JPH06130609A - Heat developable color image forming method - Google Patents

Abstract

PURPOSE:To prevent defects such as white dots and to obtain a sharp picture image even when a photosensitive material is used for a long period by specifying the temp. of dampining water, specifying the range of saturated water swelling of the photosensitive material and the image receiving material, and specifying the addition amt. of dampening water. CONSTITUTION:The temp. of dampening water to be added to a heat developable photosensitive material having photosensitive silver halide, reducing agent, binder and dye-donating compd. is specified to >=45 deg.C. The saturated water swelling at this temp. of the dampening water is 10-20mum for the photosensitive material and 5-10mum for the image receiving material. The addition amt. of dampening water is specified to <=90% of the sum of the saturated water swelling of the photosensitive material and image receiving material. When the temp. of dampening water is >=50 deg.C, the addition amt. of dampening water is <=80% of the sum of saturated water swelling. The dampening water is added by passing the photosensitive material at a const. rate in a dampening water tank and successively removing the excess water on the surface of the photosensitive material with a nip roller. Thus, a const. amt. is always given.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a thermal development color image forming method capable of providing a color image free from image stain even when used for a long period of time. Furthermore, the present invention relates to a heat-development color image forming method capable of stably providing a print having excellent resolution.

[0002]

2. Description of the Related Art Photothermographic materials are well known in the art, and the photothermographic material and its process are described, for example, in "Basics of Photographic Engineering", Non-silver salt photograph edition (1982, published by Corona Publishing Co., Ltd.), pages 242 to 255. Page, US Patent No. 450062
No. 6, etc.

In addition, for example, a method of forming a dye image by a coupling reaction between an oxidized product of a developing agent and a coupler is described in US Pat. Nos. 3,761,270 and 4,021,240. Further, a method of forming a positive color image by a photosensitive silver dye bleaching method is described in US Pat. No. 4,235,957.

Recently, there has been proposed a method of releasing or forming a diffusible dye imagewise by heat development and transferring the diffusible dye to a dye fixing element. In this method, a negative dye image or a positive dye image can be obtained by changing the kind of dye-donor compound used or the kind of silver halide used. More specifically, U.S. Pat. Nos. 4,500,626, 4,483,914 and 45,
03137, 4559290 and JP-A-58-14.
9046, JP-A-60-133449, 59-2.
No. 18443, No. 61-238056, European Patent Publication 220746A2, Open Technical Report 87-6199, European Patent Publication 210660A2, and the like.

Many methods have been proposed for obtaining a positive color image by heat development. For example, in U.S. Pat. No. 4,559,290, a so-called DRR compound, which is an oxidized type compound having no color image releasing ability, is allowed to coexist with a reducing agent or a precursor thereof, and the reducing agent is added according to the exposure amount of silver halide by heat development. A method has been proposed in which the diffusible dye is released by being oxidized and reduced by the reducing agent remaining without being oxidized. In European Patent Publication No. 220746A and Kokai Giho No. 87-6199 (Vol. 12, No. 22), NX bond (X is oxygen atom, nitrogen atom or sulfur) is used as a compound that releases a diffusible dye by a similar mechanism. Photothermographic materials are described which use compounds which release diffusible dyes by the reductive cleavage of (representing atoms).

[0006]

As a simple image forming method using such a photothermographic material, a small amount of dampening water is applied to the surface of the photosensitive layer of the photosensitive material, which is then superposed on the image receiving material and heated. JP-A No. 64-13546 discloses a method of forming a color image on the image receiving layer by developing silver halide and transferring the dye in one step. There are various conceivable methods for applying the dampening water, but in any method, the dampening water is liable to stain due to decay or the like while being stored in the image forming apparatus. It has been found that white spot-like image defects may occur (hereinafter referred to as image stain). Such contamination of water is an important problem in a device that is used for a long period of time, because the water left in the device is continuously used.

As a measure for preventing image stains caused by such dampening water stains, it is conceivable to use a filter for removing stains or to add a fungal growth inhibitor or bactericide, which increases the cost of the apparatus. However, there is a drawback that the maintenance work such as the replacement of the filter and the addition of the bactericide is increased. Further, it is generally well known that heating is used as a sterilizing method, but when a fountain solution is applied at a high temperature, the swelling amount of the light-sensitive material increases, and as a result, the sharpness of the formed image decreases and a sharp image is obtained. It turns out that I can not get.

Therefore, an object of the present invention is to provide a heat-development color image forming method capable of stably obtaining a sharp full-color image free from image defects such as white spots even when the apparatus is continuously used for a long period of time. To provide.

[0009]

As a result of intensive experiments, the present inventor has found that the above problems can be solved by the following color image forming method. That is, (1) after dampening water is applied to the photosensitive layer surface of a photothermographic material having a photosensitive silver halide, a reducing agent, a binder, and a dye-donating compound on a support, the resulting image is superposed on an image receiving material and heated. In the image forming method for forming a color image on the image receiving layer of the image receiving material, the temperature of the dampening water is 45 ° C. or higher, and the saturated water swelling amount at the dampening water temperature of the photosensitive material is 10 μm or more and 20 μm or less, similarly the saturated water swelling amount of the image receiving material is 5 μm or more and 10 μm or less, and the amount of dampening water applied is 90% or less of the sum of the saturated water swelling amounts of the light-sensitive material and the image receiving material. A color image forming method characterized by the above. (2) In the heat-development color image forming method of (1), the temperature of the dampening water is 50 ° C. or higher, and the amount of dampening water applied is the saturated water swelling amount of the light-sensitive material and the image receiving material. 80 Japanese
% Or less, a color image forming method.

The present invention will be described in detail below.

Various methods are conceivable for applying the dampening water in the present invention. For example, (1) a method in which a dampening water treatment tank is provided, a photosensitive material is allowed to pass through the tank at a constant speed, and then excess water on the surface of the photosensitive material is removed by a nip roller so that a constant amount of water is constantly applied. . (2) A method in which a coating head such as a coating rod is installed and a certain amount of dampening water is applied to the surface of the photosensitive material conveyed at a constant speed. (3) A method in which a spraying device is installed and a fixed amount of dampening water is sprayed onto the surface of the photosensitive material conveyed at a constant speed. and so on.

In each of the above examples, (1) is a water immersion method,
(2) can be collectively referred to as a water coating method, and (3) can be collectively referred to as a water spraying method, but various concrete embodiments of each method other than the above can be considered. However, in either method, excess dampening water remains in the water tank or coating section, and it is necessary to have a dampening water storage tank in the equipment. Is likely to occur. Therefore, the method of the present invention is not limited to the above example, but can be widely applied.

The amount of water swelling in the present invention can be measured using a film thickness meter. The water swelling amount at the dampening water temperature of the present invention can be measured by keeping the water to be used and the measurement portion at a predetermined temperature when measuring the film thickness at the time of swelling using a film thickness meter. The application amount of the dampening water of the present invention can be determined from the difference from the previous weight by immediately weighing the light-sensitive material, which has been weighed in advance, through the dampening water applying step.

In the heat-developable color light-sensitive material of the present invention, basically, a light-sensitive silver halide, a reducing agent, a binder and a dye-donating compound (which may also serve as a reducing agent as described later) are formed on a support. In addition, an organic metal salt oxidizing agent and the like can be added as necessary. These components are often added to the same layer,
If it is in a state where it can react, it can be divided and added to another layer. For example, when a colored dye-donating compound is present in the lower layer of the silver halide emulsion, the reduction in sensitivity can be prevented.
The reducing agent is incorporated in the photothermographic material, and further, for example, by a method of diffusing from a dye fixing element described later,
You may use together the method supplied from the outside. By incorporating a reducing agent in the light-sensitive material, an effect of promoting color image formation can be obtained.

