JPH0355544A - Heat developable color photosensitive material - Google Patents

Abstract

PURPOSE:To obtain color images which have a high image density and low stains both right after production and after the preservation with time by incorporating at least one kind of specific compds. into the above material. CONSTITUTION:At least one kind of the compds. expressed by formulas I to IV are incorporated into the heat developable color photosensitive material having at least a photosensitive silver halide, binder and a dyestuff donative compd. which releases or forms a diffusive dyestuff in correspondence or reverse correspondence to the reaction to reduce the silver halide to silver. In the formulas I to IV, X denotes -SO2-, etc.; n denotes 0 or 1 integer; R1 to R8 respectively denote a hydrogen atom, substd. or unsubstd. alkyl group, etc.; R9 to R14 respectively denote a substd. or unsubstd. alkyl group, aryl group, etc.; Z denotes the atom group which form respectively substd. or unsubstd. arom. rings or heterocycles by combining with each other. The color images having the excellent green preservable property, the high max. density of images and the low stains are obtd. in this way.

Description

Detailed Description of the Invention (Industrial Field of Application) The present invention relates to a heat-developable color photosensitive material, which has particularly good storage stability, has a high maximum image density, and is capable of producing color images with low stain. The invention relates to heat-developable color photosensitive materials.

(Background Art) Heat-developable photosensitive materials are well known in this technical field, and for information about heat-developable photosensitive materials and their processes, see, for example, "Fundamentals of Photographic Engineering" Non-Silver Salt Photography Edition (published by Corona Publishing, 1982), Volume 2.
It is described on pages 42 to 255.

Many methods have also been proposed for obtaining color images by heat development.

For example, U.S. Patent Nos. 3,531,286 and 3,761
．． No. 270, No. 4,021,240, Belgian Patent No. 802,519, Research Disclosure magazine (hereinafter referred to as RD), September 1975, pages 31-32, etc., describe the bond between an oxidized developer and a coupler. proposed a method for forming color images.

However, since the heat-developable photosensitive materials used to obtain the color images mentioned above are non-fixing type, silver halide remains even after the image is formed, and the white background gradually becomes colored when exposed to strong light or stored for a long period of time. This poses a serious problem. Furthermore, the above-mentioned methods generally require a relatively long time for development, and the resulting images have the drawbacks of high fog and low image density.

In order to improve these drawbacks, a diffusive dye is formed or released in an image form by heating, and this diffusible dye is
A method has been proposed in which images are transferred to an image-receiving material having a mordant using a solvent such as water.

(U.S. Pat. No. 4,500,626, U.S. Pat. No. 4,483,91
No. 4, No. 4,503,137, No. 4,559,290
No.: JP-A-59-165054, etc.) In the above method,
The developing temperature is still high, and the stability of the photosensitive material over time is not sufficient. Therefore, JP-A No. 59-218,443 discloses a method in which heat development is performed in the presence of a base or a base precursor and a trace amount of water to transfer the dye, thereby accelerating development, lowering the development temperature, and simplifying the processing. , same 6l-238
No. 056, European Patent No. 210.660A2, etc.

Many methods have been proposed for obtaining clear color images by heat development.

For example, US Pat. No. 4,559,290 describes the so-called DRR.
A reducing agent or its precursor is present in the oxidized form of the compound that does not have the ability to release a dye, and the reducing agent is oxidized according to the exposure amount of silver halide by heat development, and the reducing agent that remains unoxidized is A method of reducing and releasing a diffusible dye has been proposed. Also, European Patent Publication No. 22074
No. 6, Kokai Technical Report 87-6199 (Vol. 12, No. 22) describes N as a compound that releases a diffusible dye by a similar mechanism.
A heat-developable color photosensitive material using a compound that releases a diffusible dye upon reductive cleavage of a -X bond (X represents an oxygen atom, a nitrogen atom, or a sulfur atom) has been described.

(Problems to be Solved by the Invention) In the heat-developable color photosensitive material as described above, a dye-donating compound is contained in the photosensitive material film.

This dye-providing compound reacts under high pH conditions during processing, thereby producing the image form or the necessary dye. However, if this dye-forming reaction occurs during raw storage of the photosensitive material, the result is an increase in stain in the white background portion of the image, resulting in deterioration of discrimination. In particular, when bases and base precursors coexist in the membrane,
It was observed that this reaction was likely to occur, and the main reason for this is thought to be that the pH of the membrane increases during storage.

In addition to the above-mentioned dye-forming reaction, it has been found that when the pH of the film increases, various problems occur, such as the organic matter in the film being oxidized in the air and causing stains.

(Objective of the Invention) The object of the present invention is to provide a heat-developable color photosensitive material with excellent shelf life, that is, to obtain color images with high image density and low stain both immediately after production and after storage over time. The purpose of the present invention is to provide a heat-developable color photosensitive material.

(Means for Solving the Problems) An object of the present invention is to provide at least a photosensitive silver halide, a binder, and a diffusible dye on a support in response to or inversely to the reaction in which the silver halide is reduced to silver. In the heat-developable color photosensitive material having a dye-providing compound which releases or forms
This was achieved by a heat-developable color photosensitive material containing at least one of the compounds represented by V).

General formula (13 O 0 (II) O O [■] ○ [■] O II In general formulas CI) to (IV), X is 101 or -S
Indicate O2-. n represents an integer of 0 or l.

R1 to R are each a hydrogen atom, a halogen atom, a cyano group, a substituted or unsubstituted alkyl group, an aryl group, a heterocyclic group, an alkoxy group, an alkylthio group,
Represents an aryloxy group or an arylthio group.

R. -R. Two substituents selected from these or R7 and Rl may be bonded to each other to form a ring.

R. ~R. represents a substituted or unsubstituted alkyl group, aryl group, or heterocyclic group, respectively.

R. and R. may be combined with each other to form a ring. Z represents a group of atoms that are bonded to each other to form a substituted or unsubstituted aromatic ring or heterocycle.

In the present invention, compounds of general formulas (Ill to [■]) are used as acid precursors.

The acid precursor in the present invention refers to a compound that releases an acid by heat or hydrolysis.

The compounds of general formulas [I] to (■) are condensates of imide or amine and carboxylic acid or sulfonic acid, and are generally known compounds. Compounds of general formulas [I] to (II[] can be easily synthesized by reaction of imide potassium salt and sulfonic acid halide or carboxylic acid halide, and compounds of general formula (IV) Similarly, amines can be similarly synthesized by reaction with sulfonic acid halides.

The substituents contained in the compounds of general formulas (I) to (TV) will be described.

R1~R. each represents a hydrogen atom, a halogen atom, a cyano group, a substituted or unsubstituted alkyl group, an aryl group, a heterocyclic group, an alkoxy group, an alkylthio group, an aryloxy group, or an arylthio group.

