents a simple bond or linking group, and Z represents an image latent image. Corresponding to or opposite to the photosensitive silver salt having a difference in the diffusivity of the compound represented by (Dye-Y) n-Z, or releasing Dye and releasing Dye and (Dye- Y) represents a group having a property of causing a difference in diffusibility from n-Z, n represents 1 or 2, and when n is 2, two Dye-Y are the same or different. Good.

Specific examples of the dye donating compound represented by the general formula [LI] include the following compounds. In addition, the following items (1) to (4) are for forming a diffusible dye image (positive dye image) in the opposite manner to the development of silver halide, and the terms and are the diffusible dye image (corresponding to the development of silver halide ( To form a negative dye image). U.S. Pat. Nos. 3,134,764 and 3,628,19;
No. 3597200, No. 3544545, No. 3482
No. 972, etc., a dye developing agent in which a hydroquinone-based developing agent and a dye component are linked. This dye developing agent is diffusible in an alkaline environment, but it becomes non-diffusible by reacting with silver halide. As described in U.S. Pat. No. 4,053,137, a non-diffusible compound which releases a diffusible dye in an alkaline environment but loses its ability when reacted with a silver halide can be used. An example is U.S. Pat. No. 39804.
No. 79, etc., which release a diffusible nucleophile by an intramolecular nucleophilic substitution reaction, and US Pat. No. 4,199,354, etc., which release a diffusible dye by an intramolecular rewinding reaction of an isoxazolone ring. Is mentioned. U.S. Pat. No. 4,559,290, European Patent 22074
6A2, US Pat. No. 4,783,396, Open Technical Report 87
As described in -6199 etc., a non-diffusible compound which reacts with a reducing agent remaining without being oxidized by development to release a diffusible dye can also be used. Examples thereof include diffusible dyes which are described in U.S. Pat. Nos. 4,139,389, 4139379, JP-A-59-185333, 57-84453, and the like, and are reduced by a nucleophilic substitution reaction in the molecule. Releasing compounds, US Patent No. 42321
07, JP-A-59-101649 and JP-A-61-882.
57, RD24025 (1984), etc., compounds that release a diffusible dye by an intramolecular electron transfer reaction after reduction, West German Patent No. 3008588A,
JP-A-56-142530, US Pat. No. 434389.
Nos. 3,4619884 and the like, compounds that release a diffusible dye by cleavage of a single bond after reduction, and nitro, which releases a diffusible dye after electron acceptance, as described in US Pat. No. 4,450,223. Compound, US Patent No. 4
Examples thereof include compounds described in JP-A No. 609610, which release a diffusible dye after electron acceptance.

Further, as more preferable ones, European Patent No. 220746A2, Open Technical Report 87-6199, US Pat. No. 4,783,396, Japanese Patent Laid-Open No. 63-201653.
Nos. 63-2016654 and the like, compounds having an N—X bond (X represents an oxygen, sulfur or nitrogen atom) and an electron-withdrawing group in one molecule, described in JP-A-1-26842. SO ₂ -X in one molecule (X is as defined above)
And a compound having an electron-withdrawing group, JP-A-63-2713
No. 44, a compound having a PO—X bond (where X is as defined above) and an electron-withdrawing group in one molecule, JP-A-63-
No. 271341 and compounds having a C—X ′ bond (where X ′ has the same meaning as X or represents —SO ₂ —) and an electron-withdrawing group in one molecule. In addition, JP-A-1-
Compounds that release a diffusible dye by cleaving a single bond after reduction by a π bond conjugated with an electron-accepting group described in Nos. 161237 and 1-161342 can also be used.

Of these, a compound having an N—X bond and an electron-withdrawing group in one molecule is particularly preferable. Specific examples thereof include European Patent No. 220746A2 or US Patent No. 47833.
Compounds (1) to (3), (7) to (10), (1
2), (13), (15), (23) to (26), (31), (32), (35), (3
6), (40), (41), (44), (53) to (59), (64), (70), compounds (11) to (23) described in the open technical report 87-6199, etc. Is.

A compound (DDR coupler) which is a coupler having a diffusible dye as a leaving group and releases the diffusible dye by a reaction with an oxidized form of a reducing agent. Specifically, British Patent No. 1330524, Japanese Patent Publication No. 48-39165, U.S. Patent Nos. 3443940, 4474867, 448.
3914 and the like.