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

The photothermographic material may be provided with various auxiliary layers such as an undercoat layer, an intermediate layer, a yellow filter layer, an antihalation layer and a back layer, in addition to the above-mentioned protective layer.

The silver halide emulsion (emulsion containing photosensitive silver halide) in the present invention may have various shapes. Examples of these are cubes, octahedra,
Examples thereof include regular grains having regular crystals such as tetradecahedrons, tabular grains, spherical grains, and grains having irregular crystal forms such as potato grains.

As the silver halide composition of the grains, any one of silver bromide, silver iodobromide, silver iodochlorobromide, silver chlorobromide, silver chloroiodide, and silver chloride is used. Good, but
Silver bromide or silver chlorobromide is preferred. Further, it may contain silver thiocyanate, silver cyanate and the like. The silver halide composition in the grain may be uniform, may have different halogen compositions inside and outside, or may have a layered structure (JP-A-57-154232, JP-A-58-154232).
-108533, 58-248469, 59-
48755, 59-52237, U.S. Pat.
505, 068, 4,433, 048, 4, 4
44,877, European Patent 100,984, and British Patent 1,027,146).

The silver halide emulsion may be monodisperse or polydisperse, and a mixture of monodisperse emulsions may be used. The particle size is preferably 0.01 μm to 10 μm, particularly preferably 0.1 μm to 3 μm. Here, a monodisperse silver halide emulsion is defined as 95% or more of the total weight or the total number of silver halide grains contained therein is within ± 40% of the average grain size, more preferably within ± 30%. To be done.

Specifically, US Pat. No. 4,500,62
No. 6, Column 50, No. 4,628,021, Research
Disclosure magazine (hereinafter abbreviated as RD) 1702
9 (1978) and any of the silver halide emulsions described in JP-A No. 62-253159 and the like can be used.

The silver halide emulsion used in the present invention may be either a surface latent image type emulsion or an internal latent image type emulsion. The internal latent image type emulsion is used as a direct reversal emulsion in combination with a nucleating agent or an optical fogging.

In the present invention, two or more kinds of silver halides having different crystal habits, halogen compositions, grain sizes, grain size distributions and the like can be used in combination, and they can be used in different emulsion layers and / or in the same emulsion layer. It is possible to use.

In particular, tabular silver halide grains have already been reported in US Pat. Nos. 4,434,226 and 4,4.
39,520, 4,414,310, 4,43
3,048, 4,414,306, 4,45
9,353, JP-A-59-99433, 62-2.
No. 09445 discloses the production method and use technique. Further, JP-A-63-220238 and JP-A-1-
No. 201649 discloses tabular silver halide grains in which dislocations are intentionally introduced.

The ratio of the average grain diameter to the average grain thickness (hereinafter referred to as grain diameter / thickness) in the tabular grains is preferably 2 or more, more preferably 3 to 12, and especially 5
It is preferably -8. Here, the grain diameter / thickness can be obtained by averaging the grain diameters / thicknesses of all tabular grains, but a simple method is to use the ratio of the average diameter of all tabular grains to the average thickness of all average grains. You can also ask. The diameter of the tabular grains (corresponding to a circle) is 0.3 μm or more, preferably 0.3 to 10 μm, and more preferably 0.5 to
The thickness is 5.0 μm, more preferably 0.5 to 2.0 μm. The particle thickness is less than 1.0 μm, preferably 0.05
To 0.5 μm, more preferably 0.08 to 0.3 μm
Is.

In the present invention, the tabular grains account for 50% or more of the total grain projected area in the emulsion containing the tabular grains. It is preferably 70% or more, more preferably 90% or more. The grain diameter and grain thickness of tabular grains can be measured by electron micrographs of grains as described in US Pat. No. 4,434,226. Specific examples of the halogen composition of tabular grains include silver chloroiodide, silver iodobromide, silver chloride, silver chlorobromide, silver bromide, and silver chloroiodobromide. Alternatively, silver chlorobromide is preferable. It may also contain silver thiocyanate, silver cyanate and the like. Further, in the present invention, the tabular grains are preferably monodisperse. The structure and manufacturing method of monodisperse tabular grains are described in, for example, JP-A-63-151618.

In the tabular grains, silver halides having different compositions may be joined by epitaxial joining, or may be joined with compounds other than silver halide such as silver thiocyanate and oxides. These emulsion grains are described in U.S. Pat.
142,900, 4,459,353, British Patent 2,038,792, U.S. Patent 4,349,62.
No. 2, No. 4,395, 478, No. 4,433, 501
Issue 4,463,087, Issue 3,656,962
No. 3,852,067, JP-A-59-16254.
No. 0 and the like.

The silver halide grains used in the present invention are
Graphide, "Physics and Chemistry of Photography", published by Paul Montell (P. Glafkides, Chimie et P.
hysique Photographique, Pa
ul Montel, 1967), "Photographic Emulsion Chemistry" by Duffin, published by Focal Press (GF Duffi).
n, Photographic Emulsion C
chemistry, Focal Press, 196
6), "Production and Coating of Photographic Emulsions" by Zelikmann et al., Published by Focal Press (VL Zelikman et.
al, Making and Coating Pho
topographic Emulsion, Focal
Press, 1964) and the like. That is, any of an acidic method, a neutral method, an ammonia method and the like may be used, and as a method of reacting a soluble silver salt and a soluble halogen salt, any of a one-sided mixing method, a simultaneous mixing method and a combination thereof may be used. . A method of forming grains in the presence of excess silver ions (so-called reverse mixing method) can also be used. As one form of the simultaneous mixing method, a method of keeping pAg in a liquid phase where silver halide is formed constant, that is, a so-called controlled double jet method can be used. According to this method, a silver halide emulsion having a regular crystal form and a substantially uniform grain size can be obtained. In addition, 2 formed separately
A mixture of two or more silver halide emulsions may be used.

The silver halide emulsion comprising the above regular grains can be obtained by controlling pAg and pH during grain formation. For more information, for example,
Science and Engineering (Photog
radical Science and Engine
ering), Vol. 6, 159-165 (196)
2); Journal of Photographic Science (Journal of Photographics)
c Science), Volume 12, pp. 242-251 (1
964), U.S. Pat. No. 3,655,394 and British Patent No. 1,413,748.

Regarding the monodisperse emulsion, JP-A-48-
No. 8600, No. 51-39027, No. 51-8309
No. 7, No. 53-137133, No. 54-48521
No. 54-99419, No. 58-37635, No. 58-49938, Japanese Patent Publication No. 47-11386, US Pat. No. 3,655,394 and British Patent No. 1,41.
3, 748 and the like.

During the production of an emulsion containing tabular grains, a silver salt solution (eg AgN) added to accelerate grain growth.
A method of increasing the addition rate, the addition amount, and the addition concentration of the O ₃ aqueous solution) and the halide solution (for example, KBr aqueous solution) is preferably used. Regarding these methods, for example, British Patent No. 1,335,925 and US Pat. No. 3,67
2,900, 3,650,757, 4,24
No. 2,445, JP-A Nos. 55-142329 and 55-
The description of No. 158124 can be referred to.

To accelerate the ripening of silver halide grains,
Silver halide solvents are useful. For example, it is known to have excess halogen ions present in the reactor to accelerate aging. Therefore, introduction of a silver halide solution into the reactor can accelerate ripening. Other ripening agents can be used, and the total amount of these ripening agents can be added to the dispersion medium in the reactor before the addition of silver and halide salts, or 1 or 2 or more. It is also possible to add the halide salt, silver salt or peptizer of the above and to introduce them into the reactor. As another variant, the ripening agent can be introduced independently at the halide salt and silver salt addition stages.

