JPH06138622A - Heat-developable color photosensitive material - Google Patents

Abstract

PURPOSE:To enhance stability against time lapse by incorporating a hardly- soluble metal compound and a binder in a specified ratio in a protective layer between photosensitive layers different in color sensitivity and an F-containing surfactant in a protective layer farthest from a support. CONSTITUTION:The heat-developable color photosensitive material is formed by laminating multilayers comprising photosensitive silver halide, the binder, an electron transfer material, an electron donor, a reducible dye donor, and the like on a support and a nonphotosensitive layer and/or a protective layer formed between the 2 photosensitive layers different in color sensitivity contains the hardly-soluble metal compound and the binder of the nonphotosensitive layer and/or the protective layer in a ratio of 0.4-2.0, and the nonphotosensitive protective layer farthest from the support contains the F-containing surfactant. This binder is contained, preferably, in an amount of 0.40-1.60g/m<2>, thus permitting a white background and color reproduction performance to be improved without impairing the stability with time lapse of the photosensitive material.

Description

Detailed Description of the Invention

[0001]

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

[0002]

2. Description of the Related Art Photothermographic materials are known in this technical field, and the photothermographic material and its process are described, for example, in "Basics of Photographic Engineering", Non-silver photography (ed. 1982, published by Corona Publishing Co., Ltd.). ~ Page 255.

Many methods have been proposed for obtaining a color image by heat development. For example, US Pat. Nos. 3,531,286, 3,761,270 and 4,212.
No. 40, Belgian Patent No. 802519, Research Disclosure Magazine (hereinafter abbreviated as RD) September 1975, pages 31 to 32, etc., proposes a method of forming a color image by combining an oxidant of a developer with a coupler. Has been done.

However, since the photothermographic material for obtaining the above-mentioned color image is a non-fixing type, silver halide remains after the image is formed, and the white background is gradually colored when exposed to strong light or stored for a long time. Is causing a serious problem. Further, the above-mentioned various methods generally have a drawback that it takes a relatively long time for development and an obtained image has only a high fog and a low image density.

In order to ameliorate these drawbacks, a method has been proposed in which a diffusible dye is formed or released imagewise by heating, and the diffusible dye is transferred to an image-receiving material having a mordant with a solvent such as water. (US Patent No. 45
No. 00626, No. 4843914, No. 4503137
No. 4,559,920; JP-A-59-165054).

According to the above method, the developing temperature is still high, and the stability of the photosensitive material over time cannot be said to be sufficient. Therefore, a method of accelerating the development, lowering the development temperature, and simplifying the processing by heating and developing in the presence of a base or a base precursor and a small amount of water to transfer the dye is disclosed in JP-A-59-2.
18443, 61-238056, and European Patent 21.
No. 0660A2 and the like.

Many methods have been proposed for obtaining a positive color image by heat development. Among them, in U.S. Pat. No. 4,559,290, a so-called DRR compound is present in the presence of an oxidation type compound having no color image releasing ability and a reducing agent or a precursor thereof, and the reducing agent is added depending on the exposure amount of silver halide by heat development. A method has been proposed in which the diffusible dye is released by oxidizing the dye and reducing it with a reducing agent remaining without being oxidized. Further, in European Patent Publication No. 220746 and JP-A No. 64-13546, an N—X bond (X represents an oxygen atom, a nitrogen atom or a sulfur atom) as a compound that releases a diffusible dye by a similar mechanism. A heat-developable color light-sensitive material using a compound which releases a diffusible dye by reductive cleavage of is described, and it shows promise. This method comprises at least a photosensitive silver halide, a binder, an electron transfer agent, and / or a precursor thereof, an electron donor and / or a precursor thereof, and a reduced substance which is reduced to release a spreading dye on a support. Heat-developable color light-sensitive material having a multi-layered dye-donor compound is exposed and heated to oxidize an electron donor depending on the amount of silver halide, and the non-reducing dye-donor compound remains without being oxidized. In this method, a diffusible dye is released by reduction with an electron donor and transferred to a dye fixing material having a mordant to form a positive color image.

In the above-cited patent specifications, a compound which contains a sparingly soluble metal compound in a light-sensitive material and which releases a base by a dye-forming reaction between the sparingly soluble metal compound and water as a medium in a dye fixing material ( (Hereinafter referred to as a "fat-forming compound"), the light-sensitive material is exposed to light, then water is added thereto, and the mixture is heated with the dye-fixing material to form an image.

In the above-mentioned positive-working heat-developable color light-sensitive material, it is necessary to accelerate silver development in the exposed area and quickly consume the electron donor in order to improve the white background of the color image. However, in such a case, there is a problem that the color reproducibility is deteriorated. In addition, when a large amount of a sparingly soluble metal compound is contained in the light-sensitive material, there is a problem that the temporal stability of the light-sensitive material deteriorates. Various studies have been made to improve color reproducibility. For example, Japanese Patent Application No. 1-80
491 discloses a method of improving the spectral sensitivity characteristics of B, G, and R layers by optimizing them. Further, JP-A-2-110557 and JP-A-2-253253 disclose positive-type heat-developable color light-sensitive materials having a specific development inhibitor releasing redox compound in the intermediate layer. However, improvement in spectral sensitivity does not lead to sufficient improvement in color reproducibility. Further, when the above specific development inhibitor releasing redox compound is used, there is a great effect on the improvement of color reproducibility, but the white background is deteriorated, the discrimination is lowered, and the stability of the light-sensitive material with time is deteriorated. Then there was a problem.

