JPH0244356A - Heat developable color photosensitive material and image forming method using same - Google Patents

Abstract

PURPOSE:To obtain color images which have a high image density and low stains and to improve a preservable property as well by providing a hydrophilic binder layer contg. an adsorptive material having the property to adsorb a chromatic material formed at the time of image forming processing of the photosensitive material. CONSTITUTION:The heat developable color photosensitive material having at least a photosensitive silver halide, binder, and a dye donative compd. which releases or forms a diffusive dye in correspondence or reverse correspondence to the reduction of the silver halide to silver on a base has the hydrophilic binder layer contg. the material to adsorb the chromatic material formed at the time of the image forming processing of the photosensitive material. The adsorbent is used as an aq. dispersion by dispersing the same into a fine particulate state (0.2-1mum). Since the adsorptive material is used in the hydrophilic binder, the colored material unnecessary for image formation is efficiently adsorbed. The image having the low stain is obtd. in this way and the excellent preservable property with age is obtd.

Description

[Detailed Description of the Invention] <Industrial Application Field> The present invention relates to a heat-developable color phosphorescent material, and in particular, it is capable of obtaining color images with high image density and low stain, and has excellent storage stability. This invention relates to heat-developable color photosensitive materials.

Background technology> 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 & 1 (published by Corona Publishing, 1982), pages 242 to 255. Truly described.

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

For example, U.S. Pat. No. 3,531,286, U.S. Pat.
No. 270, No. 4,021,240, Belgian Patent No. 8
No. 02,519, Research Disclosure (hereinafter abbreviated as RD), September 1975, pages 31-32, proposes a method of forming a color image by combining an oxidized developer and a coupler.

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. , 61-238
No. 056, European Patent No. 210.660A2, etc.

Many methods have also been proposed for obtaining positive 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, Technical Report E17-6199 (No. 1212) describes compounds that release diffusible dyes by a similar mechanism.
A heat-developable color photosensitive material using a compound that releases a diffusible dye upon reductive cleavage of an N--X bond (X represents an oxygen atom, nitrogen atom, or sulfur atom) has been described.

<Problems to be Solved by the Invention> However, in the heat-developable color photosensitive material, coloring substances are generated due to side reactions such as decomposition of the dye-providing substance during processing and side reactions of other materials constituting the photosensitive material. It has been found that there is a problem in that transfer stains occur in the white background area, deteriorating the S/N ratio. Furthermore, when the above-mentioned photosensitive material was stored for a long period of time, the undesirable transfer stain described above was observed, and it was found that there was a problem in the storage stability of the photosensitive material over time.

The object of the present invention is to provide on a support 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. The object of the present invention is to improve the S/N ratio and storage stability over time of heat-developable color photosensitive materials.

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 reduction of silver halide to silver. A heat-developable color photosensitive material having a dye-providing compound released or formed, characterized by having a hydrophilic binder layer containing a substance having the property of adsorbing a color-preserving substance generated during image forming processing of the photosensitive material. This was achieved using heat-developable color photosensitive materials.

Examples of "substances that have the property of adsorbing colored substances" that can be used in the present invention include activated carbon, carbon black,
All generally known adsorbents for organic substances can be used, such as cationic or anionic exchange resins, silica gel, alumino silica gel, activated alumina, etc., regardless of whether the form of adsorption is physical occlusion or chemical adsorption. Among the above adsorbents, some simple examples will be given below.

Activated carbon is registered in JIS K-1, 474-75 and has physical adsorption ability. There are powdered and granular forms. Manufacturers include Three Phase Carbon, Tsurmicol, Fujisawa Pharmaceutical, Hokuetsu Carbon, Kurera Chemical, Souen Yakuhin, and Wako Pure Chemical.

Ion exchange resin: Strongly acidic cation exchange resin (Amberli) is commercially available.
te I R120B (OJ Legano), (Dowex) Dowex (Kuraikai Kagaku).

Weakly acidic cation exchange resin - (Amberlite) Ambe
rlite I RC-5Q, Diamond ion WK 1
0゜Strong basic anion exchange resin - (Amberlite) A
mberlita I RA-401, (Amberlite Asberlite I RA-410, evening ion 5A-11A1, diamond (t7SA-20
A, C') X) Dowexl, (Dowex) Dowex Z.

Weakly basic anion exchange resin - (Amberlite) Asb
Examples include erlite I R-4B, (Amberlite) Amberlita I R-45, Diaion WA20, (Dowex) Dowex 3*, etc., which are known to adsorb substances by chemical adsorption using JiltJi. The colored Th1r generated by the invention is mainly a dissociated dye, and it is preferable to use an anion exchange resin to adsorb it.

Other alumina, alumino silica gel, and silica gel that are commercially available from Sumitomo Aluminum, Mizusawa Chemical, Catalyst Kasei, Wako Pure Chemical, and other companies can be used.

In the present invention, the above adsorbent is used in the form of fine particles of LQ (0.2-1 μm).
) and used as an aqueous dispersion.

In addition to the above-mentioned solid particulate adsorbent, as an adsorbent, US Pat.
, No. 500,626, JP-A No. 61-88256, No. 6
No. 2-244036, No. 60-57836, No. 60-
No. 60643, No. 60-118834, No. 60-11
No. 9557, No. 60122940, No. 60-1229
No. 41, No. 60-122942, No. 61-46948
Mordant polymers known in, for example, No. 62-244043 can also be used.

In addition, when adding the substance, together with the dye-providing compound,
Any of the methods of adding it to the photosensitive layer, the intermediate layer or the protective layer is possible. Furthermore, it is also possible to create, in particular, - or more layers containing the substance as layers other than those mentioned above, and to provide them at any position in the multilayer photosensitive material. At that time, an intermediate layer may be provided between the layer containing the substance and the other layer.

Since the adsorbent substance of the present invention is used in a hydrophilic binder, it can efficiently adsorb coloring substances that are unnecessary for image formation. Coco? ! The ffl aqueous/<inder can be selected from hydrophilic m1CII compounds or binders used as binders for photosensitive materials and/or color z+a constant materials, which will be described later.

The amount of the adsorbent substance used in the present invention varies depending on the type of substance and the layer to be added.
The amount used is from 11 IIg to 2g, in particular from lO2 to 500g.