As the ripening agents other than halogen ions, ammonia, amine compounds, thiocyanate salts,
For example, alkali metal thiocyanate salts, especially sodium and potassium thiocyanate salts, and ammonium thiocyanate salts can be used. The use of thiocyanate ripening agents is described in US Pat. No. 2,222,264.
Nos. 2,448,534 and 3,320,06
Instructions can be found in No. 9. US Pat. No. 3,271,1
57, 3,574,628 and 3,73
Conventional thioether ripening agents as described in 7,313 can also be used. In addition, JP-A-53-8
It is also possible to use thione compounds as disclosed in 2408 and 53-144319.

The properties of the silver halide grains can be controlled by allowing various compounds to be present in the silver halide precipitation forming process. Such compounds may be initially present in the reactor. In addition, one or more salts can be added together with the salt according to a conventional method. US Patent Nos. 2,448,060 and 2,628,167
Issue 3, Issue 3,737,313, Issue 3,772,031
Issue, and Research Disclosure, Vol. 134,
June 1975, 13452, copper, iridium, lead, bismuth, cadmium, zinc, (sulfur,
The characteristics of silver halide can be controlled by allowing compounds such as chalcogen compounds such as selenium and tellurium), compounds such as gold and compounds of Group VII noble metals to be present during the silver halide precipitation formation process. Japanese Patent Publication 58-1410
Issue, Moisar et al., Journal of Photographic Science, 25, 1977.
As described on pages 19 to 27, the silver halide emulsion can reduce-sensitize the inside of the grain during the precipitation formation process.

It is also possible to carry out chemical sensitization in the presence of a chemical sensitization aid. As the chemical sensitization aid used, compounds such as azaindene, azapyridazine, and azapyrimidine which are known to suppress fog and increase sensitivity in the process of chemical sensitization are used. Examples of chemical sensitization aids are
US Pat. Nos. 2,131,038 and 3,411,91
No. 4, 3,554, 757, JP-A-58-1265.
36, JP-A-62-253159 and Duffin, "Photographic Emulsion Chemistry", pages 138 to 143 (published by Focal Press, 1966).

The silver halide grains used in the present invention are
Usually, those which have been physically aged, chemically aged and spectrally sensitized are used. The additives used in such a process are Research Disclosure No. 17643 and N
o. 18716.

Gelatin is advantageously used as the protective colloid used in the preparation of the emulsion of the present invention, but other hydrophilic colloids can also be used. For example, gelatin derivatives, graft polymers of gelatin and other polymers, proteins such as albumin and casein; cellulose derivatives such as hydroxyethyl cellulose, carboxymethyl cellulose, cellulose sulfates, etc .; sugar derivatives such as sodium alginate and starch derivatives; Polyvinyl alcohol, polyvinyl alcohol partial acetal, poly-N-vinylpyrrolidone, polyacrylic acid,
Various synthetic hydrophilic polymer substances such as single or copolymers such as polymethacrylic acid, polyacrylamide, polyvinylimidazole, polyvinylpyrazole, etc. can be used.

Examples of gelatin include lime-processed gelatin, acid-processed gelatin and Bull. Soc. Sci. Ph
oto. Japan, No. 16, P30 (1966)
You may use the enzyme-treated gelatin as described in,
Further, a hydrolyzate or an enzymatic hydrolyzate of gelatin can be used.

Various antifoggants or photographic stabilizers can be used in the present invention. Examples thereof include azoles and azaindenes described in RD17643 (1978), pages 24 to 25, JP-A-59-16844.
Nitrogen-containing carboxylic acids and phosphoric acids described in JP-A No. 2-11, mercapto compounds and metal salts thereof described in JP-A-59-111636, and acetylene compounds described in JP-A-62-87957 are used.

The silver halide used in the present invention may be spectrally sensitized with methine dyes and the like. The dyes used include cyanine dyes, merocyanine dyes, complex cyanine dyes, complex merocyanine dyes, polo polar cyanine dyes, hemicyanine dyes, styryl dyes and hemioxonol dyes. Specifically, U.S. Pat. No. 4,617,257 and JP-A-59-180550.
No. 60-140335, RD17029 (197).
8 years) sensitizing dyes described on pages 12 to 13 and the like.
These sensitizing dyes may be used alone or in combination thereof, and the combination of sensitizing dyes is often used particularly for the purpose of supersensitization.

Along with the sensitizing dye, a dye having no spectral sensitizing effect by itself or a compound which does not substantially absorb visible light and exhibits supersensitization may be contained in the emulsion (eg, US Pat. Nos. 3,615,641 and JP-A-63-23145).

The time of adding these sensitizing dyes to the emulsion may be during chemical ripening or before or after chemical ripening, or according to US Pat. Nos. 4,183,756 and 4,225,666. It may be before or after nucleation. In particular, the presence of a sensitizing dye at the time of chemical sensitization often gives a preferable effect. The addition amount is generally about 10 ⁻⁸ to 10 ⁻² mol per mol of silver halide.

Useful sensitizing dyes used in the present invention are, for example, US Pat. Nos. 3,522,052 and 3,619,1.
No. 97, No. 3,713, 828, No. 3, 615, 64
No. 3, No. 3,615, 632, No. 3,617, 293
No. 3,628,964, 3,703,377
Issue No. 3,666,480 Issue 3,667,960
Nos. 3,679,428 and 3,672,897
Issue No. 3,769,026 Issue No. 3,556,800
Issue No. 3,615,613 Issue No. 3,615,638
Nos. 3,615,635 and 3,705,809
No. 3,312,349, No. 3,677,765
Nos. 3,770,449, 3,770,440
Issue No. 3,769,025 Issue No. 3,745,014
Nos. 3,713,828 and 3,567,458
Nos. 3,625,698, 2,526,632
No. 2,503,776, JP-A-48-76525.
And Belgian Patent No. 691,807.

Photosensitive halogen used in the present invention
Silver halide coating amount is 1 mg / m in terms of silver. ³-10g / m³of
It is a range.

In the present invention, an organic metal salt may be used as an oxidizing agent together with the photosensitive silver halide. Among such organic metal salts, organic silver salts are particularly preferably used. Organic compounds that can be used to form the above organic silver salt oxidizing agents include US Pat.
There are benzotriazoles, fatty acids and other compounds described in No. 26, columns 52 to 53. In addition, JP-A-60-1
Silver salts of carboxylic acids having an alkynyl group such as silver phenylpropiolate described in 13235, and JP-A-61-161
The acetylene silver described in No. 249044 is also useful. Two or more kinds of organic silver salts may be used in combination.

The above organic silver salts are photosensitive silver halides.
0.01 to 10 moles per mole, preferably 0.1.
01 to 1 mol can be used in combination. The total coating amount of the photosensitive silver halide and the organic silver salt is preferably 50 mg to 10 g / m ² in terms of silver.

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

As the reducing agent used in the present invention, those known in the field of photothermographic materials can be used. Further, a dye-donor compound having a reducing property described later is also included (in this case, other reducing agents can be used together). Further, a reducing agent precursor which has no reducing property itself but exhibits reducing property by the action of a nucleophile or heat during the development process can also be used.

Examples of the reducing agent used in the present invention include:
U.S. Pat. No. 4,500,626, columns 49-50, 44
No. 83, col. 31, columns 31-43;
No. 4,590,152, JP-A No. 60-140335, pages (17) to (18), Nos. 57-40245, 56.
-138736, 59-178458, 59-
No. 53831, No. 59-182449, No. 59-18
No. 2450, No. 60-119555, No. 60-128
436 to 60-128439, 60-1
No. 98540, No. 60-181742, No. 61-25.
9253, 624244044, 62-131
From 253 to 62-131256, there are reducing agents and reducing agent precursors described on pages 78 to 96 of EP 220746A2. US Patent No. 303986
Combinations of various reducing agents such as those disclosed in No. 9 can also be used.