Many studies have been conducted for a long time in order to improve the temporal stability of a light-sensitive material. Recently, JP-A-2-
53049, 2-53050, 2-230143,
No. 2-235044, etc., using a specific electron transfer agent, devising a method of use, and JP-A-3-102345.
As disclosed in JP-A No. 2004-242242, a method of improving the temporal stability of a material by using an electron transfer agent precursor in combination is disclosed. However, although these methods are certainly effective, there are problems that they are still insufficient, the white background is damaged, and the color reproducibility is deteriorated. Further, in order to improve the above problems and make them compatible with each other, JP-A-2-269 and 338 describe that the addition amount of the hardly soluble metal compound is 20 to 20% of the total binder amount of the photosensitive material.
A light-sensitive material containing 60% by weight is disclosed. However, although this method is effective, it is still insufficient and further improvement is desired.

[0011]

SUMMARY OF THE INVENTION It is, therefore, an object of the present invention to provide a positive-working heat-developable color light-sensitive material which has improved stability over time of the light-sensitive material and has improved white background and color reproducibility.

[0012]

As a result of research to solve the above-mentioned object, the present inventor has found that the following light-sensitive material achieves the object. That is, the present invention comprises at least a photosensitive silver halide, a binder, and
A multilayer photothermographic material comprising an electron transfer agent, and / or a precursor thereof, an electron donor and / or a precursor thereof, and a reducible dye-donating compound which is reduced to release a diffusible dye, A non-photosensitive layer and / or a protective layer between two photosensitive layers having different color sensitivities contain a sparingly soluble metal compound, and the ratio of the sparingly soluble metal compound and the binder in the layer is 0.4 to 2.0. And a fluorine-containing surfactant in the non-photosensitive protective layer farthest from the support. In the present invention,
More preferably, the amount of binder in the non-photosensitive layer between the two photosensitive layers having different color sensitivities is 0.40 g / m ² to 1.
Set to 60 g / m ² .

In the present invention, if the binder ratio of the poorly soluble metal compound and the poorly soluble metal compound addition layer is set to 0.4 to 2.0, the stability with time, color reproducibility and white background of the light-sensitive material are improved. Was effective but still insufficient. . Further, even if only the fluorine-containing surfactant is provided in the non-photosensitive protective layer farthest from the support, no effect is exhibited. However, in the present invention in which these are combined, a completely unexpected effect that the white background and the color reproducibility are improved together with the temporal stability of the light-sensitive material was obtained. Furthermore the effect is the binder of the non-photosensitive layer between the spectral sensitivity different two photosensitive layers was obtained further pronounced by to ^{0.25g / m 2 ~1.75g / m 2} .

The photothermographic material of the present invention basically comprises a support, a photosensitive silver halide, a binder, an electron transfer agent and / or a precursor thereof, an electron donor and / or a precursor thereof, and a reduction. It has a diffusion-resistant dye-donor compound (reducible dye-donor compound) that releases a diffusible dye, and may further contain an organometallic salt oxidizing agent and the like, if necessary. These components are often added to the same layer, but if they are in a reactive state, they can be divided and added to separate layers. For example, when a dye-donating compound which is colored is present in the lower layer of the silver halide emulsion, the reduction in sensitivity is prevented. The reducing agent is preferably incorporated in the photothermographic material, but a part thereof may be supplied from the outside by, for example, a method of diffusing from a dye fixing element described later.

In order to obtain a wide range of colors in the chromaticity diagram by using the three primary colors of yellow, magenta, and cyan, a combination of at least three silver halide emulsion layers having photosensitivity in different spectral regions is used. . For example, there are combinations 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. For the photothermographic material,
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 can be provided.

In the present invention, JP-A-62-1873 is used.
The base generation method shown in U.S. Pat. No. 4,880,723 is adopted. That is, a combination of a basic metal compound which is sparingly soluble in water (a sparingly soluble metal compound) and a compound (complex forming compound) capable of undergoing a complex forming reaction with a metal ion of this compound and water as a medium is used. In this base generation method, the complex-forming compound is contained in the dye fixing material, and the sparingly soluble metal compound is contained in the photosensitive material. After exposing the light-sensitive material to light or at the same time as the light exposure, a small amount of water is added to the light-sensitive material or the dye-fixing material, and when both materials are overlapped, the complex-forming compound dissolves in water and diffuses in the light-sensitive material. , Causes a reaction with the sparingly soluble metal compound and raises the pH in the film of the photosensitive material.

Specific examples of the sparingly soluble metal compound and the complex-forming compound used in the present invention include the above-mentioned JP-A-62-1.
The compounds described in 187341, page (3), upper right column, line 17 to (6), lower left column are mentioned. The sparingly soluble metal compound which is particularly preferably used in the present invention is zinc hydroxide, zinc oxide or a mixture thereof. Slightly soluble metal compounds are disclosed in JP-A-59-174830 and JP-A-53-102.
No. 733, etc., and it is preferably contained as a fine particle dispersion having an average particle size of 50.
It is preferably μ or less, particularly preferably 5 μ or less.

In the light-sensitive material of the present invention, the fluorine-based surfactant used in the non-photosensitive protective layer farthest from the support may be a low molecular weight or a high molecular weight. As those compounds, those described in JP-A-62-245,259 can be used. In the present invention, the fluorine-based surfactant is 0.
0002 g / m ^{2 to} 0.02 g / m ² , preferably 0.
0005 g / m ^{2 to} 0.01 g / m ² is used by adding it to the non-photosensitive protective layer farthest from the support. Preferred examples of the fluorine-based surfactant used in the present invention are shown below, but the present invention is not limited thereto.