Examples of substituents for the above alkyl groups, aryl groups, etc. include halogen atoms, hydroxyl groups, nitro groups, cyano groups, sulfo groups, acyl groups, acyloxy groups, carpoxyl groups, alkoxyl groups, aryloxycarbonyl groups,
Amino group, acylamino group, alkylsulfonylamino group, arylsulfonyl group, alkylsulfonyl group, dialkylphosphoryl group, diarylphosphoryl group, carponamide group, sulfonamide group, carbamate group, ureido group, alkyl group, aryl group, alkoxy group, alkylthio group, aryloxy group, and arylthio group.

R and ~R are preferably a hydrogen atom, a substituted or unsubstituted alkyl group (preferably 20 or less carbon atoms; for example, methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, t -butyl, pentyl,
Neopentyl, amyl, benzyl, n-octyl, t-
Octyl, n-decyl, n-dodecyl, n-hexadecyl, cyclopentyl, cyclohexyl, decalyl, hydroxyethyl, chloromethyl, bromomethyl, alkoxymethyl), aryl group (preferably 20 or less carbon atoms).

For example, phenyl, tolyl, chlorophenyl, xylyl,
naphthyl, diphenyl, alkoxyphenyl, acetylphenyl), heterocyclic group (preferably 20 or less carbon atoms; for example, pyridyl, furyl, alkylbiridyl, quinolyl,
isoquinolyl, indolyl).

Also, R. ~R. each represents a substituted or substituent alkyl group, aryl group, or heterocyclic group.

Examples of substituents for the above alkyl groups, aryl groups, etc. include halogen atoms, hydroxyl groups, nitro groups, cyano groups, sulfo groups, acyl groups, acyloxy groups, carboxyl groups,
Alkoxycarbonyl group, aryloxycarbonyl group, amino group, acylamino group, alkylsulfonylamino group, arylsulfonyl group, alkylsulfonyl group,
dialkylphosphoryl group, diarylphosphoryl group, carponamide group, sulfonamide group, carbamate group,
ureido group, alkyl group, aryl group, alkoxy group,
Examples include an alkylthio group, an aryloxy group, and an arylthio group.

R, to R+4 will be explained in more detail. R. ~R
+ 4 is a substituted or unsubstituted alkyl group (preferably 20 or less carbon atoms; for example, methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, t-
Butyl, Bentyl, Neopentyl, Amyl, Benzyl,
n-octyl, t-octyl, n-decyl, n-dodecyl, n-hexadecyl, cyclopentyl, cyclohexyl, decalyl, hydroxyethyl, chloromethyl, bromomethyl, alkoxymethyl), aryl group (2 carbon atoms)
It is preferably 0 or less. For example, phenyl, tolyl, chlorophenyl, xylyl, naphthyl, diphenyl, alkoxyphenyl, acetylphenyl), heterocyclic groups (20 carbon atoms
The following are preferred. For example, biridyl, furyl, alkylbiridyl, quinolyl, isoquinolyl, indolyl).

2 is a substituted or unsubstituted aromatic ring (preferably 20 or less carbon atoms; for example, benzene, toluene, xylene, naphthalene, anthracene, phenanthrene, birene, biphenyl, chlorobenzene, bromobenzene,
methoxybenzene, cyanobenzene), or a heterocyclic ring (preferably 20 or less carbon atoms; for example, pyridine, furan, thiophene, quinoline).

When using compounds of general formulas [■] to (IV) as the acid precursor, it is also possible to use one type of the compound alone, or it is similarly possible to use two or more types in combination. In addition, as a method for adding it to the sensitive material film, it is possible to first use an emulsion dispersion method known in the art. At this time, the acid precursor may be added after being emulsified together with other hydrophobic additives, or may be added after being emulsified alone. As yet another addition method, JP-A-59-17
It is also possible to use a known fine particle dispersion method such as in No. 4830. Among the above addition methods, the compound of the present invention (
I)~[. For [IV], it is preferable to use a fine particle addition method. In addition, the additive layer includes a photosensitive layer, a protective layer,
Any of the intermediate layers is possible, and it may be added to only one of the above layers, or it may be added divided into two or more layers.

The amount of the acid breaker to be used has a wide range, but is preferably in the range of 5 to 1,000 cubic centimeters, more preferably 50 to 500 cubic centimeters, per 1 inch of light-sensitive material.

Specific examples of compounds of general formulas [I] to [■] are listed below, but the acid precursor used in the present invention is not limited to these.

AP-1 -AP-2 AP-3・ AP-4 O 0 0 O O O O AP-5 0 O O O O AP-9 0 0 AP-1 0 O AP-11 0 O AP-12 0 AP-1 3 O O AP-14 O AP-1 5 O O AP-16 O AP-1 7 AP-1 8 AP-1 9 AP-20 O O O O 0 O O AP-22 AP-23 AP-2 4 O 0 0 O O 0 AP-25 AP-26 AP-2 7 AP-28 O O 0 O O 0 AP-2 9 AP-31 0 O O 0 0 AP-35 AP-36 0 O 0 O AP-38 AP-40 O 0 0 AP-43 AP-44 0 O O 0 AP-45 0 AP-4 9 AP-5 2 U AP-5 9 the law of nature AP-8 1 O The AP-1 merger method will be described below.

<Synthesis of AP-1> 190 g of p-1 toluenesulfonyl fluoride was added dropwise to a solution of 185 g of potassium phthalate in 11 acetonitrile which was being stirred in a water bath so that the solution temperature did not exceed 5°C. After completing the dropwise addition, remove the reaction container from the water bath, and when the temperature has returned to room temperature, the formed crystals are separated by filtration and washed with water.
After drying, 247 g of AP-1 crystals were obtained. (Yield 82
%) Other compounds can be synthesized in the same manner.

The heat-developable photosensitive material of the present invention basically has a photosensitive silver halide, a paint compound, and a dye-providing compound (which may also serve as a reducing agent as described later) on a support, and further includes Available depending on the situation! i Gold II4 salt oxidizing agent and the like can be contained.

These components are often added to the same layer, but they can also be added to separate layers if they are in a reactionable state. For example, if a colored dye-providing compound is present in the lower layer of the silver halide emulsion, a decrease in sensitivity can be prevented. It is preferable that the reducing agent be incorporated into the photothermographic material, but it may also be supplied from the outside, for example by diffusing it from a dye fixing material, which will be described later.

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, the blue-sensing layer, the green-sensing layer, and the red-sensing layer. 1l combination, green sensitive layer, red 5! ! ．． There are combinations of layers, infrared-sensitive layers, etc. Is each photosensitive layer made of regular color photosensitive material? Various arrangement orders can be adopted.

Further, each of these photosensitive layers may be divided into 2/I1 or more if necessary.

The heat-developable photosensitive material can be provided with various auxiliary layers such as a protective layer, an undercoat layer, an intermediate layer, a yellow filter layer, an antihalethane 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 chloroiodide 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 nuclear agent or a photofog. 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.