A compound (DDR compound) which is reducible to a silver halide or an organic silver salt and releases a diffusible dye when its partner is reduced. Since this compound does not need to use another reducing agent, it is preferable because there is no problem of image contamination due to oxidative decomposition products of the reducing agent. Typical examples thereof are U.S. Pat. Nos. 3,928,312, 4,053,312 and 405.
No. 5428, No. 4336322, JP-A-59-658.
No. 39, No. 59-69839, No. 53-3819,
51-104343, RD17465, U.S. Pat. Nos. 3,725,062, 3,728,113 and 3,443.
939, JP-A-58-116537, 57-17.
9840, U.S. Pat. No. 4,500,626 and the like. Specific examples of the DDR compound include the compounds described in the above-mentioned U.S. Pat. No. 4,500,626, columns 22 to 44, among which the compounds (1) to (3) described in the U.S. Pat. (10) ~ (13), (16) ~ (19), (28)
To (30), (33) to (35), (38) to (40), and (42) to (64) are preferable. Further, the compounds described in US Pat. No. 4,639,408, columns 37 to 39 are also useful.

In addition to the above-mentioned couplers and dye-providing compounds other than the general formula [LI], dye silver compounds in which an organic silver salt and a dye are bonded (Research Disclosure, May 1978, pp. 54-58). , Etc., azo dyes used in the heat developable silver dye bleaching method (US Pat.
957, Research Disclosure, April 1976, pages 30-32, etc.), Leuco dyes (US Pat. No. 3).
985565, No. 4022617, etc.) can also be used.

Hydrophobic additives such as dye-donor compounds and anti-diffusion reducing agents can be incorporated into the layers of the photographic material by known methods such as the method described in US Pat. No. 2,322,027. In this case, JP-A-59-83154,
59-178451, 59-178452, 59-178453, 59-178454, 5
9-178455, 59-178457 and the like, a high boiling point organic solvent, if necessary, a boiling point of 50 ° C.
It can be used in combination with an organic solvent having a low boiling point of up to 160 ° C. The amount of the high boiling point organic solvent is 10 g or less, preferably 5 g or less, relative to 1 g of the dye-donor compound used. Further, 1 cc or less, more preferably 0.5 cc or less, and especially 0.3 cc or less is suitable for 1 g of the binder. The dispersion method using a polymer described in JP-B-51-39853 and JP-A-51-59943 can also be used. In the case of a compound which is substantially insoluble in water, fine particles can be dispersed and contained in a binder in addition to the above method. When dispersing the hydrophobic compound in the hydrophilic colloid, various surfactants can be used. For example, JP-A-59-1
The surfactants listed on pages (37) to (38) of No. 57636 can be used.

In the present invention, a compound capable of activating the development of the light-sensitive material and stabilizing the image at the same time can be used. Specific compounds preferably used are described in US Pat. No. 4,500,626, columns 51 to 52. In a system for forming an image by diffusion transfer of a dye, a dye fixing material is used together with a light-sensitive material. The dye fixing material may be applied separately on a support different from the photosensitive material, or may be applied on the same support as the photosensitive material. 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 relationship described in column 57 of US Pat. No. 4,500,626 can be applied to the present application.

The dye fixing material preferably used in the image forming method of 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 US Pat. No. 4,500.
626, columns 58 to 59 and JP-A-61-88256, pages (32) to (41), the mordants described in JP-A-62-2.
Those described in No. 44043, No. 62-244036 and the like can be mentioned. Also, US Pat.
A dye-accepting high molecular compound as described in No. 9 may be used. If necessary, the dye fixing material may be provided with auxiliary layers such as a protective layer, a peeling layer, and an anti-curl layer. In particular, it is useful to provide a protective layer.

In the constituent layers of the light-sensitive material and the dye-fixing material, a high-boiling organic solvent can be used as a plasticizer, a slipping agent, or an agent for improving the peelability of the light-sensitive material and the dye-fixing material. Specifically, JP-A-62-253159 (2
5), No. 62-245253 and the like. Further, various silicone oils (all silicone oils from dimethyl silicone oils to modified silicone oils obtained by introducing various organic groups into dimethyl siloxane) can be used for the above purpose. As examples thereof, various modified silicone oils described in “Modified Silicone Oil” technical material P6-18B issued by Shin-Etsu Silicone Co., Ltd., particularly carboxy-modified silicone (trade name X-22-3710) are effective. Further, the silicone oils described in JP-A Nos. 62-215953 and 63-46449 are also effective.