[0019]

[Chemical 1]

[0020]

[Chemical 2]

[0021]

[Chemical 3]

[0022]

[Chemical 4]

The silver halide usable in the present invention may be any of silver chloride, silver bromide, silver iodobromide, silver chlorobromide, silver chloroiodide and silver chloroiodobromide. The silver halide emulsion used in the present invention may be either a surface latent image type emulsion or an internal latent image type emulsion. The internal latent image type emulsion is used as a direct reversal emulsion in combination with a nucleating agent or an optical fogging. Further, it may be a so-called core-shell emulsion in which the inside of the grain and the surface layer of the grain have different phases. The silver halide emulsion may be monodisperse or polydisperse, and monodisperse emulsions may be mixed and used. The particle size is preferably 0.1 to 2 μm, particularly preferably 0.2 to 1.5 μm. The crystal habit of silver halide grains is cubic, octahedral,
It may be a tetrahedron, a flat plate having a high aspect ratio, or the like. Specifically, US Pat. No. 4,500,626, column 50, U.S. Pat. No. 4,628,021, Research Disclosure (hereinafter abbreviated as RD) 17029 (19).
1978), JP-A-62-253159, JP-A-3-1.
No. 10555, No. 2-236546, No. 1-1677
Any of the silver halide emulsions described in No. 43, etc. can be used.

The silver halide emulsion may be used as it is after ripening, but it is usually chemically sensitized before use. The known sulfur sensitizing method, reduction sensitizing method, noble metal sensitizing method, selenium sensitizing method and the like can be used alone or in combination for the emulsion for a conventional type light-sensitive material. These chemical sensitizations can be carried out in the presence of a nitrogen-containing heterocyclic compound (JP-A-62-25315).
No. 9). The coating amount of the photosensitive silver halide used in the present invention is in the range of 1 mg to 10 g / m ² in terms of silver.

In the present invention, an organic metal salt can 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 those described in US Pat.
There are benzotriazoles, fatty acids and other compounds described in Nos. 0,626, columns 52 to 53. In addition, JP-A-60
No. 113235, a silver salt of a carboxylic acid having an alkynyl group such as silver phenylpropiolic acid, and JP-A-6-63.
The acetylene silver described in No. 1-249044 is also useful.
Two or more kinds of organic silver salts may be used in combination. The above organic silver salt may be used in an amount of 0.01 to 10 mol, preferably 0.01 to 1 mol, per 1 mol of photosensitive silver halide. 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, JP-A-59-111636 and JP-A-4-73
The mercapto compound and its metal salt described in JP-A No. 649, the acetylene compounds described in JP-A-62-87957 and JP-A-4-255845 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, holopolar 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 especially 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 (for example, US Pat. No. 3). , 615, 641, JP-A-63-23145, etc.). These sensitizing dyes may be added to the emulsion at the time of chemical ripening or before or after the chemical ripening, or according to U.S. Pat. Nos. 4,183,756 and 4,225,666 before and after the nucleation of silver halide grains. Good. The addition amount is generally about 10 ^-8 to 10 ^-2 mol per mol of silver halide.

A hydrophilic binder is preferably used for the binder of the constituent layers of the light-sensitive material 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 preferably 20 g or less per 1 m ² , particularly 10 g or less, and more preferably 7 g or less.

The constituent layers (including the back layer) of the light-sensitive material or the dye-fixing element are 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. .

As the electron donor used in the present invention, those known in the field of photothermographic materials can be used. 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 electron donors used in the present invention include US Pat. No. 4,500,626.
No. 49-50, No. 4,483,914 No. 30
~ Column 31, ibid. 4,330,617, ibid. 4,590,1
52, JP-A-60-140335 (17)-
(18), No. 57-40245, No. 56-1387.
No. 36, No. 59-178458, No. 59-53831.
No. 59-182449 and 59-182450.
Nos. 60-119555, 60-128436 to 60-128439, 60-19854.
No. 0, No. 60-181742, No. 61-259253.
Nos. 62-244044, 62-131253 to 62-131256, European Patent No. 220,
There are electron donors and electron donor precursors described on pages 78 to 96 of 746A2. US Patent 3,033
Combinations of various electron donors such as those disclosed in 9,869 can also be used.

The electron transfer agent or its precursor can be selected from the above-mentioned electron donors or its precursors. It is desirable that the electron transfer agent or its precursor has a mobility higher than that of the diffusion-resistant electron donor. Particularly useful electron transfer agents are 1-phenyl-3-pyrazolidones or aminophenols. The diffusion-resistant electron donor used in combination with the electron transfer agent may be one that does not substantially move in the layer of the light-sensitive material among the above-mentioned reducing agents, and preferably hydroquinones and sulfonamidephenols. , Sulfonamide naphthols, and compounds described as electron donors in JP-A No. 53-110827. In the present invention, the total amount of the electron donor and the electron transfer agent added is 0.01 to 20 mol, and particularly preferably 0.1 to 10 mol, based on 1 mol of silver.

In the present invention, the reducible dye-donating compound is represented by US Pat. No. 4,559,290 and European Patent No. 22.
0,746A2, U.S. Pat. No. 4,783,396,
As disclosed in Published Technical Report 87-6199, it indicates a non-diffusible compound that reacts with the reducing agent remaining without being oxidized by development to release a diffusible dye.