The silver halide emulsion may be monodisperse or polydisperse, and a mixture of monodisperse emulsions may be used. Particle size is 0.1-2
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. Patent @4,500.62f3 No. 50
column, No. 4,628,021, Research Disclosure magazine (hereinafter abbreviated as RD) 17029 (197
Any of the silver halide emulsions described in JP-A-62-253159 and the like can be used.

Although the silver halide emulsion may be used unripe, it is usually used after being chemically sensitized. For emulsions for conventional light-sensitive materials, known sulfur sensitization methods, reduction sensitization methods, noble metal sensitization methods, etc. can be used alone or in combination. These chemical sensitizations can also be carried out in the presence of a nitrogen-containing heterocyclic compound (JP-A-62-253159).

The coating amount of the photosensitive silver halide used in the present invention is in the range of IH to 10 g/1 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, Aritsuki silver salt is particularly preferably used.

Organic compounds that can be used to form the above-mentioned organic silver salt oxidizing agent include U.S. Pat. No. 4,500,626, 52
-53s etc., there are penzotriazoles, fatty acids and other compounds. Also, JP-A-60-1 1 3235
Silver salts of carboxylic acids having a 7-rukynyl group such as silver 7-enylpropiolate described in JP-A-Sho (31-2490)
Acetylene silver described in No. 44 is also useful. Ariiso Ginshio is 2
You may use more than one species in combination.

The above-mentioned organic silver salts contain, per mol of photosensitive silver halide,
0.01 to 10 mol, preferably 0.01 to 1
Moles can be used together. The total coating amount of photosensitive silver halide and Wi silver salt is 50g to 10g in terms of silver.
/ Spear 2 is appropriate.

Various anticapri agents or photographic stabilizers can be used in the present invention. An example is RDI76
43 (1978) 24-25, the hepazoles and azaindenes described in JP-A-59-168442, the nitrogen-containing carboxylic acids and phosphorus W1s described in JP-A-59-168442, or the mercapto compounds described in JP-A-59-111636. and metal salts thereof, acetylene compounds described in JP-A No. 62-87957, and the like.

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 cy7ine pigments, composite merocyanine pigments, holopolar cyanine pigments,
Hemicyanine dyes, styryl dyes and hemioxo/-
color dyes are included.

Specifically, U.S. Pat.
RD17029 (1978), pages 12-13.

These sensitizing dyes may be used alone or in combination, and combinations of sensitizing dyes are often used particularly for the purpose of supersensitization.

Along with the sensitizing dye, the emulsion may contain a dye that 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. 615.841, JP-A-63-23
145 etc.). These sensitizing dyes may be added to the emulsion at or before chemical ripening, or as disclosed in US Pat. No. 4,188.
According to No. 3.756 and No. 4,225,666, the nuclear shape of the silver halide grains may be before or after the grain size. The amount added is generally about 10" to 10"2 moles per mole of silver halide.

Hydrophilic materials are preferably used for the binder in the structural layer of photosensitive materials and dye-fixing materials. Examples include those described on pages (26) to (28) of JP-A-62-253159. For military purposes, transparent or translucent hydrophilic baingu is preferable, and includes natural compounds such as proteins or cellulose derivatives such as gelatin and gelatin derivatives, polysaccharides such as starch, gum arabic, dextran, and pullulan, and polyvinyl alcohol. , borivinylpyrrolidone, acrylamide polymer, and other polymeric compounds. Also, JP-A-62-24
5260 etc., i.e., a homopolymer of vinyl monomers having 1000M or -So,M (M is a hydrogen atom or an alkali metal), these vinyl monomers or other vinyl monomers (e.g., sodium methacrylate, ammonium methacrylate, Sumiki Del L-5 manufactured by Sumitomo Chemical Co., Ltd.)
8) is also used. These binders can also be used in combination of 211 or more.

When employing a system that performs thermal development by supplying a small amount of water, the use of the above-mentioned highly water-absorbing polymer allows rapid absorption of water. Furthermore, 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 2 per lm''.
0. The following is preferable, particularly 10 g or less, more preferably 7 g or less.

The structural layers (including the back layer) of photosensitive materials or dye-fixing materials contain various materials 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. Polymer latex can be included. Specifically, JP-A-62-245258 and JP-A-62-136
Any of the polymer latexes described in No. 648, No. 62-110066, etc. can be used. In particular, if a polymer latex with a low glass transition point (40°C or less) is used for the mordant layer, cracking of the mordant layer can be prevented, and if a polymer latex with a high glass transition point is used for the back layer, curling can be prevented. is obtained.

As the reducing agent used in the present invention, those known in the field of photothermographic materials can be used. Also included are dye-donating compounds with reducing properties, which will be described later (in this case, other reducing agents can also be used in combination). Further, a reducing agent precursor that does not itself have reducing properties but exhibits reducing properties by the action of a nucleophile or heat during the development process can also be used.

Examples of reducing agents used in the present invention include U.S. Pat.
, No. 500, 626, columns 49-50, same! *4,4
8 3, 9 1 4 No. 30-3111ll, same No. 4
, No. 330,617, No. 4,5 9 0, 1 5 2
No. (17) to (18) of JP-A-60-140335
) page, No. 57-40245, No. 56-138736, No. 59-178458, No. 59-53831, No. 59-182449, No. 59-182450, No. 6
No. 0-119555, No. 60-128436 to No. 6
Up to No. 0-128439, No. 60198540, No. 6
No. 0-181742, No. 61-259253, No. 62
-244044, 62-131253 to 62
-131256, European Patent No. 220,746A2
There are reducing agents and reducing agent precursors described on pages 78 to 96 of the issue.

Combinations of various reducing agents can also be used, such as those disclosed in US Pat. No. 3,039,869.

When using diffusion-resistant reduction, an electron transfer agent and v/* are optionally added to promote electron transfer between the diffusion-resistant reducing agent and the developable silver halide. can be used in combination with an electron transfer agent precursor.

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 17-enyl-3-virazolidone Wi or amino-7-yls.