/ / / /' / 7/ The heat-developable photosensitive material of the present invention basically has a photosensitive silver halide and a binder on a support, and if necessary, an organic metal salt oxidizing agent and a dye. Donating compound (
(As described below, it may also serve as a reducing agent).

These components are often added to the same layer, but if they are in a reactable state, they can be added separately to separate layers. For example, if a colored dye-providing compound is present in the lower layer of the silver halide emulsion, a decrease in sensitivity can be prevented. Although the reducing agent is preferably incorporated into the photothermographic material, 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 of yellow, magenta, and cyan, at least three silver halide emulsion layers each having light sensitivity on different spectra are used in combination.

For example, a 3/W combination of a blue-sensitive layer, a green-sensitive layer, and a red-sensitive layer,
There are combinations of green-sensitive layers, red-sensitive layers, and infrared-sensitive layers.

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

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

The 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 antihalation layer, and a back layer.

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

The silver halide emulsion used in the present invention may be a surface latent image type emulsion or an internal latent image type emulsion.The internal latent image type emulsion is directly combined with a nucleating agent and a photofog. Used as a reversal emulsion. *Also, 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.
Silver halide emulsions may be monodisperse or polydisperse, and monodisperse emulsions may be mixed and used. Grain size is 0.1 to 2.
[mu], particularly preferably 0.2 to 1.5 [mu].The crystal habit of the halogenated paper particles may be any of the cubic, octahedral, tetradecahedral, tabular with a high aspect ratio, and the like.

Specific information! , U.S. Patent M4,500,626 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.

Silver halide emulsions may be used as they are after ripening, but they are usually used after being chemically sensitized. These methods can be used alone or in combination. These chemical sensitizations can also be performed in the presence of nitrogen-containing bicyclic compounds (
JP-A-62-253159).

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

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

Among these organic salts, there are 8! Silver salts are particularly preferably used.

Organic compounds that can be used to form the above-mentioned organic silver salt oxidizing agent include Japanese Patent No. 4,500.626 No. 52
There are benzotriazoles, fatty acids and other compounds described in columns 53 and the like. Also useful are silver salts of carboxylic acids having a furkynyl group, such as silver 7enylprobiol, described in JP-A-113235, and acetylene silver, described in JP-A-61-249044. Organic silver salt is 2Fl1
The organic silver salts of 6 or more, which may be used in combination, are as follows: per mole of photosensitive silver halide,
0.01 to 10 mol, preferably o.

01 to 1 mole can be used in combination. The total coating amount of photosensitive silver halide and organic silver salt is suitably 50 mg to 10 g7m'' in terms of silver.

Various antifoggants or photographic stabilizers can be used in the present invention. An example is RD176
43 (1978) 24-25, azole necks and 7 Zaindenes, #? frlI! Showa 59-168442
Nitrogen-containing carboxylates and phosphoric acids described in No. 59-111636, furcapto compounds and metal salts thereof described in JP-A-59-111636, acetylene compounds described in JP-A-62-87957, and the like are used.

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

Specifically, U.S. Pat.
17029 (1978), pages 12-13, and the like.

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

Along with the sensitizing dye, 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 US Pat. 3.615,641, patent application 1986-
226294 etc.).

These sensitizing dyes may be added to the emulsion during or before or after chemical ripening.
It may be carried out before or after nucleation of silver halide grains according to No. 756 and No. 4,225.666.

The amount added is generally about 10-1 to 10-2 mol per mol of silver halide.

A hydrophilic binder is preferably used for the structure 1' and layer of the photosensitive material or dye fixing material. Examples include those described on pages (26) to (28) of JP-A-62-253159. Specifically, transparent or translucent hydrophilic baingu is preferred, such as proteins such as gelatin and gelatin derivatives, or cellulose derivatives,
Natural compounds such as polysaccharides such as starch, gum arabic, dextran, pullulan, etc. and polyvinyl alcohol,
Examples include polyvinylpyrrolidone, acrylamide polymer, and other synthetic polymer compounds. Also, JP-A-62-
Super absorbent polymers described in No. 245260, i.e. homopolymers of vinyl momers having -COOM or -3o, M (M is a hydrogen atom or an alkali metal), or copolymers of these vinyl momers with each other or with other vinyl momers (For example, sodium methacrylate, ammonium methacrylate, Sumikagel L from Sumikagaku Co., Ltd. 91)
-58) is also used. Two or more of these binders can also be used in combination.

When using a system that performs thermal development by supplying water, the use of the above-mentioned super absorbent polymer makes it possible to quickly absorb 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 transferred from the dye-fixing material to another material after transfer.

In the present invention, the amount of binder applied is 2 per 1-2.
It is preferably 0g or less, preferably 1oTl or less, and more preferably 7g.
It is appropriate to do the following.

The composition M (including the pack layer) of the photosensitive material or dye fixing material contains various polymers for the purpose of improving film properties such as dimensional stabilization, prevention of curling, prevention of adhesion, prevention of film cracking, and prevention of pressure sensitivity. It can contain latex. ! 4
:Specifically, JP-A-62-245258, JP-A No. 62-1
Any of the polymer latexes described in No. 36f348, No. 62-11006 (No. 3, etc.) can be used. In particular, if a polymer latex with a low glass transition point of 1 (40°C or lower) is used for the mordant layer, cracking of the mordant layer can be prevented. In addition, when a polymer latex with high positive transition and α is used in the pack layer, an anti-curl effect can be obtained.

As the reducing agent used in the present invention, those known in the field of photothermographic materials can be used. It also includes dye-donating compounds that have reducing properties, which will be described later (in this case, other reducing agents can be used at the same time), and although they themselves do not have reducing properties, they can be used as nucleophilic reagents during the development process. A reducing agent precursor that exhibits reducing properties by the action of heat can also be used.