An example is US Pat. No. 4,139,3.
89, 4,139,379, JP-A-59-185.
333, 57-84453, etc., compounds that release a diffusible dye by a nucleophilic substitution reaction in the molecule after reduction, US Pat. No. 4,232,107,
JP-A-59-101649, JP-A-61-88257,
A compound described in RD24025 (1984), which releases a diffusible dye by an intramolecular electron transfer reaction after reduction, West German Patent No. 3,008,588A, JP-A-56-142530, US Patent No. 4,343,89
No. 3,6,6,884, etc., compounds that release a diffusible dye by cleavage of a single bond after reduction, electron acceptors described in US Pat. No. 4,450,223, etc. Examples thereof include a nitro compound which releases a diffusible dye later, a compound which releases a diffusible dye after electron acceptance described in US Pat. No. 4,609,610 and the like.

More preferably, European Patent No. 22
0,746A2, Open Technical Report 87-6199, U.S. Pat. No. 4,783,396, JP-A-63-201653.
Nos. 63-2016654 and the like, compounds having an N—X bond (X represents an oxygen, sulfur or nitrogen atom) and an electron-withdrawing group in one molecule, described in JP-A-1-26842. SO ₂ -X in one molecule (X is as defined above)
And a compound having an electron-withdrawing group, JP-A-63-2713
No. 44, a compound having a PO—X bond (where X is as defined above) and an electron-withdrawing group in one molecule, JP-A-63-
Compounds having a C—X ′ bond (X ′ has the same meaning as X or represents —SO ₂ —) and an electron-withdrawing group in one molecule described in No. 271341. In addition, JP-A 1-1
Compounds described in JP 61237 and JP 1-161342, which release a diffusible dye by cleavage of a single bond after reduction by a π bond conjugated with an electron-accepting group, can also be used.

Among these, a compound having an N—X bond and an electron-withdrawing group in one molecule is particularly preferable. Specific examples thereof are EP 220,746A2 or US Pat.
Compounds (1) to (3) described in No. 83,396,
(7) to (10), (12), (13), (15),
(23) to (26), (31), (32), (35),
(36), (40), (41), (44), (53)-
(59), (64), (70), Public Technical Report 87-619
9 are compounds (11) to (23) and the like.

In the present invention, the development inhibitor releasing redox compound can be used as described above. For example, JP-A-6
1-213,847, 62-260,153, JP-A-2-68,547, 2-110,557, 2-253,253, 1-150,135. It can be used. The synthesis method of the development inhibitor releasing redox compound used in the present invention is described in, for example, JP-A-61-213,847 and JP-A-62-260,153.
No. 4,684,604, JP-A 1-26.
9936, U.S. Patents 3,379,529, 3,
620,746, 4,377,634, 4,3
32,878, JP-A-49-129,536, 5
6-153,336 and 56-153,342.

The development inhibitor-releasing redox compound of the present invention is 1 × 10 ^{-6 to} 5 × 10 ^-2 per mol of silver halide.
It is used in an amount of 1 mole, more preferably 1 × 10 ⁻⁵ to 1 × 10 ⁻² mole. The development inhibitor releasing redox compound used in the present invention is a suitable water-miscible organic solvent, for example, alcohols (methanol, ethanol, propanol, fluorinated alcohol), ketones (acetone, methyl ethyl ketone), dimethylformamide, dimethyl sulfoxide. , Dissolved in methyl cellosolve, etc. Further, by well-known emulsification dispersion method, dibutyl phthalate, triresyl phosphate, oil such as glyceryl triacetate or diethyl phthalate, dissolved using an auxiliary solvent such as ethyl acetate or cyclohexanone, mechanically emulsified dispersion Can also be created and used. Alternatively, the development inhibitor-releasing redox compound powder may be dispersed in water by a ball mill, a colloid mill, or ultrasonic waves according to a method known as a solid dispersion method.

The heat-developable color light-sensitive material of the present invention preferably contains at least one of dextran, pullulan and derivatives thereof. Dextran and pullulan are types of polysaccharides and are polymers of D-glucose. The dextran used in the present invention preferably has a molecular weight of 20,000 to 2,000,000, and particularly preferably 100,000 to 800,000. The pullulan is preferably 20,000 to 2,000,000. Examples of dextran and pullulan derivatives include those in which a sulfinic acid group, an amino group or the like is introduced into dextran or pullulan so that they can easily react with a hardener. Dextran, pullulan and their derivatives can be used alone,
You may use 2 or more types together. The layer containing dextran, pullulan and derivatives thereof may be any layer of the photothermographic material, but it is preferably contained in the intermediate layer or the protective layer. The amount of dextran, pullulan and / or derivatives thereof used is in the range of 0.01 to 10 g / m ² , preferably 0.05 to 5 g / m ² . The reason for using such a range is that if the amount is less than 0.01 g / m ² , the present invention is not effective, and if the amount exceeds 10 g / m ² , the film quality deteriorates.

Hydrophobic additives such as dye donating compounds, diffusion resistant reducing agents and electron donors are described in US Pat. No. 2,322,0.
It can be incorporated into the layer of the light-sensitive material by a known method such as the method described in No. 27. In this case, JP-A-59
-83154, 59-178451, 59-1
78452, 59-178453, 59-17.
No. 8454, No. 59-178455, No. 59-178.
A high boiling point organic solvent as described in No. 457 and the like can be used in combination with a low boiling point organic solvent having a boiling point of 50 ° C. to 160 ° C., if necessary. The amount of 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. Also, 1 g per 1 g of binder
cc or less, more preferably 0.5 cc or less, particularly 0.3 cc or less is suitable. JP-B-51-39853, JP-A-51-59
A dispersion method using a polymer described in No. 943 can also be used. In the case of a compound which is substantially insoluble in water, fine particles can be dispersed and contained in a binder in addition to the above method. When dispersing the hydrophobic compound in the hydrophilic colloid, various surfactants can be used. For example, 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. 4,50.
0,626, columns 51-52.