The diffusion-resistant reducing agent (electron donor) used in combination with the electron transfer agent may be one of the above-mentioned reducing agents as long as it does not substantially migrate in the layer of the photosensitive material, and preferably hydroquinones, Sulfonamide 7-functional/-ols, sulfone 7-midona 7-tols, compounds described as electron donors in JP-A-53-110827, and dye-donating compounds with diffusion resistance and reducing properties described below, etc. Listed below. In the present invention, the amount of reducing agent added is 1! 0,00,i to 2-0 mol per 1 mol, particularly preferably 0
．． 01 to 10 moles. An example of a dye-providing compound that can be used in the present invention is a compound (kapfu) that forms a dye through an oxidative coupling reaction. This coupler is 4
It may be an equivalent coupler or a 2-equivalent coupler. Also preferred are two-equivalent couplers that have a diffusion-resistant group as a leaving group and form a diffusible dye through an oxidative coupling reaction. This diffusion-resistant group may form a polymeric nodule. Specific examples of color developers and couplers are given in "The Theory of the 7 Otographic Process" by Noames, 4th edition (T
．． H. James"The Theory of t
he Photographic Process”)
291 to 334 pages and 354 to 361 pages, JP-A-58-123533, JP-A-58-149046
No. 58-149047, No. 59-111148, No. 59-124399, No. 59-174835,
59-2 31539, 59-231540, eo-2950, 60-2951, 60-
No. 14242, No. 60-23474, No. 50-66
It is described in detail in issues such as No. 249. Another example of a dye-donating compound is a compound that has the function of releasing or diffusing a diffusible dye in an imagewise manner. This type of compound can be represented by the following general formula (Ll).

(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 a linking group, and Z
corresponds to or inversely corresponds to the photosensitive silver salt having a latent image (Dye-Y), or causes a difference in the diffusivity of the compound represented by n-Z, or releases Dye, and represents a group having a property that causes a difference in diffusivity between Dye and (Dye-Y) n-Z, and n
represents 1 or 2, and when n is 2, two Dye-Y
may be the same or different.

Specific examples of the dye-providing compound represented by the general formula (LI) include the following compounds (1) to (2).
In addition, the following ■ to ■ are those that form a diffusive dye image (bodi dye image) in inverse response to silver halide development.
■ and ■ form a diffusive dye image (negative dye image) in response to silver halide development. ■U.S. Patent No. 3,1 3 4.7 6 4, U.S. Patent No. 3,
No. 362,819, No. 3,597,200, No. 3
, No. 544,545, No. 3,482,972, etc., dye developers in which a hydroquinone developer and a certain dye are linked. This dye developer is diffusible in an alkaline environment, but becomes non-diffusible when it reacts with silver halide.

■As described in U.S. Patent No. 4,503,137, etc., there are also non-diffusible compounds that release diffusible dyes in an alkaline environment but lose that ability when they react with silver halide. Can be used. For example, U.S. Pat.
, 980.479, etc., compounds that release diffusible dyes through intramolecular nucleophilic substitution reactions, U.S. Patent No. 4,1
Examples include compounds that release diffusible dyes through an intramolecular rewinding reaction of the inoxazolone ring, as described in No. 99, No. 35-4. ■US patent t! 44,559,290, European Patent No. 220746A2, U.S. Patent No. 4,783,
As described in No. 396, Kokai Gi@87-6199, etc., non-diffusible compounds that release diffusible dyes by reacting with the reducing agent remaining unoxidized during development can also be used.

Examples include U.S. Pat.
No. 9, No. 4, 1 3 9, 3 7 9, Taiyo 59
Compounds that undergo an intramolecular nucleophilic substitution reaction and release a diffusible dye after being reduced, as described in US Pat. No. 4,232,1.
No. 07, JP-A-59-101649, JP-A No. 61-882
No. 57, RD24025 (1984 sheep), etc., a compound that releases a diffusive dye by an intramolecular electron transfer reaction after being reduced, West German patent f:lS3,008,5
No. 88A, JP-A-56-142530, U.S. Patent No. 4
, 3 4 3, 8 9 3, 4, 6 1 9, 8
Compounds whose single bonds are cleaved after reduction to release a diffusible dye, as described in U.S. Patent Nos. 4 and 4, etc.
Nitro compounds that release diffusible dyes after accepting electrons, as described in U.S. Pat.
Examples include compounds that release a diffusible dye after accepting electrons, as described in Nos. 609, 610, and the like.

Also, more preferably, European Patent No. 220,7
No. 46A2, Published Technical Report 87-6199, U.S. Patent No. 4,
7 8 3, 3 9 6, JP 63-201653
No. 63-201654, etc., N in one molecule.
-X bond (X represents oxygen, sulfur t.l! or nitrogen atom)
and a compound having an electron-withdrawing group, patent application No. 1068/1986
SQ.85 in one molecule. -X (X has the same meaning as above) and an electron-withdrawing group, JP-A-63-27
A compound having a po-x bond (X is the same R as above) and an electron-withdrawing group in one molecule, described in No. 1344, Tainansho 6
3-271341, which has a C-X' bond (X' is synonymous with X or represents -S O 2-) and an electron-withdrawing group in one molecule. Moreover, a single bond is formed after reduction by a π bond conjugated with an electron-accepting group described in Japanese Patent Application No. 62-319989 and No. 62-320771. Compounds that release diffusible dyes upon cleavage are also available.

Among these, compounds having an N-X bond and an electron-withdrawing group in one molecule are particularly preferred. A specific example is European Patent Brother 22
0,746A2* or compounds (1) to (3), (7) to (10) described in U.S. Patent No. 4,783.396
, (12), (13), (15), (23)-(26)
, (31), (32), (35), (36), (40)
, (41), (44), (53) to (59), (64)
, (70), Compound of [87-6199] <11
) to (23), etc. ■A compound that is a coupler that has a diffusible dye as a leaving group and releases the diffusible dye upon reaction with the oxidized form of a reducing agent (D
DR coupler). Specifically, British Patent No. 1,330,
No. 524, Special Publication No. 48-39.165, U.S. License TL
No. S3,443,940, No. 4,47 4.8 G
There are those described in No. M, TjS4, 4 8 3, 9 1 4, etc.

■Reducing to silver halide or organic silver salts,
A compound that releases a diffusible dye upon reduction of its partner (DR
Compound R) is preferable because it does not require the use of other reducing agents and there is no problem of image staining due to oxidative decomposition products of the reducing agent. A typical example is U.S. Patent No. 3.92
No. 8,312, No. 4,053,312, No. 4.0
5 5, 4 2 8, 4, 3 3 6, 3 2
No. 2, No. 5 9-6 5 8 No. 39, No. 5 9
-6 9 8 3 9, 53-3819, 51
-104,343, RD17465, U.S. Patent No. 3
．． 7 2 5, 0 6 2, same No. 3,728,113
No. 3,443,939, JP-A-58-116,
No. 537, No. 57-179840, U.S. Patent No. 4,5
It is described in No. 00,626, etc. Specific examples of DRR compounds include the aforementioned U.S. Patent No. 4,500.
, 6 2 6, columns 22 to 44, among which compounds (1) to (3), (10) to (13), ( 16)
~(19), (28) ~(30), (33) ~(35)
, (38) to (40), and (42) to (64) are preferred. Also, U.S. Patent No. 4,639,408 No. 37
Compounds listed in columns 3 to 3 are also useful.