An anti-fading agent may be used in the light-sensitive material and the dye-fixing material. As the anti-fading agent, there are, for example, an antioxidant, an ultraviolet absorber, or a kind of metal complex.
Examples of the antioxidant include chroman compounds, coumarane compounds, phenol compounds (for example, hindered phenols), hydroquinone derivatives, hindered amine derivatives, and spiroindane compounds. The compounds described in JP-A-61-159644 are also effective. Examples of ultraviolet absorbers include benzotriazole compounds (US Pat. No. 3,533,794, etc.), 4-thiazolidone compounds (US Pat. No. 3,352,681, etc.), benzophenone compounds (JP-A-46-2784, etc.), and others. No. 54-48535, No. 62-136641
No. 61-88256 and the like. Further, the ultraviolet absorbing polymer described in JP-A-62-260152 is also effective. As the metal complex, US Pat.
No. 241155, No. 4245018, columns 3 to 36, No. 4254195, columns 3 to 8, JP-A No. 62-17474.
1, No. 61-88256, pages (27) to (29), No. 63-199248, JP-A-1-75568, No. 1
There are compounds described in, for example, -74272. Examples of useful anti-fading agents are disclosed in JP-A-62-215272 (12).
5) to (137).

The anti-fading agent for preventing the fading of the dye transferred to the dye-fixing material may be contained in the dye-fixing element in advance, or may be supplied to the dye-fixing element from the outside such as a light-sensitive material. May be. The above-mentioned antioxidant, ultraviolet absorber, and metal complex may be used in combination.

A fluorescent whitening agent may be used in the light-sensitive material and the dye-fixing material. In particular, it is preferable to incorporate a fluorescent whitening agent in the dye fixing material or supply it from the outside such as a light-sensitive material. For example, see “The Chemis” edited by K. Veenkataraman.
try of Synthetic Dyes ", Volume V, Chapter 8, JP-A-61-
The compound described in 143752 etc. can be mentioned. More specifically, stilbene compounds, coumarin compounds, biphenyl compounds, benzoxazolyl compounds, naphthalimide compounds, pyrazoline compounds, carbostyryl compounds and the like can be mentioned. The fluorescent whitening agent can be used in combination with an anti-fading agent.

The hardener used in the constituent layers of the dye fixing material is described in US Pat.
9-116655, 62-245261, 61
Hardeners described in No. 18942 and the like can be mentioned. More specifically, aldehyde hardeners (formaldehyde etc.), aziridine hardeners, epoxy hardeners, vinyl sulfone hardeners (N, N'-ethylene-bis (vinylsulfonylacetamide)) Ethane, etc.), N-methylol type hardeners (dimethylol urea, etc.), or polymer hardeners (compounds described in JP-A-62-234157).

In the constituent layers of the light-sensitive material and the dye-fixing material, various surfactants can be used for the purposes of coating aid, improvement of peeling property, improvement of sliding property, antistatic property, acceleration of development and the like. Specific examples of the surfactant are disclosed in JP-A-62-173463.
No. 62-183457 and the like.

The constituent layers of the light-sensitive material and the dye-fixing material may contain an organic fluoro compound for the purpose of improving slipperiness, preventing electrification and improving releasability. Typical examples of organic fluoro compounds include Japanese Patent Publication No. 57-9053, columns 8 to 17,
Fluorine-based surfactants described in JP-A-61-29444, JP-A-62-135826 and the like, oil-like fluorinated compounds such as fluorinated oil, or solid fluorinated compound resins such as tetrafluoroethylene resin Hydrophobic fluorine compounds may be mentioned.

A matting agent can be used in the light-sensitive material and the dye-fixing material. Matting agents such as silicon dioxide, polyolefins, polymethacrylates, etc.
In addition to the compounds described on page 1-88256 (29), benzoguanamine resin beads, polycarbonate resin beads, AS resin beads and the like are disclosed in JP-A-63-274944.
No. 63-274952. In addition, the constituent layers of the light-sensitive material and the dye-fixing material may contain a thermal solvent, a defoaming agent, an antibacterial / antifungal agent, colloidal silica and the like. Specific examples of these additives are disclosed in JP-A-61-8.
No. 8256, pages (26) to (32).