When a diffusion resistant reducing agent is used, an electron transfer agent and / or an electron transfer agent is optionally added to promote electron transfer between the diffusion resistant reducing agent and the developable silver halide.
Alternatively, electron transfer agent precursors can be used in combination. The electron transfer agent or its precursor can be selected from the above-mentioned reducing agent or its precursor. It is desirable that the electron transfer agent or its precursor has a mobility higher than that of the diffusion resistant reducing agent (electron donor). Particularly useful electron transfer agents are 1-phenyl-3-pyrazolidones or aminophenols.

The diffusion-resistant reducing agent (electron donor) used in combination with the electron transfer agent may be any of those reducing agents which do not substantially move in the layer of the photosensitive element.
Hydroquinones, sulfonamide phenols, sulfonamide naphthols, JP-A-53-11 are preferred.
Examples thereof include compounds described as electron donors in No. 0827, and dye-donating compounds having diffusion resistance and reducing properties described below.

In the present invention, the reducing agent is added in an amount of 0.001 to 20 mol, and particularly preferably 0.001 to 1 mol of silver.
It is from 01 to 10 mol.

In the present invention, when a silver ion is reduced to silver under a high temperature condition, a compound which produces or releases a mobile dye in response to this reaction or in the opposite reaction, that is, a dye-donor is provided. It may also contain a sex compound. Examples of the dye-donating compound that can be used in the present invention include a compound (coupler) that forms a dye by an oxidative coupling reaction. The coupler may be a 4-equivalent coupler or a 2-equivalent coupler. A 2-equivalent coupler having a diffusion resistant group as a leaving group and forming a diffusible dye by an oxidative coupling reaction is also preferable. The diffusion resistant group may form a polymer chain.
For specific examples of color developers and couplers, see TH James “Th
e Theory of the Photographic Process "4th Edition 291
To 334 and 354 to 361, JP-A-58-1
No. 23533, No. 58-149046, No. 58-14
No. 9047, No. 59-111148, No. 59-124
No. 399, No. 59-174835, No. 59-2315.
No. 39, No. 59-231540, No. 60-2950.
No. 60, No. 60-2951, No. 60-14242, No. 6
0-23474, 60-66249 and the like.

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

Specific examples of the dye-donating compound represented by the general formula [LI] include the following compounds (1) to (4). In addition, the following items (1) to (4) are for forming a diffusible dye image (positive dye image) in the opposite manner to the development of silver halide, and the terms and are the diffusible dye image (corresponding to the development of silver halide ( To form a negative dye image).

US Pat. Nos. 3,134,764 and 336.
2819, 3597200, 3544545.
No. 3,482,972 and the like, a dye developer in which a hydroquinone-based developer and a dye component are linked. This dye developing agent is diffusible in an alkaline environment, but becomes non-diffusible when it reacts with silver halide.

As described in US Pat. No. 4,053,137, a non-diffusible compound which releases a diffusible dye in an alkaline environment but loses its ability when reacted with silver halide can be used. Examples thereof include compounds that release a diffusible dye by an intramolecular nucleophilic substitution reaction described in US Pat. No. 3,980,479, and US Pat. No. 4,199.
Compounds that release a diffusible dye by the intramolecular rewinding reaction of the isoxazolone ring described in JP-A No. 354 and the like.

US Pat. No. 4,559,290, European Patent 220720A2, US Pat. No. 4,783,396,
As described in Published Technical Report 87-6199, a non-diffusible compound which releases a diffusible dye by reacting with a reducing agent left unoxidized by development can also be used.

As an example, US Pat. No. 4,133,938.
No. 9, 4139379, JP-A-59-185333.
Nos. 57-84453 and the like, which release a diffusible dye by a nucleophilic substitution reaction in the molecule after reduction, U.S. Pat.
No. 101649, No. 61-88257, RD240
25 (1984) and the like, which release a diffusible dye by intramolecular electron transfer reaction after reduction, West German Patent No. 3008588A, JP-A-56-14.
2530, U.S. Pat. Nos. 4,343,893 and 4619.
Compounds that release a diffusible dye by cleavage of a single bond after reduction, as described in U.S. Pat.
Examples thereof include nitro compounds described in U.S. Pat. No. 223, which release a diffusible dye after electron acceptance, compounds described in U.S. Pat. No. 4,609,610 which release a diffusible dye after electron acceptance, and the like.

Further, as more preferable ones, European Patent No. 220746A2, Kokai Giho No. 87-6199, US Pat. No. 4,783,396, and Japanese Patent Laid-Open No. 63-201653.
No. 63, 2016-654, etc.
A compound having a —X bond (X represents an oxygen, sulfur or nitrogen atom) and an electron-withdrawing group, SO ₂ —X (X has the same meaning as above) in one molecule described in JP-A-1-26842. Compound having electron-withdrawing group, JP-A-63-271344
Compounds having a PO-X bond (X has the same meaning as above) and an electron-withdrawing group in one molecule described in JP-A-63-27.
C-X 'bond (X' in marked within one molecule in 1341 issue X synonymous or or -SO ₂ - and represented) include compounds having an electron-withdrawing group.

Among these, a compound having an N—X bond and an electron-withdrawing group in one molecule is particularly preferable. Specific examples thereof include the compound (1) described in EP 220746A2
(3), (7) to (10), (12), (13), (15), (23) to (26), (3
1), (32), (35), (36), (40), (41), (44), (53) to (5
9), (64), (70), compound (1) of Open Technical Report 87-6199
1) to (23).

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

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

Other than the above-mentioned couplers and dye-donating compounds other than the general formula [LI], dye silver compounds in which an organic silver salt and a dye are bound (Research Disclosure, May 1978, pages 54 to 58). , Etc., azo dyes used in the heat developable silver dye bleaching method (US Pat.
957, Research Disclosure, 1976.
Year 4 issue, pages 30 to 32, etc.), leuco dyes (US Pat. Nos. 3,985,565 and 4,022,617, etc.) can also be used.

Hydrophobic additives such as dye-donor compounds and anti-diffusion reducing agents can be incorporated into the layer of the photographic material by known methods such as the method described in US Pat. No. 2,322,027. In this case, JP-A-59-83154,
59-178451, 59-178452, 59-178453, 59-178454, 5
9-178455, 59-178457 and the like, a high boiling point organic solvent, if necessary, a boiling point of 50 ° C.
It can be used in combination with an organic solvent having a low boiling point of up to 160 ° C.

The amount of the high boiling point organic solvent is 10 g or less, preferably 5 g or less, relative to 1 g of the dye-donor compound used. Further, 1 cc or less, more preferably 0.5 cc or less, and especially 0.3 cc or less is suitable for 1 g of the binder.

JP-B-51-39853, JP-A-51-
The dispersion method using a polymer described in 59943 can also be used.

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

When dispersing the hydrophobic compound in the hydrophilic colloid as a binder, various surfactants can be used. For example, the surfactants listed on pages (37) to (38) of JP-A-59-157636 can be used.

In the present invention, a compound capable of activating development and stabilizing an image at the same time can be used in the light-sensitive material. Specific compounds preferably used are described in US Pat. No. 4,500,626, columns 51 to 52.

In a system for forming an image by diffusion transfer of a dye, a dye fixing element is used together with a light-sensitive material. The dye-fixing element may be applied separately on a support different from the photosensitive element, or may be applied on the same support as the photosensitive element. Regarding the relationship between the light-sensitive element and the dye fixing element, the relationship with the support, and the relationship with the white reflective layer, the relationship described in column 57 of US Pat. No. 4,500,626 can be applied to the present application.

In order to include the form in which the light-sensitive element and the dye-fixing element are coated on the same support as described above, the light-sensitive material of the present invention will be referred to as the light-sensitive element hereinafter for the sake of convenience. explain. The dye fixing element is also called a dye fixing material.