In addition, the above-mentioned couplers and dye-silver compounds in which an organic silver salt and a dye are combined with a dye-donating compound other than the general formula [L I 1 (Research Disclosure Magazine 19
May 1978 issue, pages 54-58), azo dyes used in heat-developable silver dye bleaching methods (U.S. Pat. No. 4,235,9)
5 No. 7, Research Disclosure Magazine, 197
June issue, April issue, pp. 30-32), leuco dye (U.S. Patent P143,985,565, 4,022,6)
1, 7, etc.) can also be used.

Hydrophobic additives such as dye-donating compounds and diffusion-resistant reducing agents can be introduced into the layers of the photosensitive material by known methods such as those described in U.S. Pat. No. 2,322,027. ．． In this case, Japanese Patent Application Laid-Open No. 59-83154,
5 - No. 178451, No. 59-178452, No. 59-178453, No. 59-178454, No. 5
A high boiling point organic solvent such as those described in No. 9-178455 and No. 59-178457 can be used in combination with a low boiling point organic solvent having a boiling point of 50° C. to 160° C., if necessary.

The amount of high-boiling organic solvent is 1 g of the dye-donating compound used.
10. It is preferably 5g or less. Also, 1gl of banhgu: less than ice, and even 0.5
cc or less, especially 0.3cc or less is suitable. Dispersion methods using polymers described in Japanese Patent Publication No. 51-39853 and Japanese Patent Application Laid-open No. 51-59943 can also be used. In the case of a compound that is substantially insoluble in water, it can be dispersed and contained in the form of fine particles in the binder in addition to the method described above.

Various surfactants can be used when dispersing hydrophobic compounds in hydrophilic colloids. For example, JP-A-59
The surfactants listed on pages (37> to (38)) of No.-157636 can be used.

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 Nos. 4 and 5.
It is described in columns 51-52 of No. 00,626.

In a system in which an i[1 image is formed by diffusion transfer of dyes, a dye-fixing material is used together with a light-sensitive material. The dye fixing material may be coated separately on a support separate from the light-sensitive material, or may be coated on the same support as the light-sensitive 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 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 examples thereof include U.S. Pat. No. 4,500,626 No. 58-5.
91! l and JP-A No. 61-88256 (32) to (4)
1), the mordant described in JP-A-62-244043,
Examples include those described in No. 62-244036. Also, dye-receiving polymeric compounds such as those described in US Pat. No. 4,463,079 may be used.

The dye fixing material can be provided with auxiliary layers such as a protective layer, a release layer, and an anti-curl layer, if necessary. It is especially useful to provide a protective layer. A high boiling point organic solvent can be used as a plasticizer, a slippery agent, or a peelability improver between the light-sensitive material and the dye-fixing material in the structural layers of the light-sensitive material and the dye-fixing material. Specifically, there are those described in JP-A-62-253-159, page (25), JP-A-62-245253, and the like.

Furthermore, various silicone oils (
All silicone oils can be used, from dimethyl silicone oil to modified silicone oils in which various organic groups are introduced into zomethylsiloxane. For example,
“Modified Silicone Oil J” published by Shin-Etsu Silicone Co., Ltd.
Various modified silicone oils, especially carboxy-modified silicone (trade name X-22-
3710) etc. are effective. Also, JP-A-62-215953 and JP-A No. 63-46449.
The silicone oil described in this issue 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 gold R complexes.

Examples of antioxidants include chroman compounds, coumaran compounds, and 7.
These include enol jl[), hydroquinone derivatives, hindamine derivatives, and spiroindanes. Also,
Compounds described in JP-A-61-159 (344) are also effective.

As ultraviolet absorbers, penzotriazole compounds (
U.S. Pat. No. 3,533.794, etc.), 4-thiazolidone compounds (U.S. Pat. No. 3,352,681, etc.), penzo-7 enone compounds (JP-A-46-27
84, etc.), and other compounds described in JP-A-54-4-8535, JP-A No. 62-1366419, JP-A No. 61-88256, etc. Also, JP-A-62-260152
The ultraviolet #j absorbing bonomer described in the above issue is also effective.

As a metal complex, U.S. Pat. No. 4,241.155,
No. 4,245,018, columns 3-36, No. 4,254,195, columns 3-8, JP-A-62-174
No. 741, No. 61-88256 (pages 27) to (29), No. 63-199248, Patent Application No. 62-234103
There are compounds described in No. 62-230595 and the like.

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 antioxidants, ultraviolet absorbers, and complexes mentioned above 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. “The
Ches+istry of Syntheti
c Dyes J Volume v Chapter 8, JP-A-61-1437
Examples include compounds described in No. 52 and the like. More specifically, stilbene compounds, coumarin compounds, biphenyl compounds, penzoxazolyl compounds, nattalimide compounds, birazoline compounds,
Examples include carbostyryl compounds. Optical brighteners can be used in combination with anti-fade agents. Examples of dura abrasions used for groove layers of photosensitive materials and dye-fixing materials include U.S. Pat.
Examples include hardeners described in No. 1-18942 and the like. More specifically, aldehyde-based hardeners (formaldehyde, etc.), 7-noridine-based hardeners, epoxy-based hardeners (nylsulfonyl 7-cetamide) ethane, etc.), N-methylol-based hardeners (di/thyrolurea, etc.) ), or polymeric hardeners (compounds described in JP-A No. 62-234157, etc.).For the structural layers of photosensitive materials and dye-fixing materials, coating aids, peelability-improving agents, and slipping-improving agents can be used. , various surfactants can be used for the purpose of preventing static electricity, promoting development, etc. Specific examples of surfactants are disclosed in JP-A-62-173463 and JP-A-62-173-1.
It is described in No. 83457, etc. The structural layers of photosensitive materials and dye-fixing materials include improved slipperiness,
An organic 7-fluoro compound may be included for the purpose of preventing static electricity and improving peelability. Representative examples of organic 7-fluoro compounds include Japanese Patent Publication No. 57-9053, columns 8 to 17,
20944, 62-135826, etc., or oily fluorine compounds such as fluorine oil, or solid fluorine compounds such as tetra7fluoroethylene resin 1! Examples include hydrophobic fluorine compounds such as f-fats. A matting agent can be used in the photosensitive material and the dye fixing material. As a matting agent, JP-A-61-8825 such as silicon dioxide, polyolefin, polymethacrylate, etc.
Flit of the compound described in issue 6 (page 29), penzoguanamine resin beads, polycarbonate! F fat beads, A
Patent Application No. 110064/1988 for resin beads, etc.
2-1 100 (There is a compound described in No. 35. In addition, the constituent layers of the light-sensitive material and the dye fixing material may contain a heat solvent, an antifoaming agent, an anti-foaming agent, a colloidal silicate agent, etc.). Specific examples of additives are given in JP-A-61-
No. 88256 ffi pages (26) to (32).