In the image forming method of the present invention, an image forming accelerator can be used in the light-sensitive material and / or the dye fixing material. The image formation accelerator includes a redox reaction between a silver salt oxidizing agent and a reducing agent, a reaction such as generation of a dye from a dye-donor substance, decomposition of the dye or release of a diffusible dye, and a light-sensitive material layer. Has a function of accelerating the transfer of the dye from the dye to the dye fixing layer, and from the physicochemical function, a base or a base precursor, a nucleophilic compound, a high boiling organic solvent (oil), a thermal solvent, a surfactant, silver Alternatively, they are classified into compounds that interact with silver ions. However, these substance groups generally have a composite function, and usually have some of the above-mentioned accelerating effects together. For details of these, see U.S. Pat. No. 4,678,739 Nos. 38-4.
It is described in column 0.

Examples of the base precursor include salts of an organic acid and a base that are decarboxylated by heat, compounds that release amines by intramolecular nucleophilic substitution reaction, Rossen rearrangement or Beckmann rearrangement. A specific example is US Pat. No. 45114.
93, JP-A-62-65038 and the like. In a system in which heat development and dye transfer are performed simultaneously in the presence of a small amount of water, it is preferable to add a base and / or a base precursor to the dye-fixing material in order to enhance the storage stability of the light-sensitive material.

In addition to the above, European Patent Publication 210660
No. 4,740,445, and combinations of sparingly soluble metal compounds and compounds capable of complex-forming reaction with metal ions constituting the sparingly soluble metal compounds (referred to as complex-forming compounds), and JP-A-61-232451. Compounds that generate a base by electrolysis as described in No. 1 can also be used as the base precursor. The former method is particularly effective. It is advantageous to add the hardly soluble metal compound and the complex-forming compound separately to the light-sensitive material and the dye-fixing material.

In the present invention, various development stoppers can be used in the light-sensitive material and / or the dye-fixing material for the purpose of always obtaining a constant image with respect to variations in processing temperature and processing time during development. The development terminator here means
After suitable development, a compound that neutralizes or reacts with a base to quickly lower the concentration of the base in the film to stop the phenomenon or a compound that interacts with silver and a silver salt to suppress development,
Specifically, an acid precursor that releases an acid by heating,
Examples thereof include an electrophilic compound that causes a substitution reaction with a coexisting base upon heating, or a nitrogen-containing heterocyclic compound, a mercapto compound and a precursor thereof. Further details are described in JP-A-62-253159, pages (31) to (32).

As the support for the light-sensitive material and the dye-fixing material used in the image forming method of the present invention, those which can withstand the processing temperature are used. Generally, paper and synthetic polymer (film) are used. Specifically, polyethylene terephthalate, polycarbonate, polyvinyl chloride, polystyrene, polypropylene, polyimide, celluloses (for example, triacetyl cellulose) or those films containing a pigment such as titanium oxide, and polypropylene are used. The film method synthetic paper, mixed paper made from synthetic resin pulp such as polyethylene and natural pulp, Yankee paper, baryta paper, coated paper (particularly Cascote paper), metal, cloth and glass are used. These can be used alone or as a support having one or both sides laminated with a synthetic polymer such as polyethylene. In addition to this, JP-A-62-253159 (2
The supports described on pages 9) to (31) can be used. A hydrophilic binder, a semiconductor metal oxide such as alumina sol or tin oxide, carbon black and other antistatic agents may be coated on the surface of these supports.

As a method for exposing and recording an image on a light-sensitive material, for example, a method of directly photographing a landscape or a person with a camera or the like, a method of exposing through a reversal film or a negative film with a printer or an enlarger, A method of scanning and exposing an original image through a slit or the like using an exposure device of a copying machine, a method of exposing image information by emitting light from a light emitting diode or various lasers through an electric signal, a CRT, a liquid crystal display of image information, There is a method of outputting to an image display device such as an electroluminescence display and a plasma display, and exposing directly or through an optical system.

As a light source for recording an image on a photosensitive material,
As described above, the natural light, tungsten lamp, light emitting diode, laser light source, CRT light source, etc.
The light source described in 500626, column 56 can be used.

Image exposure can also be performed using a wavelength conversion element in which a non-linear optical material and a coherent light source such as laser light are combined. Here, the non-linear optical material is a material capable of exhibiting non-linearity between polarization and electrolysis, which appears when a strong optical electric field such as laser light is applied, such as lithium niobate and potassium dihydrogen phosphate (KD).
P), lithium iodate, inorganic compounds represented by BaB ₂ O _4, etc., urea derivatives, nitroaniline derivatives such as 3
-Methyl-4-nitropyridine-N-oxide (PO
Nitropyridine-N-oxide derivatives such as M) and the compounds described in JP-A Nos. 61-53462 and 62-210432 are preferably used. As the form of the wavelength conversion element, a single crystal optical waveguide type, a fiber type and the like are known, and any of them is useful.