Examples of reducing agents used in the present invention include U.S. Pat.
, No. 500,626, columns 49-50, same No. 4,483
, No. 914 No. 30-31@, No. 4゜330.617
No. 4,590. IS No. 2, JP-A-60-14
No. 0335, pages (17) to (18), 57-402
No. 45, No. 56-13873G, No. 59-17845
No. 8, No. 59-53831, No. 59-182449, No. 59-182450, No. 60-119555,
From No. 60-128436 to No. 60-128439, No. 60-60-198540, No. 80-1817
No. 42, No. 61-259253, No. 62-24404
No. 4, No. 62-131253 to No. 62-13125
6, European Patent No. 220,746A2, No. 78-
There are reducing side and reducing agent precursor described on page 96 etc.

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

If a diffusion-resistant reducing agent is used, an electron transfer agent and/or electron transfer agent may be added as necessary to facilitate electron transfer between the diffusion-resistant reducing agent and the developable silver Combinations of transfer agent precursors can be used.

The electron transfer agent or its precursor can be selected from the listed 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 (m-child donor). Particularly useful electron transfer agents are 17-enyl-3-pyrazolidones or 7-enyl-3-pyrazolidones.

The diffusion-resistant reducing agent (electron donor) used in combination with the electron transfer agent may be any of the reducing agents mentioned above, as long as it does not substantially migrate in the layer of the photosensitive N material, and hydroquinone is preferable. sulfonamide 7 di/-ols, sulfone 7 midna 7 toll vf1511 1977 3 1 1
0 8 2 7 9 2 1 Child donor To L Te Examples include the compounds described above and the dye-donating compounds that are diffusion resistant and have a basic property described below 6 In the present invention, the addition of a reducing agent The amount is from 0.001 to 20 mol, particularly preferably from 0.01 to 10 mol, per mol of silver.

In the present invention, silver can be used as the image forming substance. It also contains a compound that generates or releases a mobile dye in response to or inversely to this reaction when silver ions are reduced to silver under high temperature conditions, that is, a dye-donating compound. You can also do it.

Examples of dye-providing compounds that can be used in the present invention include compounds (couplers) that form dyes through an oxidative two-bring reaction.

This coupler may be a 4-equivalent coupler or a 2-equivalent coupler. Also preferred are 2-fifJ Buller, which has a diffusion-resistant group as a leaving group and forms a diffusible dye through an oxidative coupling reaction. The second M-diffusible group may form a polymer chain. Power 2 - Specific examples of developers and couplers can be found in Noames M's ``The Theory Opza 7↑ Toge Rough Ink Process'' 4th edition (TJ(,,Lames'Tbe T
theory of tbe Photo.

2 9 1 -
3, 3, 4 pages, and 35, 4 to 36 pages, JP-A-1988-
No. 123533, No. 58-149046, No. 58-1
No. 49047, No. 59-111148, No. 59-12
No. 4399, No. 59-174835, No. 5 9-2
No. 31539, No. 59-231540, No. 60-29
It is described in detail in No. 50, No. 60-2951, No. 60-142/S2, No. GO-23414, No. 60-66249, etc.

Further, as another example of the dye-donating compound, there may be mentioned a compound having a function of releasing or diffusing a diffusible dye in an 81I image form. This type of compound has the following general formula (Ll)
It can be expressed as

(Dye-Y) n-Z (LI) Dye represents a dye group, -temporarily shortened dye group or dye precursor group, Y represents a simple bond or linking group, Z
corresponds to or inversely corresponds to the photosensitive silver salt having a latent image in image form, and causes a difference in the diffusivity of the compound represented by (Dye - Y) n - Z, or releases Dye,
Represents a group having the property of causing a difference in diffusivity between the released Dye and (Dye-Yen Z, n represents 1 or 2, and when n is 2, two D
ye-Y may be the same or different.

Specific examples of color donor compounds represented by general 2 (Ll) include the compounds listed in (1) and (2) below. A diffusible dye image (bright dye image) is formed, and (■) and (2) form a diffusive color 1 image (black dye image) in response to silver halide development.

■U.S. Patent No. 3,1 3 4,7 6 4, U.S. Patent No. 3,
362, 819, same No. 3.597.200, same No. 3
, No. 544,545, No. 3,482,972, etc., in which a hydroquinone developer and a dye component 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., it releases diffusible dyes in an alkaline environment.
Non-diffusible compounds can also be used which lose their ability to react with the silver halide. For example, U.S. Patent 1
No. 93,980,479, etc., a compound that releases a diffusible dye through an intramolecular nucleophilic substitution reaction, US Pat.
Examples thereof include compounds that release a diffusible dye through an intramolecular rewinding reaction of an inoxacilone ring, as described in No. 4,199.354 and the like.

■U.S. Patent No. 1,559,290, European Patent No. 22
0.746. As described in No. A2, Kokai Technical Report 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 the intramolecular after reduction described in U.S. Pat. Compound that releases a diffusible dye by nucleophilic substitution reaction of
24025 (1984) etc., a compound which releases a diffusible dye by an intramolecular electron transfer reaction after being reduced, West German Patent No. 3,008,588Δ, JP-A No. 5
6-142530, U.S. Pat. No. 4,343,893, U.S. Pat.
Nitro compounds that release diffusible dyes after accepting electrons, such as those described in U.S. Patent No. 4,450,223, etc.; Nitro compounds that release diffusible dyes after accepting electrons, such as those described in U.S. Patent No. 4,609,610, etc. Examples include compounds that

Also, as a more desirable one, European Patent No. 220.7
No. 46A2, Public Technical Report 87-6199, Patent Application 1986-3
No. 4953, No. 62-34954, etc., a compound having an N-X bond (Xl represents an oxygen, sulfur, or nitrogen atom) and an electron-withdrawing group in one molecule, M@G2-1
No. 06885, a compound having an electron-withdrawing group in one molecule (so, -xcx has the same meaning as above), patent application No. 1982
-106895, a po-x bond (
(X has the same meaning as above) A compound having an electron-withdrawing group, 1.1mc per molecule as described in Japanese Patent Application No. 106887/1987
-X'M combination (X'?fX, ! represents a or * or -3O,-) and a compound having an electron-withdrawing group.

Among these, compounds having an N-X bond and an electron-withdrawing group in the molecule are particularly preferred.
Compounds (1) to (3), (
7) to (10), (12), (13), (15), (2
3) - (26), (31), (32), (35), (3
6), (40), (41), (44), (53) to (5
9), (64), (70), and compounds (11) to (23) of Kokai Technical Report 87-6199.