In the present invention, an image forming accelerator can be used in the light-sensitive material and/or the dye-fixing material. Image-forming or accelerating agents include promoting redox reactions between silver salt oxidizing agents and reducing agents, promoting reactions such as the growth of dyes from dye-donating substances, decomposition of dyes, and release of diffusible dyes, and photosensitizers. It has functions such as promoting the movement of dye from the material layer to the dye fixed layer, and from a physicochemical function, it is a base or base precursor, a nucleophilic compound, a high boiling point organic solvent (oil), a thermal solvent, and a surfactant. 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.

As a base precursor, I1! ! , salts of carbonated W1R and bases, compounds that release amines through intramolecular nucleophilic substitution reactions, Rossen rearrangements, or Beckman rearrangements. An example of such a weapon is U.S. Patent No. 4,511,4
No. 93, JP-A No. 62-65038, etc.

In a system in which thermal development and dye transfer are carried out simultaneously in the presence of a small amount of water, it is preferable to include a base and/or a basic precursor in the dye fixing material in order to improve the storage stability of the photosensitive material.

In addition to the above, there are also sparingly soluble metal compounds described in European Patent Publication No. 210,660 and US Pat. Combinations of compounds (referred to as complex compounds) and compounds that generate bases by electrolysis as described in JP-A-61-232451 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 complex 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 a'iit child compounds, nitrogen-containing heterocyclic compounds, merkabut compounds, and precursors thereof, which undergo a substitution reaction with a coexisting base when heated.

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, a support that can withstand 11 processing temperatures is used. Generally, paper and polymer (7ilm) are mentioned. Specifically, polyethylene teretalate, polycarbonate, polyvinyl chloride, polystyrene, polypropylene,
Polyimide, cellulose (e.g. triacetyl cellulose) or films containing pigments such as titanium oxide, film coatings made from polypropylene, paper, composite resin valves such as polyethylene, and natural pulp. Mixed paper, Yankee paper, Paraita paper, coated 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 polymer such as polyethylene.

In addition, JP-A-62-253159 (29) to (3)
The supports described on page 1) can be used. The surface of these supports may be coated with hydrophilic paint, alumina sol, semiconductive metal oxide such as tin oxide, carbon black, or other antistatic agent.

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 copying machines. 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., and exposed to light; a method in which image information is transmitted to a CRT, liquid crystal display, electroluminescence, etc. There is a method of outputting the image to an image display device such as a display or a plasma display and exposing it 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., as disclosed in US Pat. No. 4,500.
, f3 2 The light source described in f3 No. 561 can be used. Further, it is also possible to perform imagewise exposure using a wave conversion element that combines 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 charging field such as laser light is applied, and include lithium niobate, potassium dihydrogen phosphate (KDP) ), lithium iodate, BaB20. Inorganic compounds such as urea derivatives, nitro-7-niline derivatives, such as 3-methyl-4-nitrovirinone-N-oxide (POM>'s ionanitroviridine-N-oxide thick form, w Kaisho 61-5
Compounds described in No. 3462 and No. 62-210432 are preferably used. As the form of the wavelength conversion element, single crystal optical waveguide type, fiber type, etc. are known, and both are useful.

The above-mentioned image information includes image signals obtained from video cameras, electronic still cameras, etc., television signals represented by the Nippon Television Signal Standard (NTSC), and images obtained by dividing an original image into a large number of pixels using a scanner. signal, CG, C
AD′? Image signals generated using typical computers 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 an antistatic layer.

The heating temperature in the heat development step can be developed at about 50°C to about 250°C, and particularly useful is about 80°C to about 180°C. 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 it is particularly preferable to use a temperature of 50° C. or higher and 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 below the boiling point of the solvent. 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 the development and/or prevent the transfer of the diffusible dye to the dye fixed layer include water or a basic aqueous solution containing an alkali metal salt or an organic base (
Examples of these bases include those described in the section on image forms and promoters. Furthermore, a mixed solution of a low boiling point solvent or a low boiling α solvent and water or a basic aqueous solution can also be used. Further, a renal surfactant, an antifoggant, a sparingly soluble metal salt, a complex compound, and the like may be included in the solvent.

These solvents can be used to apply them to dye-fixing materials, photosensitive materials, or both. The amount used may be as small as less than the weight of the solvent corresponding to the maximum swelling volume of the entire coating (particularly less than the weight of the solvent corresponding to the maximum swelling volume of the entire coating minus the weight of the entire coating).

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 (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. In addition, the layer to be incorporated is a black agent layer,
Although it may be an intermediate layer, a protective layer, or a dye fixing layer, it is preferably incorporated in the dye fixing layer and/or its adjacent layer.

Examples of hydrophilic heat solvents include ureas, pyrinones, amides, sulfonamides, imides, alnyls, oximes, and other heterocycles.

Further, in order to promote dye transfer, a high-boiling point 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, a hot plate, a hot shaker, a hot roller, a halodenum lamp heater, an infrared or far-infrared lamp heater, etc. or passing through a high-temperature atmosphere.

The photosensitive material and the dye-fixing material are superimposed, and 'I! ! The pressure conditions and method of applying pressure when applying the pressure are described in JP-A-Sho (31-
The method described in No. 147244, page 27 can be applied.

Any of a variety of thermal development vcrf1 can be used in processing the photographic elements of this invention. For example, JP-A-59-7524
No. 7, No. 59-177547, No. 59-181353
Apparatuses described in Japanese Utility Model Application No. 60-18951, Japanese Utility Model Application Publication No. 62-25944, etc. are preferably used.

Example l> The method for preparing the fifth layer emulsion (1) will be described.

A well-stirred gelatin aqueous solution (20 g of gelatin 1 3 g of potassium bromide in 800 cc of water, and HO (CH2
)! Add 0.3g of S(CH!)23(CH2)20H and keep it warm at 55°C), add the following (1) liquid and (2)
The liquids were added simultaneously over a period of 30 minutes. Thereafter, the following solutions (3) and (4) were simultaneously added over 20 minutes.

Further, after starting the addition of the liquid (3), the following dye solution was added over a period of 18 minutes from 5 minutes.

After washing with water and desalting, 20 g of lime-treated ossein gelatin was added to adjust the pH to 6.2 and pAg to 8.5, and then sodium thiosulfate and 4-hydroxy-6-methyl-L3 were added.
．． Optimal chemical sensitization was carried out by adding 3a,7-tetrazaindene and chloroauric acid. In this way, the average particle size, 0.
600 g of a 40 μm monodispersed tetradecahedral silver iodobromide emulsion was obtained.

dye solution 0. 12g 0. 12g is dissolved in 160cc of methanol.

The method for preparing the third layer emulsion (n) will be described.

A well-stirred aqueous solution (20 g of gelatin in 7 30 ml of water, 0.30 g of potassium bromide, 6 ml of sodium chloride)
g and 0.015 g of the following chemical A and kept at 60.0°C), the following solutions (1) and (n) were added at the same time for 60 g.
Added at equal flow rates over minutes. After the addition of solution (I) was completed, a methanol solution (III) of the following sensitizing dye was added.