Further, the image information is a video camera,
An image signal obtained from an electronic still camera or the like, a television signal represented by Nippon Television Signal Standard (NTSC),
An image signal obtained by dividing an original image into a large number of pixels such as a scanner, or an image signal created by using a computer represented by CG and CAD can be used.

The light-sensitive material and / or the dye-fixing material are
It may have a form having a conductive heating element layer as a heating means for heat development or dye diffusion transfer. In this case, the transparent or opaque heating element is disclosed in
Those described in No. 145544 and the like can be used. In addition,
These conductive layers also function as antistatic layers.

The heating temperature in the heat development step is about 50 ° C. to about 250 ° C., and development is possible, but especially about 80 ° C. to about 180 ° C.
C is useful. The dye diffusion transfer process may be performed simultaneously with the heat development, or may be performed after the end of the heat development process. In the latter case, the heating temperature in the transfer step can be transferred in the range from the temperature in the heat development step to room temperature, but it is more preferably 50 ° C. or higher and about 10 ° C. lower than the temperature in the heat development step. Although the transfer of the dye occurs only by heat, a solvent may be used to accelerate the transfer of the dye. Further, JP-A-59-218443 and 61-
As described in detail in No. 238056, a method of performing development and transfer 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 preferably 50 ° C. or higher and not higher than the boiling point of the solvent. For example, when the solvent is water, it is preferably 50 ° C. or higher and 100 ° C. or lower.

Examples of the solvent used for accelerating the development and / or transferring the diffusible dye to the dye-fixing layer include water or a basic aqueous solution containing an inorganic alkali metal salt or an organic base (these bases). Examples thereof include those described in the section of the image formation accelerator). Further, a low boiling point solvent, or a mixed solution of a low boiling point solvent and water or a basic aqueous solution can be used. Further, a surfactant, an antifoggant, a sparingly soluble metal salt and a complex forming compound may be contained in the solvent.

These solvents can be used by a method of applying them to the dye fixing material, the photosensitive material 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 or less (particularly the amount of the solvent corresponding to the maximum swelling volume of the entire coating film less the weight of the total coating film). Examples of the method for applying a solvent to the photosensitive layer or the dye fixing layer include, for example, JP-A-61-147244 (2).
6) There is a method described on page. Alternatively, the solvent may be contained in a microcapsule in advance and incorporated in the light-sensitive element or the dye-fixing element or both.

In order to promote dye transfer, a method in which a hydrophilic thermal solvent that is solid at room temperature and dissolves at high temperature is incorporated in the light-sensitive material or the dye-fixing material can also be used. The hydrophilic thermal solvent may be incorporated in either the light-sensitive material or the dye fixing material, or may be incorporated in both. 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 its adjacent layer. Examples of hydrophilic thermal solvents include ureas, pyridines, amides, sulfonamides, imides, alcohols, oximes and other heterocycles. Further, in order to promote dye transfer, a high boiling point organic solvent may be contained in the light-sensitive material and / or the dye fixing material. Hereinafter, the present invention will be specifically described by way of examples, but the present invention is not limited to these examples.

[0071]

EXAMPLE A method for preparing the silver halide emulsion (I) for the fifth layer will be described.

To the well-stirred aqueous solution having the composition shown in Table 1, the solutions I and II having the compositions shown in Table 2 were added over 10 minutes, and then the solutions III and IV having the compositions shown in Table 2 were added. Add over 25 minutes.

[0073]

[Table 1]

[0074]

[Table 2]

Compound-1 shown in Table 1 is shown in Chemical formula 5.

After washing with water and desalting (performed at pH = 4.1 using the precipitating agent a shown in Chemical formula 7), 22 g of gelatin was added to adjust pH = 6.0 and pAg = 7.9. , 60
Chemically sensitized at ℃. The compounds used for chemical sensitization are shown in Table 3.

Immediately before the chemical sensitization, 50 cc of a 1% solution of the sensitizing dye shown in Chemical formula 6 (a mixed solvent of methanol: water = 1: 1) was added.

The yield of the obtained emulsion was 630 g, and it was a monodisperse cubic emulsion having a coefficient of variation of 10.3%, and the average grain size was 0.21 μm.

[0079]

[Table 3]

[0080]

[Chemical 5]

[0081]

[Chemical 6]

[0082]

[Chemical 7]

The method for preparing the silver halide emulsion (II) for the third layer will be described.