The dye fixing element preferably used in the present invention has at least one layer containing a mordant and a binder. As the mordant, those known in the photographic field can be used, and specific examples thereof include US Pat. No. 4,500,626, columns 58 to 59 and JP-A No. 61-88256 (32).
The mordant described on page (41), JP-A-62-244043.
No. 62-244036 and the like. Further, a dye-receptive polymer compound as described in US Pat. No. 4,463,079 may be used. If necessary, a protective layer, a release layer,
An auxiliary layer such as an anti-curl layer can be provided. In particular, it is useful to provide a protective layer.

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

When a system in which a small amount of water is supplied for thermal development is adopted, it becomes possible to quickly absorb water by using the above superabsorbent polymer. Also, the use of superabsorbent polymers in the dye-fixing layer or its protective layer can prevent the dye from retransferring from the dye-fixing element to another after transfer.

In the present invention, the coating amount of the binder is 1
It is preferably 20 g or less per m ² , particularly 10 g or less, more preferably 7 g or less.

As the hardener used in the constituent layers of the light-sensitive element and the dye-fixing element, US Pat. No. 4,678,739, No. 4 can be used.
Column 1, JP-A-59-116655 and JP-A-64-2452.
No. 61, No. 61-18942, etc. are mentioned. More specifically, aldehyde type hardeners (formaldehyde etc.), aziridine type hardeners, epoxy type hardeners, vinyl sulfone type hardeners (N, N'-ethylene-
Bis (vinylsulfonylacetamide) ethane etc.), N
-Methylol type hardeners (such as dimethylol urea) and polymer hardeners (compounds described in JP-A-62-234157).

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

Examples of the base precursor include salts of an organic acid and a base which are decarboxylated by heat, compounds which release amines by intramolecular nucleophilic substitution reaction, Rossen rearrangement or Beckmann rearrangement. A specific example is US Pat. No. 45114.
93, JP-A-62-65038 and the like.

In a system in which heat development and transfer of a dye are simultaneously carried out in the presence of a small amount of water, it is preferable to add a base and / or a base precursor to the dye-fixing element in order to improve the storage stability of the light-sensitive element.

In addition to the above, a combination of a sparingly soluble metal compound described in European Patent Publication No. 210660 and a compound capable of undergoing a complex forming reaction with a metal ion constituting the sparingly soluble metal compound (called a complex forming compound), JP-A-61-2
The compounds that generate a base by electrolysis as described in No. 32451 can also be used as the base precursor. The former method is particularly effective. The sparingly soluble metal compound and the complex-forming compound are advantageously added separately to the light-sensitive element and the dye-fixing element.

In the light-sensitive element and / or the dye-fixing element of the present invention, various development terminators can be used for the purpose of always obtaining a constant image against variations in processing temperature and processing time during development. The term "development terminating agent" as used herein refers to a compound that immediately neutralizes or reacts with a base to reduce the concentration of the base in the film to stop the development after proper development, or inhibits development by interacting with silver and a silver salt. Compound. Specific examples thereof include an acid precursor that releases an acid when heated, an electrophilic compound that causes a substitution reaction with a coexisting base when heated, or a nitrogen-containing heterocyclic compound, a mercapto compound and a precursor thereof. For more details, see JP-A-62-25
No. 3159, pages (31) to (32).

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

In the constituent layers of the light-sensitive element and the dye-fixing element, a plasticizer, a slipping agent, or a high boiling point organic solvent can be used as a peelability improving agent between the light-sensitive element and the dye-fixing element. A specific example is (2) in JP-A-62-253159.
5), No. 62-245253 and the like.

Further, various silicone oils (all silicone oils from dimethylsilicone oil to modified silicone oils obtained by introducing various organic groups into dimethylsiloxane) can be used for the above purpose. For example, various modified silicone oils described in “Modified Silicone Oil” technical data P6-8B issued by Shin-Etsu Silicone Co., Ltd., particularly carboxy-modified silicone (trade name X-22-3710) are effective. In addition, JP-A-6
The silicone oils described in JP-A No. 2-219553 and JP-A No. 63-46449 are also effective.

An anti-fading agent may be used in the dye fixing element. As the anti-fading agent, there are, for example, an antioxidant, an ultraviolet absorber, or a kind of metal complex.

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

As the ultraviolet absorber, benzotriazole compounds (US Pat. No. 3,533,794, etc.), 4-
Thiazolidone compounds (US Pat. No. 3,352,681, etc.), benzophenone compounds (JP-A-46-2784)
Etc.) and others, JP-A Nos. 54-48535 and 62-
There are compounds described in Nos. 136641 and 61-8256. Further, the ultraviolet absorbing polymer described in JP-A-62-260152 is also effective.

Examples of the metal complex include US Pat. No. 4,2411,
55, 42425018, columns 3 to 36, 4,25
4,195, columns 3 to 8, JP-A-62-174741.
No. 61-88256, pages (27) to (29), JP-A-1-75568, JP-A-62-31096, JP-A-1.
There are compounds described in, for example, -74272.

Examples of useful anti-fading agents are disclosed in JP-A-62-21.
5272 (125)-(137).

An anti-fading agent for preventing fading of the dye transferred to the dye-fixing element may be contained in the dye-fixing element in advance, or may be supplied to the dye-fixing element from the outside such as a light-sensitive element. May be.

The above-mentioned antioxidant, ultraviolet absorber and metal complex may be used in combination with each other.

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

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

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

A matting agent can be used in the light-sensitive element and the dye fixing element. Matting agents such as silicon dioxide, polyolefins, polymethacrylates, etc.
Japanese Patent Application No. 62-110064, such as benzoguanamine resin beads, polycarbonate resin beads, AS resin beads and the like, in addition to the compounds described on page 1-88256 (29).
No. 62-110065.

In addition, the constituent layers of the light-sensitive element and the dye-fixing element may contain a thermal solvent, a defoaming agent, an antibacterial / antifungal agent, colloidal silica and the like. Specific examples of these additives are described in JP-A-61-88256, pages (26) to (32).

As the support for the light-sensitive element and the dye-fixing element of the present invention, those which can withstand the processing temperature are used. Generally, paper and synthetic polymer (film) are used. Specifically, polyethylene terephthalate (P
ET), polycarbonate, polyvinyl chloride, polystyrene, polypropylene, polyimide, celluloses (for example, triacetyl cellulose) or those films containing a pigment such as titanium oxide, and synthetic film made by polypropylene or the like. Blended paper made from synthetic resin pulp such as polyethylene and natural pulp, Yankee paper, baryta paper, coated paper (particularly Cascote paper), metal, cloth, glass and the like are used.

These can be used alone or
It can also be used as a support having one or both sides laminated with a synthetic polymer such as polyethylene. In addition to these, the supports described in JP-A-62-253159, pages (29) to (31) can be used. A hydrophilic binder, a semiconductive metal oxide such as alumina sol or tin oxide, carbon black and other antistatic agents may be coated on the surface of these supports.

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

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

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

In the present invention, water is used to promote the migration of the dye released during the development process (this water is referred to as dampening water in the present invention). That is, JP-A-59-21
As described in detail in No. 8443, No. 61-238056 and the like, development and transfer are carried out simultaneously or successively by heating in the presence of a small amount of solvent (particularly water). In this method,
The heat development temperature is preferably 50 ° C. or higher and 100 ° C. or lower. In this case, the amount of water used is equal to or less than the weight of water corresponding to the maximum swelling volume of the entire coated film (especially, less than or equal to the amount of water corresponding to the maximum swelling volume of the entire coated film minus the weight of the entire coated film). A small amount is enough.

As a heating method in the developing and / or transferring step, a heated block or plate is contacted, or a hot plate, a hot presser, a heat roller, a halogen lamp heater, an infrared or far infrared lamp heater or the like is contacted. And passing through a high temperature atmosphere. Further, a resistance heating element layer may be provided on the photosensitive element or the dye fixing element, and the resistance heating element layer may be energized for heating. As the heating element layer, those described in JP-A-61-145544 can be used.