■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, Japanese Patent Publication No. 48-39゜165, U.S. Patent No. 3
, No. 443,940, No. 4.474,867, m.
No. 4,483,914 etc. 1! There are things that have been done.

■Silver helodenide or 8! A compound (D
RR compound), this compound does not require the use of other reducing M, so there is no problem of image staining due to oxidative decomposition products of the reducing agent, which is preferable.A representative example thereof is US Patent M3.9.
No. 28,312, No. 4,053,312, m4,
No. 055,428, Pt54,336,322, JP-A-59-65839, 11m59-69839,
No. 53-3819, No. 51-104.343, RD
U.S. Pat. No. 3,725,062, U.S. Patent No. 3,728.113, U.S. Pat.
JP-A-58-116.537, JP-A No. 57-179840
No. 4,500,626, etc. As a specific example of the DRR compound, the above-mentioned U.S. Pat.
．． 500.62G, columns 22 to 446, among which compounds (1) to (3), (10) to (13), and (1) described in the above-mentioned U.S. patent can be mentioned.
6)-(19), (28)-(30), (33)-(3
5), (38) to (iO), and (i2) to (64) are preferred, and U.S. Pat.
Also useful are the compounds listed in column 9.

In addition, as dye-donating compounds other than the above-mentioned couplers and general formula [L I ], dye silver compounds in which an organic silver salt and a dye are combined (Research Disk a-E' + -
Magazine May 1978, 54-58W, etc.), 7zo dye used in heat-developable silver dye bleaching method (U.S. Pat. No. 4,23
5.957, Research Disclosure Magazine, 19
April 1976 issue, pp. 30-32), leuco dyes (U.S. Pat. No. 3,985,565, U.S. Pat. No. 4,022,617, etc.) can also be used.

Hydrophobic additives such as dye-donating compounds and diffusion-resistant reducing agents can be incorporated into the layers of the light-sensitive material by known methods such as those described in U.S. Pat. No. 2,322,027. In this case, Japanese Unexamined Patent Application Publication Nos. 59-83154 and 59-83154,
No. 178451, No. 59-178452, No. 59-1
No. 78453, No. 59-178454, No. 59-17
No. 8455, No. 59-178457, etc., a high boiling point organic solvent with a boiling point of 50°C to 160°C is used as necessary.
It can be used in combination with a low boiling point organic solvent at ℃.

The amount of high-boiling organic solvent is 1 g of the dye-donating compound used.
for 10= or less, preferably 5I? It is as follows. Also, binder 1. less than lcc, even 0.5
cc or less, particularly 0.3 cc or less is suitable.

Japanese Patent Publication No. 51-39853, Japanese Patent Application Publication No. 1983. -59943
The dispersion method using polymers described in No.

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 bangu, in addition to the above-mentioned method.

When dispersing a hydrophobic compound in an aqueous colloid, various surfactants can be used.
-157636, pages (37) to (38), those listed as surfactants 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 No. 4,50.
It is described in columns 51-52 of No. 0.62G.

In systems that form images by diffusion transfer of dyes, a dye-fixing material is used together with a light-sensitive material.1 Even if the dye-fixing material is coated separately on a support separate from the light-sensitive material, 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 is described in U.S. Pat. No. 4.500.626, which may be coated on the same support. The relationship described in column 57 is also applicable to this condyle.

The dye fixing material preferably used in the present invention has at least IN a layer containing a mordant and a binder. ! As the dye, dyes known in the photographic field can be used, and specific examples thereof include U.S. Pat. No. 4,500.626 No. 58-59S
and the mordant described in JP-A No. 61-88256, pages (32) to (41), Jikai @ No. 62-244043, No. 62-
Examples include those described in No. 244036 and the like.

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

The dye fixing material may be provided with auxiliary layers such as a protective layer, a release layer, and an anti-curl layer, if necessary.

In particular, it is useful to provide a protective layer.

A high boiling point organic solvent can be added to the constituent layers of the light-sensitive material and the dye-fixing material as a plasticizer, a slippery agent, or a peelability improving agent between the light-sensitive material and the dye-fixing material. Specifically, page (25) of ￥Fma No. 62-253159, 6
There is one described in No. 2-245253.

Furthermore, various silicone oils (
) From methyl silicone oil to dimethyl siloxane, there are various types 8! All silicone oils can be used, including modified silicone oils that have introduced groups. Examples include various modified silicone oils, especially carboxy-modified silicone (product name: X-22
-3710) etc. are effective.

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

Photosensitive materials and dye-fixing materials may contain anti-fading M. Examples of anti-fading agents include antioxidants, ultraviolet absorbers, and certain metal complexes.

Examples of antioxidants include taloman compounds, coumaran compounds, 7-ether compounds (for example, hindered phenol M), hydroquinone derivatives, hindered amine derivatives, and spiroindane compounds. Compounds described in JP-A-61-159644 are also effective.

As ultraviolet M@ collectors, benzotriazole compounds (
U.S. Patent No. 3,533.794, etc.), 4-thiazolidone compounds (U.S. Pat. No. 3,352,681, etc.),
Benzophenone compounds (JP-A-46-2784, etc.), other JP-A-54-48535, JP-A-62-136
There are compounds described in No. 641, No. 61-88256, and the like. Further, the ultraviolet absorbing polymer described in JP-A No. 62-260152 is also effective.

As metal complexes, US Pat. No. 4,241,155,
Same number t144,245,018 PIS3~364fl,
No. 4,254.195, columns 3 to 8, JP-A-62-1
No. 74741, No. 61-88256 (27) - (29
) Makoto, Patent Application No. 62-234103, No. 62-3109
There are compounds described in Japanese Patent Application No. 62-230596, etc.

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

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

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

A fluorescent brightener may be used in the light-sensitive material or the dye-fixing material. In particular, it is preferable to incorporate the fluorescent brightener into the dye-fixing material or to supply it from outside the light-sensitive material. Examples include K. , edited by VeenkataramanrThe
CI + chemistry of 5ynthetic D
Examples include compounds described in yesJ, Volume V, Chapter 8, JP-A-61-143752, and the like. More specifically, stilbene compounds, coumarin compounds,
Examples include biphenyl compounds, benzoxacylyl compounds, naphthalimide compounds, pyrazoline compounds, and carbostyryl compounds.