In this way, a monodisperse cubic emulsion adsorbed with a dye having an average grain size of 0.45 μm was prepared.

After washing with water and desalting, add 20g of gelatin and adjust the pH to 6.4.
After adjusting pAg to 7.8, chemical sensitization was performed at 60.0°C. The chemical used at this time was triethylthiourea 1
．． 6■ and 4-hydroxy-6-methyl-1.3.3a,
The aging time was 55 minutes using 100 μl of 7-tetrazaindene. The yield of this emulsion was 635 g.

(Drug A) CH. 1 C Hs (Sensitizing dye C) The method for preparing the first layer emulsion (I[[) will be described.

A well-stirred gelatin aqueous solution (20 g of gelatin 1 lg of potassium bromide in 800 m of water and 80 (C)
l! )IS(CH!)! OH 0. The following solutions (I), (II) and (II) were simultaneously added at equal flow rates over 30 minutes. In this way, a monodisperse silver bromide emulsion having an average grain size of 0.42 μm and adsorbing a dye was prepared.

After washing with water and desalting, add 20g of lime-treated ossein gelatin.
After adjusting H to 6.4 and pAg to 8.2, the temperature was kept at 60°C, and sodium thiosulfate was added to 9cm, and chloroauric acid was added to 0. 6 ml of Ol% aqueous solution, 4-hydroxy-6-methyl-1. 3
．． 190 μl of 3a,7-tetrazaindene was added and chemical sensitization was performed for 45 minutes.

pigment (a) pigment (b) A method for preparing a dispersion of zinc hydroxide will be described.

12.55g of zinc hydroxide with an average particle size of 0.2μ
As a dispersant, 1 g of carboxymethylcellulose 1 g of sodium polyacrylate was added to 100 c of a 4% gelatin aqueous solution.
In addition to C, the mixture was ground in a mill for 30 minutes using glass beads with an average particle size of 0.75 mm.

The glass beads were separated to obtain a dispersion of zinc hydroxide.

Next, a method for preparing an activated carbon dispersion will be described.

Wako Pure Condiments activated carbon powder (reagent, special grade) 2.5g 1 Dispersant: Kao Soap ■ Demol Nlg, polyethylene glycol nonyl phenyl ether 0. 2 5 g to 5
% gelatin aqueous solution, and mill it with an average particle size of 0.
．． Grinding was performed using 75 am glass beads for 120 minutes. The glass beads were separated to obtain an activated carbon dispersion with an average particle size of 0.5 μm.

Next, a method for preparing a dispersion of an electron transfer agent will be described.

Add 10g of the electron transfer agent below, 0.5g of polyethylene glycol nonyl phenyl ether as a dispersant, and 0.5g of the anionic surfactant below to a 5% aqueous gelatin solution, and mill to form glass beads with an average particle size of 0.75ma. for 60 minutes. Separate glass beads, average particle size 0
．． A 3μ electron transfer agent dispersion was obtained.

Electron transfer agent Anionic surfactant C H t C O O C H ! CI(C!Hl
)C*}Is1 Naps S CHCOOCHtCH(C*Ha)C
．． HsNext, the preparation of a gelatin dispersion of a dye-providing compound will be described.Yellow, magenta, and cyan were each added to 50 cc of ethyl acetate according to the following formulations, and heated and dissolved at about 60°C to form a uniform solution. 1 of this solution and lime-treated gelatin
After stirring and mixing 100 g of 0% aqueous solution, 0.6 g of sodium dodecylbenzenesulfonate, and 50 cc of water, the mixture was dispersed using a homogenizer at 10,000 rpm for 10 minutes. This dispersion dye-donating compound (1) Dye-donating compound (2) Dye-donating compound (3) Electron donor ■ Rih High boiling point solvent ■ Electron transfer agent precursor ■ O Next, the electron donor for the intermediate layer ■ We will describe how to make a gelatin dispersion.

The following electron donor ■23.6g and the above high boiling point solvent ■8
．． 5 g was added to 30 cc of ethyl acetate to form a homogeneous solution.

This solution and 100 g of a 10% aqueous solution of lime-treated gelatin,
Sodium bisulfite 0. 25g1 After stirring and mixing 0.3g of sodium dodecylbenzenesulfonate and 30cc of water, the mixture was heated with a homogenizer at 10,000 rpm for 10 minutes.
Dispersed at m. This dispersion is called a gelatin dispersion of electron donor (1).

Electron Donor ■ Using the above materials, the results are shown in Table 1 below. A heat-developable color photosensitive material 101 having a multilayer structure was prepared.

Table 1. Table 1 of photosensitive material 101. Continued Note 1) Surfactant ■ CH. COOCH. CH (C2 H5')C.
H9Nap. S-CHCOOCHt CH (C2H
．． ) C. H. Note 3) Water-soluble polymer Note 4) Antifoggant ■ Note 6) Polyvinyl alcohol (molecular weight 2000) Note 7) Surfactant ■ Note 8) Electron transfer agent ■ Note 9) Hardener [phase] 1, 2-bis(vinylsulfonylacetamide) Kotano Note 10) Antifoggant ■H Next, we will discuss how to make the dye fixing material.

Dye fixing material R- with the composition shown in the following table I made 1.

Table 2 Constituents of Image Receiving Material R-1 Constituents of Support (1) Silicone Oil (1) Surfactant (1) Surfactant (2) ? ．． Fl? SO■NCH2COOK C. H, Surfactant (3) Surfactant (4) Ct Hs CH2 COOCH2 CHC- H-NaOa S
CHCOOCH2CHC4H-Ct Hs Fluorescent brightener (1) 2,5-bis(5-tert-butylbenzoxazole (2)) Thiophene surfactant (5) Ca Ht 嘗C* Fl? SO! N- (CH2 CH2 057
-i: CH2 f 804 Na water-soluble polymer (1) Sumiriki Gel L5-H (Sumitomo Chemical Co., Ltd.) Water-soluble polymer (2) Dextran (molecular weight 70,000) Mordant KiIt) High boiling point solvent (1) Matting agent (2r Penzoguanamine resin (average particle size 15 μm) Furthermore, photosensitive materials 102 to 122 were prepared with exactly the same composition of 1O1 except that additives were added as shown in [Table 3] to photosensitive material 101. .

In addition, for the agent to which the additive is added, a fine particle dispersion is prepared using the same method as for the electron transfer agent dispersion described above.
This was added.

Comparative Compound (1) <Table 3> Table 3 Continued Color photosensitive materials 101 to 112 with the above multilayer structure using a tungsten light bulb, B and G with continuously changing concentrations
, R, and gray color separation filters at 5,000 lux for 1/10 second. While feeding this exposed photosensitive material at a linear speed of 20 mm/sec, 15 ml of water was poured onto the emulsion surface using a wire bar. Immediately thereafter, the image-receiving material and the film were superimposed so that their surfaces were in contact with each other.