Superimposing the light-sensitive element and the dye-fixing element,
The pressure condition and the method for applying the pressure when closely contacting each other are disclosed in Japanese Patent Laid-Open Publication No.
The method described in page 1-147244 (27) can be applied.

Any of a variety of heat developing apparatus can be used in processing the photographic elements of this invention. For example, JP-A-59-7
No. 5247, No. 59-177547, No. 59-181.
No. 353, No. 60-18951, No. 62-259.
The device described in No. 44 etc. is preferably used.

[0106]

The present invention will be described with reference to the following examples.
The present invention is not limited to these.

Example 1

A method for preparing a dispersion of zinc hydroxide will be described. Zinc hydroxide with an average particle size of 0.2 μm 12.5
g, 1 g of carboxymethyl cellulose as a dispersant, and 0.1 g of sodium polyacrylate as a 4% gelatin aqueous solution 10
In addition to 0 ml, it was ground in a mill for 30 minutes using glass beads having an average particle size of 0.75 mm. The glass beads were separated to obtain a zinc hydroxide dispersion.

Next, a method for preparing a dispersion of the electron transfer agent will be described. 10 g of electron transfer agent (1), 0.5 g of polyethylene glycol nonylphenyl ether as a dispersant, and 0.5 g of anionic surfactant (1) were added to a 5% gelatin aqueous solution, and glass beads having an average particle size of 0.75 mm were milled. Was used for 60 minutes. The glass beads were separated to obtain a dispersion of the electron transfer agent having an average particle size of 0.35 μm.

[0110]

[Chemical 1]

[0111]

[Chemical 2]

Next, a method for preparing a dye trapping agent dispersion will be described. Polymer latex (A) (13% solid content)
While stirring a mixed solution of 108 ml, 20 g of the surfactant (1) and 1232 ml of water, 600 ml of a 5% aqueous solution of the anionic surfactant (1) was added over 10 minutes. Using the ultrafiltration module, the dispersion thus prepared is 500 ml.
It was concentrated and desalted. Next, 1500 ml of water is added, and the same operation is repeated once more to repeat the dye trapping agent dispersion 500.
g was obtained.

[0113]

[Chemical 3]

[0114]

[Chemical 4]

Next, a method for preparing a gelatin dispersion of the hydrophobic additive will be described. Cyan, magenta, yellow, and electron donor gelatin dispersions were prepared according to the formulations in Table 1, respectively. That is, each oil phase component was dissolved by heating at about 60 ° C. to form a uniform solution, and this solution and an aqueous phase component heated at about 60 ° C. were added, and the mixture was stirred and mixed, followed by a homogenizer for 13 minutes,
Dispersed at 12000 rpm. Water was added to this and stirred to obtain a uniform dispersion.

[0116]

[Table 1]

[0117]

[Chemical 5]

[0118]

[Chemical 6]

[0119]

[Chemical 7]

[0120]

[Chemical 8]

[0121]

[Chemical 9]

[0122]

[Chemical 10]

[0123]

[Chemical 11]

[0124]

[Chemical 12]

[0125]

[Chemical 13]

[0126]

[Chemical 14]

Next, a method for preparing a photosensitive silver halide emulsion will be described.

Photosensitive Silver Halide Emulsion (1) [For red-sensitive emulsion layer] Well-stirred aqueous gelatin solution (20 g of gelatin, 0.5 g of potassium bromide, 3 g of sodium chloride in 480 ml of water).
g and 30 mg of the chemical (A) were added and kept at 45 ° C.), the solutions (I) and (II) in Table 2 were simultaneously added at an equal flow rate for 20 minutes. After 5 minutes, solution (III) and solution (IV) in Table 2 were simultaneously added at the same flow rate for 25 minutes. In addition, 10 minutes after the start of addition of the liquids (III) and (IV), an aqueous solution of a gelatin dispersion of the dye (containing 105 g of water, 1 g of gelatin, 70 mg of the dye (a), 139 mg of the dye (b), and 5 mg of the dye (c)) was added. (Incubated at 45 ° C.) was added over 20 minutes.

After washing with water and desalting by a conventional method, 22 g of lime-treated ossein gelatin was added to adjust pH to 6.2 and pAg to 7.7, and sodium thiosulfate and 4-hydroxy- were added.
6-Methyl-1,3,3a, 7-tetrazaindene and chloroauric acid were added for optimum chemical sensitization at 60 ° C., and then an antifoggant (2) was added, followed by cooling. Thus, 635 g of a monodisperse cubic silver chlorobromide emulsion having an average grain size of 0.30 μm was obtained.

[0130]

[Chemical 15]

[0131]

[Table 2]

[0132]

[Chemical 16]

Photosensitive Silver Halide Emulsion (2) [For red-sensitive emulsion layer] Well-stirred aqueous gelatin solution (20 g of gelatin, 0.5 g of potassium bromide, 6 g of sodium chloride in 783 ml of water).
g and 30 mg of the chemical (A) were added and kept at 65 ° C.), the solutions (I) and (II) in Table 3 were simultaneously added at an equal flow rate for 30 minutes. After 5 minutes, solution (III) and solution (IV) in Table 3 were added simultaneously at the same flow rate for 15 minutes. Two minutes after the addition of the solutions (III) and (IV), an aqueous solution of a gelatin dispersion of a dye (0.9 g of gelatin in 76 ml of water, 76 mg of the dye (a),
The dye (b) (150 mg) and the dye (c) (5 mg) which had been kept at 50 ° C.) were added over 18 minutes.

After washing with water and desalting by a conventional method, 22 g of lime-treated ossein gelatin was added to adjust the pH to 6.2 and pAg to 7.8, and sodium thiosulfate and 4-hydroxy- were added.
6-Methyl-1,3,3a, 7-tetrazaindene and chloroauric acid were added and optimal chemistry was performed at 60 ° C, and then an antifoggant (1) was added and then cooled. Thus, monodisperse cubic silver chlorobromide emulsion 6 having an average grain size of 0.50 μm
35 g were obtained.

[0135]

[Chemical 17]

[0136]

[Table 3]

Photosensitive Silver Halide Emulsion (3) [For Green Sensitive Emulsion Layer] Well stirred gelatin aqueous solution (20 g gelatin in 690 ml water, 0.5 g potassium bromide, 4 g sodium chloride)
g and 15 mg of the chemical (A) were added and kept at 48 ° C.), the solutions (I) and (II) in Table 4 were simultaneously added at an equal flow rate for 8 minutes. After 10 minutes, solution (III) and solution (IV) in Table 4 were simultaneously added at the same flow rate for 32 minutes. In addition, 1 minute after the addition of the solutions (III) and (IV), an aqueous solution of a gelatin dispersion of the dye (2.5 g of gelatin and 250 mg of the dye (d) in 100 ml of water and kept at 45 ° C.) was put together. Was added.

After washing with water and desalting by a conventional method, 20 g of lime-treated ossein gelatin was added to adjust pH to 6.0 and pAg to 7.6, and sodium thiosulfate and 4-hydroxy- were added.
6-Methyl-1,3,3a, 7-tetrazaindene and chloroauric acid were added for optimum chemical sensitization at 68 ° C., antifoggant (1) was added, and then the mixture was cooled. Thus, a monodisperse cubic silver chlorobromide emulsion 63 having an average grain size of 0.27 μm was obtained.
5 g was obtained.