Optical brighteners can be used in combination with antifade agents.

Hardeners used in constituent layers of photosensitive materials and dye-fixing materials include U.S. Pat.
Hard IIIM described in JP 61-18942 and the like can be mentioned. More specifically, aldehyde-based hardeners (formaldehyde, etc.), anolisine-based hardeners, epoxy-based hardeners (nylsulfonylacetamide) ethane, etc.), tomethylol-based hardeners (such as Tumethyrol R), Alternatively, polymer hardeners (compounds described in JP-A No. 62-234157, etc.) may be used.

Various surfactants can be used in the constituent layers of the photosensitive material and the dye-fixing material for the purposes of aiding coating, improving peelability, improving slipperiness, preventing electrification, promoting development, and the like. Specific examples of surfactants are given in JP-A-62-173463 and JP-A-62-18.
It is described in No. 3457, etc.

The constituent layers of photosensitive materials and dye-fixing materials include improved slipperiness,
1g for the purpose of preventing static electricity and improving peelability! -Y fluoro compound may be included, yes 8! Typical examples of fluoro compounds include fluorine-based surfactants described in Japanese Patent Publication No. 57-9053, columns 8 to 17, Japanese Patent Publication No. 61-20944, 62-13582G, etc., or 77 base oil, etc. Examples include hydrophobic fluorine compounds such as oily 77 element-based compounds and solid fluorine compound resins such as ethylene tetra7thanide.

A matting agent can be used in the photosensitive material and the dye fixing material. Examples of matting agents include silicon dioxide, polyol/fin, 1i-bottom methacrylate, etc.
In the pond of compounds described on page 256 (2), benzoguanamine resin beads, polycarbonate resin beads, ASυ
(Patent application No. 1982-1.100 G 4 for fat beads, etc.)
There is a compound described in No. 52-110065.

In addition, thermal solvents, antifoaming agents, anti-foaming agents, colloidal silicate agents, etc. may be included in the Nlt layer of photosensitive materials and dye-fixing materials.Specific examples of these additives are given in JP-A-6
No. 1-88256, pages (26) to (32).

In the present invention, an image formation accelerator can be used in the light-sensitive material and/or the dye-fixing material. The S image formation accelerator promotes the redox reaction between the silver salt oxidizing agent and the reducing agent, promotes reactions such as generation of dye from a dye-donating substance, decomposition of the dye, or release of diffusible dye, and is used in photosensitive materials. It has functions such as promoting the movement of dye from the layer to the dye fixed layer, and from a physicochemical function, it has the following functions: base or base precursor, nucleophilic compound, high boiling point, alpha organic solvent (oil), thermal solvent, surfactant. agents, fli, or compounds that interact with silver ions. However, these substance groups generally have multiple functions and usually have some of the above-mentioned promoting effects. Details of these can be found in U.S. Patent 4,
No. 678,739, columns 38 to 40.

Base precursors include salts of organic acids and bases that are decarboxylated by heat, and intramolecular nucleophilic ra11! reactions, such as compounds that release amine necks by Rossen rearrangement or Beckmann rearrangement. A specific example is U.S. Patent No. 4,511,493.
No., #n [62-65038, etc.].

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

In addition to the above, combinations of a poorly soluble metal compound and a compound (referred to as an I-forming compound) that can undergo a complex formation reaction with a metal ion constituting this hardly soluble metal compound, as described in European Patent Publication No. 210,660, and vfrfR Showa 61 232
Compounds that generate bases by Saletail electrolysis as described in No. 451 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-forming compound to the light-sensitive material and the dye-fixing material separately.

The photosensitive material and/or dye-fixing material of the present invention may be subjected to treatment during development. 1. Various development stoppers can be used for the purpose of always obtaining a constant image despite variations in temperature and processing time.

The development stopper referred to here is a compound that neutralizes the base immediately after proper development or reacts with the base to lower the base concentration in the film and stop development, or a compound that inhibits development by interacting with silver and silver salts. It is a compound that

Specifically, an acid precursor that releases acid upon heating;
Examples include electrophilic compounds that undergo a substitution reaction with a coexisting base when heated, nitrogen-containing heterocyclic compounds, /rukabuto compounds, and precursors thereof.

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

As a support for the light-sensitive material or dye-fixing material of the present invention, one that can withstand processing temperatures is used. -For boat fishing, paper and synthetic polymers (films) can be used. Specifically, polyethylene tele7, W tallate, polycarbonate, polyvinyl chloride, polystyrene, polypropylene, polyimide, cellulose
(e.g. thria-7tylcellulose) or films containing pigments such as titanium oxide,
Furthermore, film method synthetic paper made from polypropylene etc., synthetic υ4 fat pulp such as polyethylene and natural pulp (mixed paper to be mixed, Yankee paper, baryta paper, cast coated paper on footed paper FVF), metals, fabrics. , 〃2s■ etc. are used.

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

In addition, JP-A-62-253159 (29) to (3)
1) The support described in i can be used.

The surface of these supports may be coated with hydrophilic binder, alumina sol, semiconductive gold R oxide such as tin oxide, carbon blank, 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 using a copying machine. A method in which the original image is scanned and exposed through a slit using an exposure device, etc., a method in which the image status information is transmitted via an electric M, and a light emitting diode, various lasers, etc. are emitted for exposure, and image information is transferred to a CRT, liquid crystal display, or electro There is a method of outputting the image to an image display device such as a luminescence display or a plasma display and exposing it directly or through an optical system.

As the light source for recording the l11 image on the photosensitive material, as mentioned above, natural light, tungsten lamp, light emitting diode,
US Patent No. 4.500 for laser light source, CRT light source, etc.
, 626, column 56 can be used.