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 light-sensitive material, or may be applied on the same support as the light-sensitive material. Regarding the relationship between the light-sensitive material 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. 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.
00,626, columns 58 to 59 and JP-A-61-8825.
No. 6, pages (32) to (41), mordants described in JP-A-6-61
Examples thereof include those described in Nos. 2-244043 and 62-244036. Also, US Pat.
A dye-accepting high molecular compound as described in No. 63,079 may be used. If necessary, the dye fixing element can be provided with auxiliary layers such as a protective layer, a peeling layer and an anti-curl layer. In particular, it is useful to provide a protective layer.

In the constituent layers of the light-sensitive material and the dye-fixing element, a high boiling point organic solvent can be used as a plasticizer, a slipping agent, or an agent for improving the releasability of the light-sensitive material 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 dimethyl silicone oils to modified silicone oils obtained by introducing various organic groups into dimethyl siloxane) can be used for the above purpose. Examples thereof include various modified silicone oils described in "Modified Silicone Oil" technical material P6-18B issued by Shin-Etsu Silicone Co., Ltd., particularly carboxy-modified silicone (trade name X
-22-3710) is effective. In addition, JP-A-62
Silicone oils described in JP-A-215953 and JP-A-63-46449 are also effective.

An anti-fading agent may be used in the light-sensitive material and 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, coumarane compounds, phenol compounds (for example, hindered phenols), hydroquinone derivatives, hindered amine derivatives, and spiroindane compounds. The compounds described in JP-A-61-159644 are also effective. Examples of ultraviolet absorbers include benzotriazole compounds (US Pat. No. 3,533,794), 4-thiazolidone compounds (US Pat. No. 3,352,681),
Benzophenone compounds (JP-A-46-2784 and the like), JP-A-54-48535 and JP-A-62-13
There are compounds described in Nos. 6641 and 61-88256. Further, the ultraviolet absorbing polymer described in JP-A-62-260152 is also effective. Examples of the metal complex include U.S. Pat. Nos. 4,241,155, 4,245,018, columns 3 to 36, and 4,254,195, columns 3 to 8,
There are compounds described in JP-A-62-174741, JP-A-61-88256, pages (27) to (29), JP-A-63-199248, JP-A-1-75568 and JP-A-1-74272.

Examples of useful anti-fading agents are disclosed in JP-A-62-21.
5272 (125)-(137). The anti-fading agent for preventing the 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 material. . The above-mentioned antioxidant, ultraviolet absorber, and metal complex may be used in combination. A fluorescent whitening agent may be used in the light-sensitive material and the dye fixing element. In particular, whether to incorporate a fluorescent whitening agent in the dye fixing element,
It is preferably supplied from the outside such as a photosensitive material. As an example, K. Veenkataraman edition `` The Chemistry of
Synthetic Dyes ", Volume V, Chapter 8, JP-A-61-143
Examples thereof include the compounds described in No. 752. More specifically, stilbene compounds, coumarin compounds, biphenyl compounds, benzoxazolyl compounds, naphthalimide compounds, pyrazoline compounds, carbostyryl compounds and the like can be mentioned. The fluorescent whitening agent can be used in combination with an anti-fading agent.

As the hardener used in the constituent layers of the light-sensitive material and the dye fixing element, US Pat. No. 4,678,739, No. 4,
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). Particularly preferably, JP-A-3
The vinyl sulfone type hardener described in -114,043 is used.

In the constituent layers of the light-sensitive material and the dye-fixing element, various 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 material and the dye-fixing element may contain an organic fluoro compound for the purpose of improving slipperiness, preventing electrification, improving peelability and the like. As typical examples of organic fluoro compounds, JP-B-57-9053, columns 8 to 17, JP-A-61-20
No. 944, No. 62-135826, or the like, or a fluorochemical surfactant such as a fluorochemical compound such as a fluorocarbon oil or a solid fluorochemical resin such as a tetrafluoroethylene resin. Can be mentioned.

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

In the present invention, an image formation accelerator can be used in the light-sensitive material 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. Details thereof are described in US Pat. No. 4,678,739, columns 38 to 40. Examples of the base precursor include salts of organic acids and bases that are decarboxylated by heat, compounds that release amines by intramolecular nucleophilic substitution reaction, Rossen rearrangement or Beckmann rearrangement. A specific example is U.S. Pat. No. 4,511,493.
And JP-A-62-65038.

In a system in which heat development and dye transfer are carried out simultaneously in the presence of a small amount of water, it is preferable to add a base and / or a base precursor to the dye fixing element in order to enhance the storage stability of the light-sensitive material. In the present invention, European Patent Publication No. 210,660 and US Pat. No. 4,740,4
A combination of a sparingly soluble metal compound described in No. 45 and a compound capable of undergoing a complex forming reaction with a metal ion constituting the sparingly soluble metal compound (referred to as a complex forming compound) is used. Specifically, JP-A-2-269,338 (2) to
It is described on page (6). Particularly preferred compounds as the sparingly soluble metal compound are zinc hydroxide, zinc oxide and a mixture of both.

In the present invention, various development terminators can be used in the light-sensitive material and / or the dye-fixing element for the purpose of always obtaining a constant image with respect to fluctuations 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 to inhibit 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).