To the well-stirred aqueous solution having the composition shown in Table 4, the solutions I and II having the compositions shown in Table 5 were added over 18 minutes, and then the solutions III and IV having the compositions shown in Table 5 were added. Added over 24 minutes.

[0085]

[Table 4]

[0086]

[Table 5]

Compound-1 shown in Table 4 is shown in Chemical formula 5.

After washing with water and desalting (performed at pH = 3.9 using the precipitating agent b shown in Chemical formula 7), 22 g of gelatin was added to adjust pH = 5.9 and pAg = 7.8. , 70
Chemically sensitized at ℃. During the chemical sensitization, 19.5 cc of a 1% methanol solution of the sensitizing dye shown in Chemical formula 8 (p-toluenesulfonic acid 0.2N) was added. The compounds used for the chemical sensitization are shown in Table 6.

The yield of the obtained emulsion was 645 g, which was a monodisperse cubic emulsion having a coefficient of variation of 9.7%, and the average grain size was 0.24 μm.

[0090]

[Table 6]

[0091]

[Chemical 8]

A method for preparing the silver halide emulsion (III) for the first layer will be described.

Solution I and solution II having the composition shown in Table 8 were added to a well-stirred aqueous solution having the composition shown in Table 7 over 18 minutes, and then solution III and solution IV having the composition shown in Table 8 were added. Add over 25 minutes.

[0094]

[Table 7]

[0095]

[Table 8]

Compound-1 shown in Table 7 is shown in Chemical formula 5.

After washing with water and desalting (performed at pH = 4.1 using the precipitating agent a shown in Chemical formula 7), 22 g of gelatin was added to adjust pH = 7.4 and pAg = 7.6. , 60
Chemically sensitized at ℃. During the chemical sensitization, 7.5 cc of a 0.2% methanol solution of the sensitizing dye shown in Chemical formula 9 (p-toluenesulfonic acid 0.1N) was added. The compounds used for the chemical sensitization are shown in Table 9.

The yield of the obtained emulsion was 650 g, and it was a monodisperse cubic emulsion having a coefficient of variation of 12.6%, and the average grain size was 0.25 μm.

[0099]

[Table 9]

[0100]

[Chemical 9]

[0101]

[Chemical 10]

[0102]

[Chemical 11]

[0103]

[Chemical 12]

[0104]

[Chemical 13]

Next, a method for preparing a gelatin dispersion of zinc hydroxide will be described.

12.55 g of zinc hydroxide having an average particle size of 0.25 μm, 1 g of carboxymethyl cellulose as a dispersant, and 0.1 g of sodium polyacrylate were added to 100 cc of a 4% gelatin aqueous solution, and the average particle size was 0.75 mm with a mill.
The glass beads were crushed for 30 minutes. The glass beads were separated to obtain a gelatin dispersion of zinc hydroxide.

Next, a method for preparing a gelatin dispersion of the hydrophobic additive will be described. The oil phase components shown in Table 10 were each dissolved in 250 cc of ethyl acetate to obtain a uniform solution at 60 ° C. To this, add the water phase component heated to 60 ° C, and use a dissolver with a diameter of 8 cm for 30 minutes for 500 minutes.
Dispersed at 0 rpm. To this was added post-hydration and stirred to form a uniform dispersion. This is called a gelatin dispersion of hydrophobic additives.

[0108]

[Table 10]

By using these materials and the materials described in Chemical formulas 14 to 20, heat-developable color light-sensitive materials 100 having multilayer constitutions shown in Tables 11 to 13 and dye fixing material R-1 having constitutions shown in Tables 14 to 15 were prepared. .

[0110]

[Table 11]

[0111]

[Table 12]

[0112]

[Table 13]

[0113]

[Table 14]

[0114]

[Table 15]

[0115]

[Chemical 14]

[0116]

[Chemical 15]

[0117]

[Chemical 16]

[0118]

[Chemical 17]

[0119]

[Chemical 18]

[0120]

[Chemical 19]

[0121]

[Chemical 20]

Next, evaluation was performed by the following exposure and processing. Photographic property Using a laser exposure device described in Japanese Patent Application No. 2-129625, exposure was carried out under the conditions shown in Table 16, water of 11 cc / m ² was supplied to the emulsion surface of the exposed light-sensitive material with a wire bar, and thereafter, The dye-fixing material and the film surface were superposed so that the film surface was in contact. The dye-fixing material was peeled off from the light-sensitive material by using a heat drum whose temperature was adjusted so that the temperature of the absorbed film was 83 ° C., and the image was obtained on the dye-fixing material. Next, the concentration was measured under the status A condition of X-RITE, and the relative sensitivity at Dmin and Dmin +0.8 was examined.