It is also possible to perform III image exposure using a wavelength conversion element that combines a nonlinear optical material and a coherent light source such as a laser beam. It is a material that can exhibit the nonlinearity between polarization and electric field that sometimes appears, and it is a material that can be used for inorganic compounds such as lithium niobate, potassium dihydrogen phosphate (KDP), lithium iodate, BaBzO-, and urea derivatives. , nitroaniline derivatives, e.g. nitrobilinone-N-oxide yj conductors such as 3-methyl-4-nitrobilinone-N-oxide (POM), compounds described in JP-A-61-53462 and JP-A-62-210-432. is preferably used. As the form of the wavelength conversion element T, single crystal guided waveguide type, fiber type, etc. are known, and both are useful.

In addition, direct image information is obtained from video cameras, electronic still cameras, etc. (2 (I), TV I3 (represented by the Japan Television Concert Signal Standard (NTSC)), and the original image is divided into a large number of pixels by a scanner etc. The image signal obtained by C
It is possible to use image signals created using a computer such as G, CAD.

The photosensitive material and/or the dye-fixing material may be in the form of an electrically 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. Furthermore, these guides? The '11 layer also functions as an antistatic layer.

The heating temperature in the heat development step can be developed at about 0°C to about 250°C, and particularly useful is about 0°C to about 180'C. The dye diffusion transfer step may be performed simultaneously with heat development or 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 more preferably 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
As detailed in No. 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 (water) is also useful. In this method, the heating temperature is 5
The temperature is preferably 0°C or higher and the boiling point of the solvent or lower. For example, when the solvent is water, the temperature is preferably 50°C or higher and 100°C or lower.

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

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

The amount used can be as small as less than the weight of the solvent corresponding to the maximum swelling volume of the entire coating film (especially less than the amount calculated by subtracting the in of the total coating film from the 'mff1 of the solvent corresponding to the maximum swelling volume of the entire coating film). .

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

In order to promote dye transfer, a method may also be adopted in which a hydrophilic thermal solvent, which is solid at room temperature and dissolves at high temperature, is incorporated into the light-sensitive material or dye-fixing material. The UL aqueous thermal solvent may be incorporated into either the photosensitive material or the dye fixing material.
The layer may be incorporated in both, and the layer to be incorporated may be an emulsion layer, an intermediate layer, a protective layer, or a dye fixing layer.
It is preferable to incorporate the dye fixing layer into/or a layer adjacent thereto.

Examples of hydrophilic thermal solvents include ureas, pyridines, amides, sulfonamides, imides, fournyl, oximes, and other ester rings.

Further, in order to promote dye transfer, a high boiling point organic solvent may be included in the light-sensitive material and/or the dye fixing material.

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

The pressure conditions and method of applying pressure when superimposing a photosensitive material and a dye-fixing material are disclosed in Japanese Patent Application Laid-open No. 61-1472.
The method described in No. 44, page 27 can be applied.

Any of a variety of thermal development equipment can be used to process the photographic elements of this invention; for example, JP-A-59-75247;
Apparatuses described in Japanese Utility Model No. 59-177547, No. 59-181353, No. 60-18951, Japanese Utility Model Application Publication No. 62-25944, etc. are preferably used.

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

A well-stirred gelatin aqueous solution (20 g of gelatin 1 g of potassium bromide in 800 ml of water, and 0H (CH
z) zs(Ctl□), 0)1 Add 0.5g and 5
The following (+) solution, (II) solution and (
I[I) solution was added at the same time at an equal flow rate 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, 20g of lime-treated ossein gelatin was added and the pH was adjusted to 6.4 and pAg to 8.2, and then heated to 60°C.
Sodium thiosulfate 9■, chlorauric acid 0.01
% aqueous solution 6ml, 4-hydroxy-6-methyl-1,3
, 3a, 7-chitrazaindene (190 μl) was added, and chemical sensitization was carried out for 45 minutes. The yield of emulsion was 635 g.

(Drug A) (Aggravating pigment C) (CHHz)asOsNa Next, the emulsion (n) for the third layer will be described.

Add 20 μg of gelatin, 0.30 g of potassium bromide, 6 g of sodium chloride, and 0.015 g of the following chemical A to a well-stirred gelatin aqueous solution (730 g of water to make 60.0
℃), add the following solution (1) and (1 solution at the same time)
Added at equal flow rate over 0 minutes. (■) After the addition of the solution, 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 lllAg to 7.8, chemical sensitization was performed at 60°0°C. The chemicals used at this time were 1.6μ of triethylthiourea and 4-hydroxy-6-methyl-1,,3,
The aging time was 55 minutes using 100 μl of 3a,7-tetozaindene. The yield of this emulsion was 635 g.

Next, how to prepare the emulsion (I[I) for the fifth layer will be described.

A well-stirred gelatin aqueous solution (30 g of gelatin 1 3 g of potassium bromide in 60 ml of water, and HO (CHz)
ts(CHz)gs(CHz)tOH0.5g was added and kept at 65°C), and the following solutions (1) and (It) were added simultaneously over 20 minutes. After that, the following (I
Solution II) and solution (IV) were added simultaneously over 30 minutes. After washing with water and adding 20 g of desalinated lime-treated ossein gelatin to adjust the pH to 6.2 and pAg to 8.5, add sodium 1,000 sulfate, chloroauric acid and 4-hydroxy-6-methyl-
Optimal chemical sensitization was achieved by adding 1,3,3a,7-chitrazaindene.

In this way, monodisperse 8 with an average particle size of 0.50 μm
600 g of hedral silver iodobromide emulsion (15) was obtained.

Next, we will describe how to make a gelatin dispersion of a dye-donating substance. 20 g of yellow dye-donating substance (1)
Weighed 13.6 g of the child donor (1r) and 10 g of tricyclohexyl phosphate, added 57-g of ethyl acetate, and dissolved them by heating at about 60°C to form a homogeneous solution.

This solution, 110 g of a 10% solution of lime-treated gelatin, 65 g of water, and 1 portion of sodium dodecylbenzenesulfonate
．． After stirring and mixing with 7 g, the mixture was dispersed using a homogenizer at 110,000 rpm for 10 minutes. This dispersion was mixed with
It is called a dispersion of a dye-donating substance.

Dispersions of magenta and cyan dye-providing substances are similar to dispersions of yellow dye-providing substances, magenta dye-providing substance (2) 0 or cyan dye-providing substance (
3) Made using th.

With these, a color photosensitive material 101 having a multilayer structure shown in [Table 1] was prepared.