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

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

As a light source for recording an image on a photosensitive material,
As described above, the light sources described in US Pat. No. 4,500,626, column 56, such as natural light, tungsten lamps, light emitting diodes, laser light sources, and CRT light sources can be used. Image exposure can also be performed using a wavelength conversion element in which a non-linear optical material and a coherent light source such as laser light are combined. Here, the nonlinear optical material is
It is a material that can develop the nonlinearity between the electric field and the polarization that appears when a strong optical electric field such as laser light is applied.
Lithium niobate, potassium dihydrogen phosphate (KDP),
Inorganic compounds represented by lithium iodate, BaB ₂ O _4, etc., urea derivatives, nitroaniline derivatives such as 3
-Methyl-4-nitropyridine-N-oxide (PO
Nitropyridine-N-oxide derivatives such as M) and the compounds described in JP-A Nos. 61-53462 and 62-210432 are preferably used. As the form of the wavelength conversion element, a single crystal optical waveguide type, a fiber type and the like are known, and any of them is useful. The above-mentioned image information is an image signal obtained from a video camera, an electronic still camera or the like, a television signal represented by Nippon Television Signal Standard (NTSC), an image obtained by dividing an original image into many pixels such as a scanner. An image signal created by using a computer represented by Signal, CG and CAD can be used.

The light-sensitive material and / or the dye fixing element may have a form having a conductive heating element layer as a heating means for heat development or diffusion transfer of dye. The transparent or opaque heating element in this case is disclosed in JP-A-61-1.
Those described in No. 45544 and the like can be used. Note that these conductive layers also function as antistatic layers. The heating temperature in the heat development step is about 50 ° C. to about 250 ° C., and development is possible, but about 80 ° C. to about 180 ° C. is particularly useful. The dye diffusion transfer process may be performed simultaneously with the heat development, or may be performed after the heat development process is completed. In the latter case, the heating temperature in the transfer step can be transferred in the range from the temperature in the heat development step to room temperature, but it is more preferably 50 ° C. or higher and about 10 ° C. lower than the temperature in the heat development step.

Although the migration of the dye occurs only by heat,
Solvents may be used to facilitate dye transfer. Also,
As described in detail in JP-A-59-218443 and JP-A-61-238056, a method of performing development and transfer simultaneously or continuously by heating in the presence of a small amount of solvent (particularly water) is also useful. is there. In this method, the heating temperature is preferably 50 ° C. or higher and not higher than the boiling point of the solvent. For example, when the solvent is water, the temperature is preferably 50 ° C or higher and 100 ° C or lower. Examples of the solvent used for accelerating the development and / or transferring the diffusible dye to the dye-fixing layer include water or a basic aqueous solution containing an inorganic alkali metal salt or an organic base (for these bases, an image). The one described in the section of the formation accelerator is used)
Can be mentioned. Further, a low boiling point solvent, or a mixed solution of a low boiling point solvent and water or a basic aqueous solution can be used. Further, a surfactant, an antifoggant, a sparingly soluble metal salt and a complex-forming compound may be contained in the solvent.

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

Further, in order to promote dye transfer, a system in which a hydrophilic thermal solvent that is solid at room temperature and dissolves at high temperature is incorporated in the light-sensitive material or the dye fixing element can be adopted. The hydrophilic thermal solvent may be incorporated in either the light-sensitive material or the dye fixing element, or may be incorporated in both. The layer to be incorporated may be any of an emulsion layer, an intermediate layer, a protective layer and a dye fixing layer, but it is preferably incorporated in the dye fixing layer and / or its adjacent layer. Examples of hydrophilic thermal solvents include ureas, pyridines, amides, sulfonamides, imides, alcohols, oximes and other heterocycles. Further, a high-boiling organic solvent may be contained in the light-sensitive material and / or the dye fixing element in order to promote dye transfer.

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. JP-A-61-1 is a method for applying a pressure condition or pressure when the light-sensitive element and the dye fixing element are superposed and closely contacted with each other.
The method described on page 27 of No. 47244 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.
44, JP-A-3-131856, and JP-A-3-13185.
The device described in No. 1 etc. is preferably used.

[0060]

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 zinc hydroxide dispersion will be described.

12.5 g of zinc hydroxide having an average particle size of 0.2 μm, 1 g of carboxymethyl cellulose as a dispersant, and 0.1 g of sodium polyacrylate were added to 100 ml of a 4% gelatin aqueous solution, and the average particle size was 0.75 mm with a mill. It was ground for 30 minutes using glass beads. 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 the following electron transfer agent, 0.5 g of polyethylene glycol nonyl phenyl ether as a dispersant
g, 0.5 g of the following anionic surfactant was added to a 5% gelatin aqueous solution, and the mixture was pulverized with a mill for 60 minutes using glass beads having an average particle size of 0.75 mm. The glass beads were separated to obtain a dispersion of the electron transfer agent having an average particle size of 0.35 μm.

[0065]

[Chemical 5]

[0066]

[Chemical 6]

Next, a method for preparing a dispersion of the dye trapping agent will be described.

The following polymer latex (solid content 13
%) 108 ml, the following surfactant 20 g, water 1232 ml
600 ml of a 5% aqueous solution of an anionic surfactant described below was added over 10 minutes while stirring the mixed solution. Using the ultrafiltration module, the dispersion thus prepared,
It was concentrated to 500 ml and desalted. Next, 1500 ml of water was added and the same operation was repeated once again to obtain 500 g of the dye trapping agent dispersion.

[0069]

[Chemical 7]

[0070]

[Chemical 8]

[0071]

[Chemical 9]

Next, a method for preparing a gelatin dispersion of a hydrophobic additive will be described.

Cyan, magenta, and yellow dye-donor compounds and electron-donor gelatin dispersions were prepared according to the formulations shown in Table 1. That is, each oil phase component was dissolved by heating at about 60 ° C. to form a uniform solution, this solution and the aqueous phase component heated at about 60 ° C. were added, and the mixture was stirred and mixed, and then dispersed with a homogenizer for 13 minutes at 12000 rpm. Add to this,
Stir to obtain a uniform dispersion.