[0123]

[Table 16]

Film Physical Properties Water is applied at 40 ° C. to the coating film of the heat-developable color photosensitive material,
It was measured how much the coating film swells. Storability Heat-developable color photosensitive material at 40 ° C and 75% RH for 14
It was preserved for a day and evaluated before and after. Manufacturing Applicability Each coating solution of the heat-developable color light-sensitive material was continuously coated for 48 hours, and the number of sloppy spot defects due to gelation of the coating solution was counted. Next, in the light-sensitive material 100, the light-sensitive material was prepared in exactly the same manner except that the hardener (31) was added in place of the first layer hardener (20) so that the coating amount was 53 mg / m ^2. 101 was produced. Further, in the light-sensitive material 100, the water-soluble polymer compound (16) for the first and second layers
Instead of, a water-soluble polymer having an intrinsic viscosity [η] = 1.2, 0.8 (the chemical structure is the same as that of the water-soluble polymer compound (16)), 12 mg / m ² in the second layer, 8 mg / m ^2, except in the first layer be added to a coating amount of ^{55mg / m 2, 37mg / m} 2, in the same manner, the photosensitive material 10
2, 103 were produced. Table 17 shows the evaluation results for the light-sensitive materials 100 to 103.

[0125]

[Table 17]

As shown in the above results, by using the hardener and the water-soluble polymer compound in the present invention, a heat-developable color light-sensitive material having excellent storage stability and manufacturability can be obtained. I understand.

[Procedure amendment]

[Submission date] June 1, 1993

[Procedure Amendment 1]

[Document name to be amended] Statement

[Name of item to be corrected] 0005

[Correction method] Change

[Correction content]

All of these generate or release a dye by heating to form an image-like distribution of the dye, and are characterized in that the image-like distribution of the dye can be obtained in a short time. Conventional photosensitive materials have blue, green and red spectral sensitivities,
A color CRT (cathode ray tube) is generally used as an exposure light source to obtain an image by using image information converted into an electric signal on such a light-sensitive material, but the CRT is a large-sized print. Is unsuitable for obtaining. Further, a light emitting diode (LED) or a semiconductor laser has been developed as a writing head capable of obtaining a large size print. However, none of these optical writing heads that efficiently emit blue light has been developed.

[Procedure Amendment 2]

[Document name to be amended] Statement

[Correction target item name] 0016

[Correction method] Change

[Correction content]

The addition amount of the compound represented by general formula (I), examples of compounds of the type, it is desirable to select the optimum amount depending on the type of gelatin, gelatin 100g per 6 × 10 ^-8 ~6 × 10 ^{- It} is preferably ⁴ mol, more preferably 3 × 10 ^{−7 to} 12 × 10 ⁻⁵ mol.

[Procedure 3]

[Document name to be amended] Statement

[Name of item to be corrected] 0025

[Correction method] Change

[Correction content]

In order to obtain a wide range of colors in the chromaticity diagram by using the three primary colors of yellow, magenta and cyan, a combination of at least three silver halide emulsion layers sensitive to different spectral regions is used. . For example, a combination of three layers of blue-sensitive layer, green-sensitive layer and red-sensitive layer, green-sensitive layer, red-sensitive layer,
There are combinations of infrared photosensitive layers. Each of the light-sensitive layers can take various arrangement orders known in a conventional type color light-sensitive material. Further, each of these photosensitive layers may be divided into two or more layers if necessary. For the photothermographic material, a protective layer,
Various auxiliary layers such as an undercoat layer, an intermediate layer, a yellow filter layer, an antihalation layer and a back layer can be provided.

[Procedure amendment 4]

[Document name to be amended] Statement

[Name of item to be corrected] 0037

[Correction method] Change

[Correction content]

In the present invention, when a silver ion is reduced to silver under a high temperature condition, a compound which produces or releases a mobile dye in response to this reaction or in the opposite reaction, that is, a dye-donor is provided. It may also contain a sex compound.