Dural side 11).

1゜ Screw (vinyl sulfoni Ruacetamide) ethane High boiling point batter solvent (1).

Tricyclohexolfuos Fate Antifoggant +11" 0CsH Antifoggant (2).

-CL-CI( SO, to Polymer (1) 1 -C11-CI+.

Surfactant (1) # Aerodur OT Electron donor (11" 0H Electron transfer agent (1) 0 Coating layers A to E shown below were added between the first layer of photosensitive material #4101 and the support. Photosensitive material 101 except that it was coated with
Heat-developable color photosensitive materials 102 to 106 having exactly the same composition as
were created respectively.

<Coating layer A> (102) Additive Addition amount (g#rl) Gelatin 0.2 Surfactant (1
)” 0.08 Hardener (11″ Water-soluble polymer (1) * Coating layer B> Additive gelatin activated carbon (1)’ Surfactant (l Bisurfactant (4) “ Surfactant (5) “Hardening agent (1)” Water-soluble polymer (1) 0 Coating NC> Additive gelatin Anion exchange resin (1)” Surfactant (1 Bisurfactant (4) “Surfactant (5)” Hardener (1).

Water-soluble polymer (1) 0 0.002 0゜ 01 Addition amount (g/n() 0.2 0.05 0.003 0.006 0.002 0.01 (l O4) Addition amount(g/n() ) 0, 2 0, 1 0,09 0.006 0.012 0.002 0,01 <Coating layer D> (105) Additive Addition amount (g/cd) Gelatin 0.2 alumina gel (1)''' 0.1 surfactant (
1)” 0.09 surfactant (4
)” o, oos surfactant (5
)" 0.012 hardener (l pi
0.002 water-soluble polymer f
i+” 0.01 Coating layer E>(10
6) Additives added! (g/rd) Gelatin 0.2 Water-soluble polymer + 41" 0.15 Surfactant (61" 0.05 Hardener + 1
1” 0.002 Furthermore,
Heat-developable color photosensitive materials 107 to 112 having exactly the same composition as photosensitive material 101 were prepared, respectively, except that additives were added to layers 2, 4, and 6 of photosensitive material 101 as shown in [Table 2]. .

Surfactant (5) # Thymol N Water-soluble polymer (4-bis) CM.

C8゜Activated carbon (Wako Pure Chemical Industries, Ltd. activated carbon (powder)) Anion exchange resin (1) "Diaion 5A-11A alumina gel (Ehi) Neutral activated alumina (Wako Pure Chemical Industries) (WO
ELM) Solid powders such as activated carbon, anion exchange resin, and alumina gel used in this example were added after a gelatin dispersion was prepared as shown below.

<Method for creating adsorbent dispersion> Activated carbon 6g, gelatin 4g, surfactant (1) "0゜5
g, surfactant (41'0°4g, surfactant (5).

0.7 g was mixed with 190 cc of water, and the mixture was stirred with a homogenizer at 110,000 rpm for 10 minutes. Transfer this to Dyno Mill, add 200g of glass beads, and
Milled at pm for 30 minutes. This is called an activated carbon gelatin dispersion.

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

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

[Table 3] Composition of dye fixing material nR-1 [Table 3] Continued silicone oil 1 Hz CH.

Hz Hz Surfactant meaning Aerosol 0T CsF+tSOtNCJCOOK C, H Tsu Hz C,H.

C,FsSOtN (CLC)ItOh-HCLTE'S
o, Ha polymer 0 Vinyl alcohol sodium acrylate copolymer (75/25 molar ratio) 1 Dextran (molecule I 70,000) High boiling point i solvent °6 Rheophos 95 (manufactured by Ajinomoto ■)
Hardener °9 /'\ (CHz)a-(Q-CHz-CH-CHz)z Cloak agent "10 Benzoguanamine resin (average particle size 15μ
) A tungsten light bulb is used in the above-mentioned multilayered color photosensitive material, and 1/1O is applied at 5000 lux through B, G, R, and gray color separation filters that change continuously by 4 degrees.
Exposure for seconds.

While feeding this exposed photosensitive material at a linear speed of 20+++ m/sec, water of 15aZ/r4 was supplied to the emulsion surface using a wire bar, and immediately thereafter, the image-receiving material and the film surface were superimposed so that they 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.

Maximum density (Dmax) and minimum density (Dmax) of gray part
Table 4 shows the results of measuring n) for each color of cyan, magenta, and yellow.

[Table 4] From [Table 4], it can be seen that compared to photosensitive materials 101 and 102, images with lower stain can be obtained with the photosensitive materials tA103 to 12 of the present invention.

Next, the photosensitive materials 101 to 112 were heated at 40°C and at a humidity of 70°C.
After storage for 7 days under conditions of
For 103 to 112, each color increased by 0.
The increase was 0.01 to 0.02. From this result, it can be seen that the photosensitive materials 103 to 112 of the present invention have good storage stability.

<Example 2> Using the same emulsion, dye-donating substance, electron donor, and electron transfer agent as in the color photosensitive material 101 of Example 1, a color photosensitive material 201 having a multilayer structure as shown in Table 5 was prepared. .

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

The organic silver salt emulsion was prepared as follows.

20 g of gelatin and 5.9 g of 4-acetylaminophenylpropiolic acid in 0.1% sodium hydroxide solution fg
, and dissolved in 1000 ml and 200 d of ethanol. This solution was kept at 40°C and stirred. Add 1 nitric acid to this solution.
A solution prepared by dissolving 4.5 g of Cucumber in 200 @l of water was added over 5 minutes. Excess salt was then removed by sedimentation. then p
11,300 g of an organic silver salt dispersion with a H content of 6.3 was obtained.

Further, an antifoggant precursor (11'' having the following structure) was added in 0.2 times the molar amount to the dye-donating substance, and was dispersed in oil according to the method of Example 1 together with the dye-donating substance and the electron donor.

[Table 5] support (Polyethylene terephthalate; thickness 100μ) Antifoggant precursor (1) 9 3t♂ton container il+“ Benzene sulfonamide H H Base precursor (1) 1 4-Chlorphenylsul Guanidine honyl acetate Electron transfer agent (2) 1 Reducing agent (2)゛ H H For the photosensitive material 201, [Table 6] as shown in Except for adding additives, Same composition as 201 Photosensitive materials 202 to 20G were prepared, respectively.