[0074]

[Table 1]

[0075]

[Chemical 10]

[0076]

[Chemical 11]

[0077]

[Chemical 12]

[0078]

[Chemical 13]

[0079]

[Chemical 14]

[0080]

[Chemical 15]

[0081]

[Chemical 16]

[0082]

[Chemical 17]

[0083]

[Chemical 18]

[0084]

[Chemical 19]

[0085]

[Chemical 20]

[0086]

[Chemical 21]

[0087]

[Chemical formula 22]

[0088]

[Chemical formula 23]

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 500 ml of water).
g and 30 mg of the following chemical (A) were added and kept at 45 ° C.), 20 parts of solution (I) and solution (II) in Table 2 were simultaneously added.
Added at equal flow rate for 1 minute. After 6 minutes, solution (III) and solution (IV) in Table 2 were simultaneously added at the same flow rate for 25 minutes. Also (II
10 minutes after the start of the addition of the solutions (I) and (IV), an aqueous solution of a gelatin dispersion of a pigment (1 g of gelatin in 105 ml of water, 70 mg of the following pigment (a), 139 mg of the following pigment (b), and the following pigment (c) ) Containing 5 mg and kept 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 7.8, and 4-hydroxy-6-methyl-1,3,3.
3a, 7-tetrazaindene was added, and then sodium thiosulfate and chloroauric acid were added for optimum chemical sensitization at 68 ° C.
Next, the following antifoggant (2) was added and then cooled. Thus, 635 g of a monodisperse cubic silver chlorobromide emulsion having an average grain size of 0.30 μm was obtained.

[0092]

[Chemical formula 24]

[0093]

[Table 2]

[0094]

[Chemical 25]

[0095]

[Chemical formula 26]

[0096]

[Chemical 27]

Photosensitive Silver Halide Emulsion (2) [For red-sensitive emulsion layer] Well-stirred aqueous gelatin solution (20 ml of gelatin, 0.5 g of potassium bromide, 6 g of sodium chloride in 800 ml of water).
g and 30 mg of the following chemical (A) were added and kept at 65 ° C.), 30 parts of the liquids (I) and (II) in Table 3 were simultaneously added.
Added at equal flow rate for 1 minute. After 5 minutes, solution (III) and solution (IV) in Table 3 were simultaneously added at an equal flow rate for 15 minutes. Also (II
2 minutes after the start of the addition of the solutions (I) and (IV), an aqueous solution of a gelatin dispersion of a dye (1.1 g of gelatin in 95 ml of water, 76 mg of the above dye (a), 150 mg of the above dye (b), and the above dye) (C) 5 mg and kept at 50 ° C.) was 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 pH to 6.2 and pAg to 7.8, and 4-hydroxy-6-methyl-1,3,3.
3a, 7-tetrazaindene was added, and then sodium thiosulfate and chloroauric acid were added for optimum chemical sensitization at 68 ° C.
Next, the following antifoggant (1) was added and then cooled. Thus, 635 g of a monodisperse cubic silver chlorobromide emulsion having an average grain size of 0.50 μm was obtained.

[0099]

[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)
solution (I) and solution (II) in Table 4 were simultaneously added at a constant 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. Also (II
I), 1 minute after the end of the addition of the (IV) solution, an aqueous solution of a gelatin dispersion of a dye (2.5 g of gelatin in 100 ml of water and 250 mg of the following dye (d) and kept at 45 ° C.) was put together. Was added.

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 7.6, and 4-hydroxy-6-methyl-1,3,3.
3a, 7-Tetrazaindene was added, and then sodium thiosulfate was added for optimum chemical sensitization at 68 ° C., and then the following antifoggant (1) was added and then cooled. Thus, 635 g of a monodisperse cubic silver chlorobromide emulsion having an average grain size of 0.27 μm was obtained.

[0102]

[Table 4]

[0103]

[Chemical 28]

Photosensitive Silver Halide Emulsion (4) [For Green Sensitive Emulsion Layer] Well-stirred aqueous gelatin solution (20 ml of gelatin, 0.3 g of potassium bromide and 6 g of sodium chloride in 700 ml of water).
g and the above-mentioned chemical (A) (15 mg) and the mixture was kept at 60 ° C.), and the liquids (I) and (II) in Table 5 were simultaneously added to 20 times.
Added at equal flow rate for 1 minute. After 10 minutes, solution (III) and solution (IV) shown in Table 5 were added simultaneously at the same flow rate for 20 minutes. Also (I
II), 1 minute after the addition of the solution (IV), an aqueous solution of a gelatin dispersion of the dye (1.8 g of gelatin in 75 ml of water and 180 mg of the dye (d) and kept at 45 ° C.) was added together. Was added.

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 7.6, and 4-hydroxy-6-methyl-1,3,3.
3a, 7-Tetrazaindene was added, and then sodium thiosulfate was added for optimum chemical sensitization at 68 ° C., and then the following antifoggant (1) was added and then cooled. Thus, 635 g of a monodisperse cubic silver chlorobromide emulsion having an average grain size of 0.45 μm was obtained.