[0139]

[Table 4]

[0140]

[Chemical 18]

Photosensitive Silver Halide Emulsion (4) [For Green Sensitive Emulsion Layer] Well-stirred aqueous gelatin solution (in 700 ml of water, 20 g of gelatin, 0.3 g of potassium bromide, 6 g of sodium chloride)
solution (I) and solution (II) shown in Table 5 were simultaneously added to the above solution at a constant flow rate for 20 minutes. After 10 minutes, solution (III) and solution (IV) in Table 5 were further added simultaneously at an equal flow rate for 20 minutes. Also (III), (IV)
One minute after the end of the addition of the solution, an aqueous solution of a gelatin dispersion of a dye (1.8 g of gelatin in 95 ml of water, 180 mg of dye (d))
Which was kept at 45 ° C.) was added all at once.

After washing with water and desalting by a conventional method, 20 g of lime-treated ossein gelatin was added to adjust pH to 6.0 and pAg to 7.6, and sodium thiosulfate and 4-hydroxy- were added.
6-Methyl-1,3,3a, 7-tetrazaindene and chloroauric acid were added for optimum chemical sensitization at 68 ° C, and then an antifoggant (1) was added, followed by cooling. Thus, 635 g of a monodisperse cubic silver chlorobromide emulsion having an average grain size of 0.45 μm was obtained.

[0143]

[Table 5]

Photosensitive Silver Halide Emulsion (5) [For Blue Sensitive Emulsion Layer] Well stirred gelatin aqueous solution (20 g gelatin in 690 ml water, 0.5 g potassium bromide, 5 sodium chloride)
solution (I) and solution (II) shown in Table 6 were simultaneously added at a constant flow rate for 8 minutes. After 10 minutes, solution (III) and solution (IV) in Table 6 were added simultaneously at the same flow rate for 32 minutes. One minute after the addition of solutions (III) and (IV) was completed, 220 mg of dye (e) and 110 mg of dye (f) were added to an aqueous solution of dye (in 95 ml of water and 5 ml of methanol).
Which was kept at 45 ° C.) was added all at once.

After washing with water and desalting by a conventional method, 22 g of lime-treated ossein gelatin was added to adjust pH to 6.0 and pAg to 7.8, and sodium thiosulfate and 4-hydroxy- were added.
6-Methyl-1,3,3a, 7-tetrazaindene was added for optimum chemical sensitization at 68 ° C, and then an antifoggant (1) was added, followed by cooling. Thus, a monodisperse cubic silver chlorobromide emulsion 635 having an average grain size of 0.30 μm
g was obtained.

[0146]

[Table 6]

[0147]

[Chemical 19]

Photosensitive Silver Halide Emulsion (6) [For Blue Sensitive Emulsion Layer] Well stirred gelatin aqueous solution (20 g of gelatin, 0.3 g of potassium bromide and 9 g of sodium chloride in 695 ml of water).
g and 15 mg of the chemical (A) were added and kept at 63 ° C.), the solutions (I) and (II) in Table 7 were simultaneously added at an equal flow rate for 10 minutes. After 10 minutes, solution (III) and solution (IV) shown in Table 7 were added simultaneously at the same flow rate for 30 minutes. Also (III), (IV)
One minute after the end of the addition of the solution, an aqueous solution of the dye (in 66 ml of water and 4 ml of methanol, 155 mg of the dye (e) and 78 mg of the dye (f)) was added.
Which was kept at 60 ° C.) was added all at once.

After washing with water and desalting by a conventional method, 22 g of lime-treated ossein gelatin was added to adjust the pH to 6.0 and pAg to 7.8, and sodium thiosulfate and 4-hydroxy- were added.
6-Methyl-1,3,3a, 7-tetrazaindene and chloroauric acid were added for optimum chemical sensitization at 68 ° C, and then an antifoggant (1) was added, followed by cooling. Thus, 635 g of a monodisperse cubic silver chlorobromide emulsion having an average grain size of 0.55 μm was obtained.

[0150]

[Table 7]

Photosensitive material 1 shown in Table 8 using the above
I made 01.

[0152]

[Table 8]

[0153]

[Table 9]

[0154]

[Table 10]

[0155]

[Chemical 20]

[0156]

[Chemical 21]

[0157]

[Chemical formula 22]

Photosensitive materials 102 to 104 having different swells were prepared in the same manner as in the photosensitive material 101 except that the amount of the hardener (1) added was adjusted in the method for preparing the photosensitive material 101. The swelling values are shown in Table 11.

[0159]

[Table 11]

Next, a method of making the image receiving material will be described. An image receiving material R101 having a constitution as shown in Table 12 was prepared.

[0161]

[Table 12]

[0162]

[Table 13]

[0163]

[Chemical formula 23]

[0164]

[Chemical formula 24]

[0165]

[Chemical 25]

[0166]

[Chemical formula 26]

[0167]

[Chemical 27]

[0168]

[Chemical 28]

[0169]

[Chemical 29]

[0170]

[Chemical 30]

Further, in the method for preparing the image receiving material R101, the image receiving materials R102 to R102 in Table 14 are exactly the same as the image receiving material R101 except that the addition amount of the hardener (2) is adjusted.
104 was prepared.

[0172]

[Table 14]

Using the above light-sensitive materials 101 to 104 and image receiving materials R101 to 104, Japanese Patent Application No. 63-13710 is used.
Processing was performed using the image recording device described in No. 4. That is, a full-color original image was scanned and exposed through a slit, the exposed light-sensitive material was dipped in water kept at 40 ° C. for 4 seconds, and then squeezed with a roller and immediately superposed so that the image-receiving material and the film surface were in contact with each other. Then, using a heat drum whose temperature has been adjusted so that the water-absorbed film surface becomes 80 ° C., the photosensitive material is peeled from the image receiving material by heating for 15 seconds, and a clear color image corresponding to the original image is obtained on the image receiving material. Was given.

Then, a gray print having a uniform density over the entire surface was obtained in the same manner as above except that a gray original was used.
The stability of the image during long-term use in the present invention was evaluated by making 50 sheets of A4 size each day for 1 month each day, and evaluating the number of white spots visually recognized in the print at this time.

The sharpness was evaluated by observing the degree of resolution deterioration when the resolution chart was printed as a document by observing with the naked eye and a magnifying glass using the above apparatus. The fundamental spatial frequency of the resolution chart used is 1
8, 16, 14, 12.5, 11, 10, 9, 8, 7.
The thing of 1, 6.3, 5.6 pieces / mm was used.

Table 15 shows the results of the above evaluations. Table 15
Experiment numbers (9) to (11) in Example 1 were performed by changing the immersion time in the dampening water tank when the dampening water was applied. As is clear from this result, according to the method of the present invention, it is possible to obtain a sharp image free from image stains such as white spots even after long-term use.

[0177]

[Table 15]

Example 2 A method for preparing the emulsion (7) will be described. (Emulsion for Fifth Layer) Solution I and solution II having the composition shown in Table 17 were simultaneously added over 15 minutes to an aqueous solution having the composition shown in Table 16 which was well stirred, and then the composition shown in Table 17 was added. Liquid III and IV 3
Added over 5 minutes.

[0179]

[Table 16]

[0180]

[Table 17]

From 18 minutes after the start of addition of the solution III,
0.5% methanol solution of sensitizing dye (a) over 7 minutes
5 cc was added. Washing with water and desalting (pH =
4.1) and then add 22 g gelatine to pH
= 6.0, pAg = 7.9, and then chemically sensitized at 60 ° C. The compounds used for the chemical sensitization are shown in Table 18. The yield of the obtained emulsion was 630 g, which was a monodisperse cubic emulsion having a coefficient of variation of 10.2%, and the average grain size was 0.31 micrometer.

[0182]

[Table 18]

The method for preparing the emulsion (8) will be described. (Emulsion for Third Layer) Solution I and solution II having the composition shown in Table 20 were simultaneously added to an aqueous solution having the composition shown in Table 19 for 10 minutes, and the composition shown in Table 20 was then added. Liquid III and IV 4
Added over 5 minutes.