Next, how to make the dye fixing material (R-2) will be described.

Poly (methyl acrylate-co-N, N, N-to-U/
(Tyl-N-ruvinylbenzylammonium chloride)
(The ratio of methyl acrylate to vinylbenzylammonium chloride is I:1) 1Qg was dissolved in 200d of water and mixed uniformly with 100g of 10% lime-treated gelatin.

A hardening agent was added to this mixed solution, and the mixture was uniformly coated to a wet film thickness of 90 μm on a paper support laminated with polyethylene in which titanium dioxide was dispersed. After drying, this sample is used as a dye fixing material (R-2) having a mordant layer.

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

In? on the membrane side of the dye fixing material (R-2)? Hit 20＠l
After supplying water, the heat-treated photosensitive materials were stacked on the fixing material so that the film surfaces were in contact with each other.

After that, the linear speed I2mm/
When both materials were peeled off after passing through the photosensitive material for 20 seconds, a positive image with good S/N ratio was obtained on the dye-fixing material in each photosensitive material.

Gray, some cyan, magenta, and yellow Dtaa
The results of measuring x and Dn+in are shown in [Table 7].

[Table 7] As shown in [Table 7], compared to photosensitive materials 201 and 202, images with lower stain were obtained with photosensitive materials 203 to 206 of the present invention.

Example 3 How to prepare silver halide emulsions for the 5th N and 1st N will be described.

A well-stirred aqueous gelatin solution (containing 20 g of gelatin and 3 g of sodium chloride in 1,000 ml of water, kept at 75°C) was mixed with an aqueous solution containing sodium chloride and potassium bromide (600 vat) and an aqueous solution of silver nitrate (600 ml of water).
117 with 0.59 mol of silver nitrate dissolved therein) was simultaneously added at an equal flow rate over 40 minutes. In this way, 11 monodispersed cubic silver chlorobromide emulsions (bromine 50 mol %) having an average grain size of 0.40 tJm were prepared.

After washing with water and desalting, sodium thiosulfate 5■ and 4hydroxy-6-methyl-1,3,3a,7-titrazaindene 2
Chemical sensitization was performed at 60°C by adding 0rw. The yield of emulsion was 600 g.

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

Add a well-stirred gelatin solution (too much water).

- Contains 20g of gelatin and 3g of sodium chloride, 7
600ff17 of an aqueous solution containing sodium chloride and potassium bromide (kept at 5℃) and a silver nitrate aqueous solution (
0.59 mol of silver nitrate dissolved in 600 ml of water) 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 0635 μm was prepared.

After washing with water and desalting, 5 cm of sodium thiosulfate and 20 cm of 4-hydroxy-6-methyl-1,3,3a,7-chitrazaindene were added to carry out chemical sensitization at 60°C. The yield of emulsion was 600 g.

This article describes how to make benzotriazole silver emulsion.

28g of gelatin and 13.2g of benzotriazole to 33g of water
It was changed to 00-. This solution was kept at 40°C and stirred. A solution prepared by dissolving 17 g of silver nitrate in 100 g of water was added to this solution over 2 minutes.

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

This article describes how to make an acetylene silver emulsion.

20g of gelatin and 4.6g of 4-acetylaminophenyl acetylene, 1000I of water and 200m of ethanol
It was dissolved in 7. 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. After adjusting the pH of this dispersion and removing excess salt by sedimentation, 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.

5 g of yellow dye-donating substance (3)'', 0.2 g of auxiliary developer (a), 0.2 g of antifoggant (b), 2-ethyl-hexyl succinate sulfonic acid as a surfactant. Weigh out 0.5 g of soda and 2.5 g of triisononylphosph, add 30 g of ethyl acetate,
The mixture was heated and melted at about 60°C to form a homogeneous solution. After stirring and mixing this solution and 100 g of a 3% solution of lime-treated gelatin, the mixture was heated at 10,000 rpII for 10 minutes using a homogenizer.
It was dispersed. This dispersion is called a yellow dye-providing substance dispersion.

Auxiliary developer (a) HC) 13 A magenta dye was prepared in the same manner as above, except that the magenta dye-donating substance (5) was used and 2.5 g of tricresyl phosphate was used as a high-boiling solvent. A dispersion of donor material 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 (61").

: Polyethylene terephthalate film thickness 180μm3 : ■ Bis(vinylsulfonylacetamide) ethane (iso CJ J) tP=0 5: Size 4μm Dye-donating substance (5)''H (6)''H OC+ Jx, (n) Next , the coating JiA-E shown in Example 1 was applied to photosensitive material 3.
Photosensitive materials 302 to 3 having exactly the same composition as 301 except that they were additionally coated under the coating layer of 01 as shown in [Table 9].
07 were created respectively.

A tungsten light bulb was used for the photosensitive materials 301 to 307 created in this way, and G, whose density was continuously changing,
R, IR three-color separation filter (G is 500-600nm
, R is a 600-700 nm bandpass filter, I
R was constructed using a filter that transmits at least 700 nm)
The film was exposed to light for 1 second at 500 lux.

12111 on the emulsion surface 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 photosensitive material after heating for 30 seconds using a heat roller whose temperature is adjusted so that the temperature of the water-absorbed film is 88 and 98 degrees Celsius, G, R, and [R] are deposited on the fixing material. Compatible with the three-color separation filter, clear images of yellow, magenta, and cyan were obtained.

The results of measuring D+max/Dmin of each color are shown in [Table 10].

0Table 10) Procedural amendment

Claims (2)

[Claims] (1) A thermal support having 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. 1. A heat-developable color photosensitive material comprising a hydrophilic binder layer containing an adsorbent substance having a property of adsorbing a colored substance generated during image forming processing of the photosensitive material. (2) The diffusible dye released or formed by heating the heat-developable color photosensitive material of claim 1 after imagewise exposure or at the same time as the heat-developable color photosensitive material is separated from the hydrophilic binder layer containing the adsorbent substance. An image forming method characterized by transferring onto a dye fixing layer.