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 it is peeled off from the image-receiving material, B, G,
Blue corresponding to R and gray color separation filters,
Clear images of green, red, and gray were obtained evenly.

Furthermore, photosensitive materials 101 to 112 were heated at 40°C and humidity 70%.
Samples stored for 7 days under these conditions were also exposed and developed in the same manner.

For both photosensitive materials 101 to 112 before storage and after storage, the maximum density (Dmax) of cyan, magenta, and yellow in the gray part and the minimum density (Dmin
) are shown in Table 4.

Example 2 A method of preparing silver halide emulsions for the fifth layer and the first layer will be described.

A well-stirred gelatin aqueous solution (containing 20 g of gelatin and 3 g of sodium chloride in 1000 ml of water, kept at 75°C) was mixed with 600 ml of an aqueous solution containing sodium chloride and potassium bromide and a silver nitrate aqueous solution (600 ml of water).
0mj! 0.59 mol of silver nitrate dissolved in the solution) was simultaneously added at an equal flow rate over 40 minutes. In this way, a monodisperse cubic silver chlorobromide emulsion (50 mol % of bromine) with an average grain size of 0.40 μm was prepared.

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

Next, a method for preparing a silver halide emulsion for the third layer will be described.

Add 600 ml of an aqueous solution containing sodium chloride and potassium bromide to a gelatin aqueous solution (containing 20 g of gelatin and 3 g of sodium chloride in too ml of water and keep warm at 75°C) that is being stirred well and add 600 ml of an aqueous solution of silver nitrate (6 ml of water).
0.59 mol of silver nitrate dissolved in 00 mA) was simultaneously added at an equal flow rate over a period of 40 minutes. In this way, a monodisperse cubic silver chlorobromide emulsion (80 mol % bromine) with an average grain size of 0.35 μm was prepared.

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

This article describes how to make penzotriazole silver emulsion.

28g of gelatin and 13.2g of penzotriazole to 33g of water
It was dissolved in 0.00ml. This solution was kept at 40°C and stirred. A solution prepared by dissolving 17 g of silver nitrate in 100 ml of water was added to this solution over 2 minutes.

The pH of the penzotriazole silver emulsion was adjusted and allowed to settle to remove excess salt. Thereafter, the pH was adjusted to 6.30, yielding 400 g of a penzotriazole silver emulsion.

This article describes how to make an acetylene silver emulsion.

20g of gelatin and 4.6g of 4-acetylaminophenyl acetylene, 1000ml of water and 20g of ethanol
Dissolved in 0 ml. This solution was kept at 40°C and stirred. A solution prepared by dissolving 4.5 g of silver nitrate in 200 ml of water was added to this solution over 5 minutes. The pH of the dispersion was adjusted and excess salt was removed by settling.

Thereafter, the pH was adjusted to 6.3 to obtain a dispersion of an acetylene silver compound in a yield of 300 g.

Next, how to make a gelatin dispersion of a dye-donating substance will be described.

Yellow dye-donating substance (5g of 3 pieces, auxiliary developer (
0.2 g of a), 0.2 g of an antifoggant, 0.5 g of sodium succinate 2-ethylhexyl ester sulfonate as a surfactant, Weighed 2.5 g of sulfate, added 30 ml of ethyl acetate,
The mixture was heated and dissolved at about 60°C to form a uniform solution. After stirring and mixing this solution and 10,0 g of a 3% solution of lime-treated gelatin, the mixture was heated at 10,000 g for 10 min using a homogenizer.
Dispersion was performed at rpm. This dispersion is called a yellow dye-providing substance dispersion.

Auxiliary developer (a) Antifoggant (b) Follow the same method as above except for using magenta dye-donating substance (5) 1 and using 2.5g of tricresyl phosphate as a high boiling point solvent. A dispersion of magenta dye-donating substance was made.

In the same manner as the yellow dye dispersion, a cyan dye-providing substance dispersion was prepared using a cyan dye-providing substance (6 pieces).

From these, a photothermographic material 201 having a multilayer structure as shown in the following table was prepared. [Table 5] (5) 1 (Jl.;+*Mss(nJ) Next, with the contents shown in [Table 6], except for the addition of additives,
Photosensitive materials 202 to 207 having exactly the same structure as 201 were prepared.

At this time, the additive was added as a fine particle dispersion in the same manner as in Example 1.

Table 6〉 A tungsten bulb was used for the photosensitive materials 201 to 207 produced in this way, and G, whose concentration was continuously changing,
RS fR three-color separation filter (G is 500 to 600
The image was exposed to light at 500 lux for 1 second through a bandpass filter with wavelengths of 600 to 700 nm for R and a filter transmitting 700 nm or more for IR.

12ml on the emulsion side of this exposed photothermographic material
/rd of water was supplied using a wire bar, and then the membrane was superimposed on the dye fixing material R-1 so that the membrane surfaces were in contact with each other.

When the dye-fixing material is peeled off from the light-sensitive material after heating for 30 seconds using a heat roller whose temperature is adjusted so that the temperature of the film that absorbs water is 93°C, G, R, IR are printed on the fixing material.
Yellow, magenta,
A clear cyan image was obtained.

In the same manner as in Example 1, 40% of the photosensitive materials 201 to 207 were
It was stored for 7 days under conditions of ℃ and 70% humidity.

The samples after storage were also exposed and developed in the same manner.

For each of the above samples, D+nax. ．． D+
The results of measuring nin for each color are shown in [Table 7].

Procedural amendment

Claims (1)

[Scope of Claims] At least a photosensitive silver halide, a binder, and a dye-donating compound that releases or forms a diffusible dye in response to or inversely to the reaction in which silver halide is reduced to silver on a support. 1. A heat-developable color light-sensitive material comprising: a heat-developable color light-sensitive material further containing at least one compound represented by the following general formulas [I] to [IV]. General formula [I] ▲There are mathematical formulas, chemical formulas, tables, etc.▼ [II] ▲There are mathematical formulas, chemical formulas, tables, etc.▼ [III] ▲There are mathematical formulas, chemical formulas, tables, etc.▼ [IV] General formula [I] ~ In [IV], X is -C- or -S
Represents O_2-. n represents an integer of 0 or 1. R_1 to R_3 are each a hydrogen atom, a halogen atom,
A cyano group represents a substituted or unsubstituted alkyl group, aryl group, heterocyclic group, alkoxy group, alkylthio group, aryloxy group or arylthio group. Two substituents selected from R_1 to R_6, or R
_7 and R_8 may be combined with each other to form a ring. R_9 to R_1_4 each represent a substituted or unsubstituted alkyl group, aryl group, or heterocyclic group. R_1_3 and R_1_4 may be combined with each other to form a ring. Z represents a group of atoms that combine with each other to form a substituted or unsubstituted aromatic ring or heterocycle.