[0106]

[Table 5]

Photosensitive silver halide emulsion (5) [for blue-sensitive emulsion layer] Well-stirred aqueous gelatin solution (20 g of gelatin in 690 ml of water, 0.5 g of potassium bromide, 5 parts of sodium chloride)
g and the above-mentioned chemical (A) (15 mg) and the mixture was kept at 51 ° C.), the solutions (I) and (II) in Table 6 were simultaneously added at an equal flow rate for 8 minutes. After 10 minutes, solution (III) and solution (IV) in Table 6 were simultaneously added at the same flow rate for 32 minutes. Also (II
One minute after the addition of the solutions (I) and (IV) was completed, an aqueous solution of the dye (water 9
235 mg of the following dye (e) in 5 ml and 5 ml of methanol
And 120 mg of the following dye (f) and kept at 45 ° C.) were 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 7.7, and 4-hydroxy-6-methyl-1,3,3.
3a, 7-Tetrazaindene was added, and then sodium thiosulfate was added for optimum chemical sensitization at 68 ° C., and then the following antifoggant (1) was added and then cooled. Thus, 635 g of a monodisperse cubic silver chlorobromide emulsion having an average grain size of 0.30 μm was obtained.

[0109]

[Table 6]

[0110]

[Chemical 29]

[0111]

[Chemical 30]

Photosensitive Silver Halide Emulsion (6) [For Blue Sensitive Emulsion Layer] Well-stirred aqueous gelatin solution (20 g of gelatin, 0.3 g of potassium bromide, 9 g of sodium chloride in 695 ml of water).
g and the above-mentioned chemical (A) (15 mg) and kept at 63 ° C.), the liquids (I) and (II) shown in Table 7 were simultaneously added to 10 parts.
Added at equal flow rate for 1 minute. After 10 minutes, solution (III) and solution (IV) in Table 7 were added simultaneously at the same flow rate for 30 minutes. Also (I
II), 1 minute after the addition of the solution (IV), an aqueous solution of the dye (water 6
155 mg of the above dye (e) in 6 ml and 4 ml of methanol
And 78 mg of the above-mentioned dye (f) and kept at 60 ° C.) were 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 7.7, and 4-hydroxy-6-methyl-1,3,3.
3a, 7-Tetrazaindene was added, and then sodium thiosulfate was added for optimum chemical sensitization at 68 ° C., and then the following antifoggant (1) was added and then cooled. Thus, 635 g of a monodisperse cubic silver chlorobromide emulsion having an average grain size of 0.52 μm was obtained.

[0114]

[Table 7]

Photosensitive material 101 shown in Table 8 was prepared using the above.

[0116]

[Table 8]

[0117]

[Table 9]

[0118]

[Table 10]

[0119]

[Chemical 31]

[0120]

[Chemical 32]

[0121]

[Chemical 33]

[0122]

[Chemical 34]

[0123]

[Chemical 35]

[0124]

[Chemical 36]

[0125]

[Chemical 37]

From photosensitive material 101 to second layer, fourth layer, fifth layer
Photosensitive material 101 except that the configurations of the layers and the sixth layer are changed
In the same manner as described above, the photosensitive materials 102 to 121 shown in Table 9
Made.

[0127]

[Table 11]

[0128]

[Table 12]

Next, how to make the image receiving material will be described.

[0130]

[Table 13]

Image-receiving material R10 having a constitution as shown in Table 10
Made one.

[0132]

[Table 14]

[0133]

[Table 15]

[0134]

[Chemical 38]

[0135]

[Chemical Formula 39]

[0136]

[Chemical 40]

Using the above-mentioned photographic materials 101 to 121 and image receiving material R101, processing was carried out using an image recording apparatus described in Japanese Patent Application No. 63-137104. That is, the original image [a test chart on which wedges of Y, M, Cy, and gray with continuously changing density are recorded] is scanned and exposed through a slit, and the exposed light-sensitive material is exposed to water kept at 40 ° C. Four
After soaking for a second, it was 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 to 80 ° C on the water-absorbed film surface, the photosensitive material is peeled off from the image receiving material by heating for 17 seconds, and a clear color image corresponding to the original image is obtained on the image receiving material. Was given.

In addition, the photosensitive materials 101 to 121 are
After leaving at -50% for 5 days, the same exposure and treatment were performed.
Furthermore, using a Fuji CC filter manufactured by Fuji Film Co., Ltd., the gray density of 0.7 was adjusted to match, and the same exposure and treatment were carried out, and the density of each of Y, M, and Cy single colors was 1.
The color turbidity component in 2 was measured and the color reproducibility was evaluated. For the density measurement, the reflection density was measured using a density measuring device X Light 404 manufactured by X Light Co. The results are shown in Tables 11 and 12.

[0139]

[Table 16]

[0140]

[Table 17]

[0141]

[Table 18]

─────────────────────────────────────────────────── ───

[Procedure amendment]

[Submission date] May 17, 1993

[Procedure Amendment 1]

[Document name to be amended] Statement

[Correction target item name] 0069

[Correction method] Change

[Correction content]

[0069]

[Chemical 7]

Claims (3)

[Claims] 1. A support, at least a light-sensitive silver halide, a binder, an electron transfer agent, and / or a precursor thereof, an electron donor and / or a precursor thereof, and a substrate which is reduced to release a diffusible dye. In a multi-layer heat-developable color light-sensitive material having a reducing dye-donating compound, a non-photosensitive layer and / or a protective layer between two light-sensitive layers having different color sensitivities contain a hardly-soluble metal compound, A photothermographic material, wherein the ratio of the metal compound to the binder in the layer is 0.4 to 2.0, and the non-photosensitive protective layer farthest from the support has a fluorine-based surfactant. 2. The binder amount of a non-photosensitive layer between two photosensitive layers having different color sensitivities according to claim 1, wherein the binder amount is 0.40 g /
A photothermographic material, characterized in that it is from m ^{2 to} 1.60 g / m ² . 3. The photothermographic material according to claim 1, wherein the sparingly soluble metal compound is zinc hydroxide, zinc oxide, or a mixture of zinc hydroxide and zinc oxide.