[0184]

[Table 19]

[0185]

[Table 20]

Further, after washing with water and desalting (performed with the compound represented by the precipitating agent a at pH = 3.9), gelatin 1 was used.
After adding 2 g and adjusting to pH = 5.9 and pAg = 7.8, it chemically sensitized at 70 degreeC. At the end of the chemical sensitization, 42 g of a gelatin dispersion of sensitizing dye (b) (gelatin 5%, sensitizing dye 0.5%) was added. The compounds used for the chemical sensitization are shown in Table 21. The yield of the obtained emulsion was 645 g, which was a monodisperse cubic emulsion having a coefficient of variation of 12.6%, and the average grain size was 0.32 micrometer.

[0187]

[Table 21]

The method for preparing the emulsion (9) will be described. (Emulsion for first layer) Solution I and solution II having the composition shown in Table 23 were simultaneously added over 15 minutes to an aqueous solution having the composition shown in Table 22 which was well stirred, and then the emulsion having the composition shown in Table 23 was added. Solution III and IV solution 2
Added over 5 minutes.

[0189]

[Table 22]

[0190]

[Table 23]

After washing with water and desalting (performed at pH = 3.8 using the compound represented by the precipitating agent a), gelatin 2 was used.
After 0 g was added to adjust pH = 6.6 and pAg = 8.0, chemical sensitization was performed at 58 ° C. At the end of the chemical sensitization, 42 g of a gelatin dispersion of sensitizing dye (c) (gelatin 5%, sensitizing dye 1%) was added. The compounds used for the chemical sensitization are shown in Table 24. The yield of the obtained emulsion was 650 g, which was a monodisperse cubic emulsion having a coefficient of variation of 9.7%, and the average grain size was 0.22 micrometer.

[0192]

[Table 24]

Next, a method for preparing a gelatin dispersion of a dye-donor compound will be described. Magenta dye-donor compound (A) 14.64 g, reducing agent A 0.8 g, antifoggant 0.20 g, surfactant 0.4 g, high boiling organic solvent (2) 5.1 g Then, 70 ml of ethyl acetate was added, and the mixture was heated and dissolved at about 60 ° C. to obtain a uniform solution. 71 g of this solution and a 14% solution of lime-processed gelatin and 220 cc of water
After stirring and mixing, the mixture was mixed with a homogenizer for 10 minutes for 100 minutes.
Dispersed at 00 rpm. This dispersion is referred to as a dispersion of a magenta dye-donor compound. 7.3 g of cyan dye-donor compound (B1), cyan dye-donor compound (B1)
2) 10.6 g, reducing agent A 1.0 g, antifoggant 0.30 g, surfactant 0.4 g, high boiling point organic solvent (2) 9.8 g, weigh 40 ml of ethyl acetate, It was heated and dissolved at about 60 ° C. to obtain a uniform solution. This solution, 71 g of a 14% lime-processed gelatin solution, and 260 cc of water were mixed by stirring, and then a homogenizer was used for 10 minutes at 10,000 rp.
dispersed at m. This dispersion is referred to as a dispersion of a cyan dye-donor compound. 18.8 g of the yellow dye-donor compound (C), 1.0 g of the reducing agent A, 0.13 g of the antifoggant, 1.5 g of the surfactant, 2.1 g of the dye a.
g and 7.5 g of high boiling point organic solvent (2) were weighed, 45 ml of ethyl acetate was added, and the mixture was heated and dissolved at about 60 ° C. to obtain a uniform solution. This solution, 71 g of a 14% lime-processed gelatin solution and 160 cc of water were mixed by stirring, and then dispersed by a homogenizer at 10,000 rpm for 10 minutes. This dispersion is referred to as a yellow dye-donor compound dispersion. With these, a photothermographic material 201 as shown in Table 25 was constructed.

[0194]

[Table 25]

[0195]

[Table 26]

[0196]

[Chemical 31]

[0197]

[Chemical 32]

[0198]

[Chemical 33]

[0199]

[Chemical 34]

[0200]

[Chemical 35]

[0201]

[Chemical 36]

[0202]

[Chemical 37]

[0203]

[Chemical 38]

[0204]

[Chemical Formula 39]

[0205]

[Chemical 40]

[0206]

[Chemical 41]

[0207]

[Chemical 42]

[0208]

[Chemical 43]

[0209]

[Chemical 44]

[0210]

[Chemical formula 45]

The high boiling organic solvent (1) is triisononyl phosphate, and the high boiling organic solvent (2) is trihexyl phosphate. A method for preparing a dispersion of zinc hydroxide will be described. Average particle size is 0.15μ
12.5 g of zinc hydroxide of 1 m, 1 g of carboxymethyl cellulose as a dispersant, and 0.1 g of sodium polyacrylate were added to 100 ml of 4% gelatin aqueous solution, and milled for 30 minutes using a glass bead with an average particle size of 0.75 mm. did. The glass beads were separated to obtain a zinc hydroxide dispersion.

Photosensitive materials 202 to 204 shown in Table 27 were prepared in exactly the same manner as the photosensitive material 201 except that the addition amount of the hardener was adjusted in the preparation of the photosensitive material 201. Further, in this embodiment, the image receiving material R of the first embodiment is used as the dye fixing material.
101 to 104 were used.

[0213]

[Table 27]

Next, evaluation was carried out by the following exposure and processing. A tungsten bulb is used as the light-sensitive material, and R, IR
1, IR2 three color separation filter (R is 650-690n
m and IR1 are bandpass filters of 730 to 770 nm, and IR2 is a filter that transmits 790 nm or more. ), Japanese Patent Application No. 63-281418,
Exposure was performed under the conditions shown in Table 28 using the laser exposure apparatus described in JP-A-63-204805. Exposed photosensitive material 2
Fountain solution was supplied to the emulsion surface of Nos. 01 to 204 by a wire bar, and then superposed so that the dye fixing material was in contact with the film surface. Using a heat roller whose temperature was adjusted so that the water-absorbed film had a temperature of 85 ° C., the dye fixing material was peeled from the photosensitive material after heating for 25 seconds, and an image was obtained on the dye fixing material.

[0215]

[Table 28]

Thus, a gray print having a uniform density was prepared, and this was used for evaluation of image stability during long-term use in the same manner as in the evaluation method of Example 1. In the same manner, a character of a commonly used size was printed, and the quality of this character was judged with the naked eye and a loupe to evaluate the sharpness. Table 29 shows the evaluation results. The experiment numbers (9) to (11) in Table 29 were carried out by changing the type of the wire bar when applying the dampening water. Table 2
As is clear from the result of No. 9, the method of the present invention can provide a sharp image with few image defects such as white spots even when used for a long period of time.

[0217]

[Table 29]

[0218]

As described above, according to the method of the present invention, it is possible to provide a sharp image without causing image defects even when used for a long period of time.

Claims (2)

[Claims] 1. A dampening water is applied to the photosensitive layer surface of a photothermographic material having a photosensitive silver halide, a reducing agent, a binder, and a dye-donating compound on a support, and the resulting layer is heated in superposition with an image receiving material. In the image forming method of forming a color image on the image-receiving layer of the image-receiving material, the temperature of the dampening water is 45 ° C. or higher, and the saturated water swelling amount of the light-sensitive material at the dampening water temperature is 10 μm or more and 20 μm
Hereinafter, similarly, the saturated water swelling amount of the image receiving material is 5 μm or more 1
A color image forming method, wherein the amount of dampening water is 0 μm or less and 90% or less of the sum of saturated water swelling amounts of the light-sensitive material and the image receiving material. 2. The temperature of the dampening water is 50 ° C. or higher, and the amount of dampening water applied is 80% or less of the sum of the saturated water swelling amounts of the light-sensitive material and the image receiving material. Claim 1
Color image forming method.