[Procedure Amendment 5]

[Document name to be amended] Statement

[Correction target item name] 0048

[Correction method] Change

[Correction content]

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 US Pat. No. 4,500,626, columns 58 to 59 and JP-A No. 61-88256 (32).
The mordant described on page (41), JP-A-62-244043.
No. 62-244036 and the like. Further, a dye-receptive polymer compound as described in US Pat. No. 4,463,079 may be used. If necessary, a protective layer, a release layer, and
An auxiliary layer such as an anti-curl layer can be provided. In particular, it is useful to provide a protective layer.

[Procedure correction 6]

[Document name to be amended] Statement

[Name of item to be corrected] 0057

[Correction method] Change

[Correction content]

In the present invention, an image formation accelerator can be used in the light-sensitive material and / or the dye-fixing material.
The image formation accelerator includes a redox reaction between a silver salt oxidizing agent and a reducing agent, a reaction such as generation of a dye from a dye-donor substance, decomposition of the dye or release of a diffusible dye, and a light-sensitive material layer. Has a function of accelerating the transfer of the dye from the dye to the dye fixing layer, and from the physicochemical function, a base or a base precursor, a nucleophilic compound, a high boiling organic solvent (oil), a thermal solvent, a surfactant, silver Alternatively, they are classified into compounds that interact with silver ions. However, these substance groups generally have a composite function, and usually have some of the above-mentioned accelerating effects together. These details are described in US Pat. No. 4,678,739, columns 38 to 40.

[Procedure Amendment 7]

[Document name to be amended] Statement

[Correction target item name] 0061

[Correction method] Change

[Correction content]

As the support for the light-sensitive material and the dye-fixing material used in the present invention, those which can withstand the processing temperature are used. Generally, paper, synthetic polymer (film)
Is mentioned. Specifically, polyethylene terephthalate, polycarbonate, polyvinyl chloride, polystyrene, polypropylene, polyimide, celluloses (for example, triacetyl cellulose) or those films containing a pigment such as titanium oxide, and polypropylene are used. The film method synthetic paper, mixed paper made from synthetic resin pulp such as polyethylene and natural pulp, Yankee paper, baryta paper, coated paper (particularly Cascote paper), metal, cloth and glass are used. These can be used alone,
It can also be used as a support having one or both sides laminated with a synthetic polymer such as polyethylene. In addition to these, the supports described in JP-A-62-253159, pages (29) to (31) can be used. A hydrophilic binder, a semiconductor metal oxide such as alumina sol or tin oxide, carbon black and other antistatic agents may be coated on the surface of these supports.

[Procedure Amendment 8]

[Document name to be amended] Statement

[Correction target item name] 0090

[Correction method] Change

[Correction content]

[0090]

[Table 6]

[Procedure Amendment 9]

[Document name to be amended] Statement

[Correction target item name] 0091

[Correction method] Change

[Correction content]

[0091]

[Chemical 8]

[Procedure Amendment 10]

[Document name to be amended] Statement

[Name of item to be corrected] 0119

[Correction method] Change

[Correction content]

[0119]

[Chemical 18]

[Procedure Amendment 11]

[Document name to be amended] Statement

[Name of item to be corrected] 0122

[Correction method] Change

[Correction content]

Next, evaluation was performed by the following exposure and processing. Photographic property Using a laser exposure device described in Japanese Patent Application No. 2-129625, exposure was carried out under the conditions shown in Table 16, water of 11 cc / m ² was supplied to the emulsion surface of the exposed light-sensitive material with a wire bar, and thereafter, The dye-fixing material and the film surface were superposed so that the film surface was in contact. Using a heat drum whose temperature was adjusted so that the temperature of the absorbed film was 83 ° C., after heating for 35 seconds, the dye fixing material was peeled off from the photosensitive material to obtain an image on the dye fixing material. Next, the concentration was measured under the status A condition of X-RITE, and the relative sensitivity at Dmin and Dmin +0.8 was examined.

Claims (1)

[Claims] 1. A heat-developable color light-sensitive material having at least a light-sensitive silver halide emulsion, a binder and a dye-donor compound on a support, and a layer hardened with a compound represented by the following general formula (I). And has a sulfonic acid group, a sulfuric acid ester group, or a carboxyl group in the side chain in the layer and / or the layer applied adjacent to the layer, and has an intrinsic viscosity [η] (0.1 N NaCl, 30 ° C) is 0.
A heat-developable color light-sensitive material comprising at least one water-soluble polymer compound of 4 to 1.5. [Chemical 1] In the formula, R represents a hydrogen atom, an alkyl group, an aralkyl group, an aryl group or a heterocyclic group. n represents 0 or 1.