JPH07219183A - Heat developable color photosensitive material - Google Patents

Abstract

PURPOSE:To lessen the minimum density and to enhance short time processing aptitude by using a silver halide emulsion layer having a specified silver chloride content in combination with an electron transfer material, an electron donor, and a specified reducible dye donor shown in a specified formula. CONSTITUTION:The silver halide emulsion layer containing the silver chloride in an amount of >=40mol% is used on a support in combination with the electron transfer material or its precursor, the electron donor or its precursor, and the reducible dye donor represented by the formula in which Eag is a group for accepting an electron from a reducible substance; D<2> is -CO- or -SO2-; D<1> is a group for forming a hetero ring containing N, O, and D<2> and cleaving the D<1>-G bond following the cleavage of the N-O bond; Dye is a diffusive dye group; X is a benzene or naphthalene ring or the like; L is a bonding group; m is an integer of >=1; and n is an integer of >=2.

Description

Detailed Description of the Invention

[0001]

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 a low minimum density and excellent suitability for short-time processing.

[0002]

2. Description of the Related Art Photothermographic materials are well known in this technical field, and the photothermographic material and its process are described, for example, in "Basics of Photographic Engineering", Non-silver photography (edited by Corona Publishing Co. in 1982), page 242. Pp. 255, U.S. Pat. No. 4,500,626. Many methods have also been proposed for obtaining a color image by heat development. For example, US Patent No.
No. 3,531,286, No. 3,761,270, No. 4,021,240, Belgian Patent No. 802,519, Research Disclosure (hereinafter abbreviated as RD), September 1975, pages 31 to 32, etc. A method of forming a color image has been proposed.

Many methods have been proposed for obtaining a positive color image by heat development. Among them, U.S. Pat. No. 4,559,290 discloses a so-called DRR compound in which an oxidized dye-donating compound having no color image releasing ability and an electron donor or a precursor thereof are present, and the exposure amount of silver halide is increased by heat development. Accordingly, there has been proposed a method of oxidizing the electron donor and reducing the remaining electron donor without being oxidized to release the diffusible dye. Also, European Patent Publication 220,
No. 746, JP-A-64-13546 discloses a reductive cleavage of an N--X bond (X represents an oxygen atom, a nitrogen atom or a sulfur atom) as a compound which releases a diffusible dye by a similar mechanism. Describes a photothermographic color photographic material using a dye-donor compound which releases a diffusible dye. The dye-donor compounds used in these systems are compounds that release a diffusible dye when reduced,
It is called a reducible dye-donating compound. Further, in these systems, an electron transfer agent or its precursor is allowed to coexist, the electron transfer agent is oxidized according to the exposure amount of silver halide, and the electron donor is cross-oxidized by the oxidized product of the electron transfer agent. , A means for improving the distinctiveness of images has been adopted.

[0004]

In recent years, various attempts have been made to reduce the time required to obtain an image. In the light-sensitive material as described above, when the time required to obtain an image is shortened, the diffusible dye-releasing reaction mainly by the reaction between the reducible dye-donating compound and the electron donor is promoted and / or the same. It is sufficient to accelerate the transfer of the dye. By the way, in the above-mentioned heat-developable color light-sensitive material, dye release due to the reaction between the reducible dye-donating compound and the electron donor and electron emission due to the oxidant of the electron transfer agent (generated by the development of silver halide). The competitive reaction with the oxidation of the donor determines the minimum density of the positive image. Therefore, when a plurality of diffusible dyes are released by one-electron reduction, there arises a problem that the minimum density of the image is increased.
In order to solve this problem, the grain size of the photosensitive silver halide may be reduced, but in this case, the minimum density is decreased, but this causes a problem of sensitivity deterioration. Therefore, an object of the present invention is to provide a heat-developable color light-sensitive material having a low minimum density and excellent suitability for short-time processing.

[0005]

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 is
A photosensitive silver halide emulsion layer comprising silver halide having a silver chloride content of 40 mol% or more is provided on a support, an electron transfer agent or a precursor thereof, an electron donor or a precursor thereof and the following general formula (I). A heat-developable color light-sensitive material having a reducing dye-providing compound represented by

[0006]

[Chemical 2]

In the formula, EAG represents a group that receives an electron from a reducing substance. N and O represent a nitrogen atom and an oxygen atom, respectively, and this single bond is cleaved after EAG receives an electron. D ² represents -CO- or -SO ₂ , and D
¹ represents a group which forms a heterocycle containing N, O and D ² and which has a property that the D ¹ -G bond is cleaved following the cleavage of the N—O bond, and the timing at which G is further decomposed by itself. You may have the ability. Dye represents a diffusible dye group, X
Represents a benzene ring, a naphthalene ring, a 5- to 8-membered heterocyclic ring containing 1 or 2 nitrogen atoms, or a chain or cyclic alkyl group having 2 to 10 carbon atoms, which has a substituent. Other saturated or unsaturated ring may be condensed, and a part of the constituent carbon atoms may be replaced with an oxygen atom or a sulfur atom. L represents a linking group. m
Is 1 or more, n is a natural number of 2 or more, and n L- (D
ye) _m may be the same, and when m is 2 or more, m
The individual Dyes may be the same or different.

The present invention will be described in detail below. The silver halide emulsion of the present invention comprises silver halide having a silver chloride content of 40 mol% or more, and specifically, silver iodobromochloride, silver iodochloride and salts having the above silver chloride content. Either silver bromide or silver chloride may be used,
Silver chlorobromide having a silver chloride content of 40 to 80 mol% is particularly preferable. The silver halide emulsion may have various shapes. Examples of them include cubic grains, octahedral grains, regular grains having regular crystal forms such as tetradecahedrons, tabular grains, spherical grains, and grains having irregular crystal forms such as potato grains. Can be mentioned. The halogen composition in the grains may be uniform, may have different halogen compositions inside and outside, or may have a layered structure. (JP-A-57-145232
No. 58-108533, No. 58-248469, No. 59-48755,
59-52237, U.S. Pat.Nos. 3,505,068 and 4,433,048.
No. 4,444,877, European Patent No. 100,984, and British Patent No. 1,027,146) The silver halide emulsion may be monodisperse or polydisperse, and a mixture of monodisperse emulsions may be used. Particle size is 0.01 μm to 10 μm, especially 0.1 μm to 3
μm is preferred. Here, the monodisperse silver halide emulsion is
95% or more of the total weight or the total number of silver halide grains contained therein is preferably within ± 40% of the average grain size, and more preferably ± 30.
Defined to be within%.

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

The silver halide emulsion used in the present invention is preferably one in which various chemical sensitizations have been applied to the grain surface of the silver halide emulsion. The above-mentioned chemical sensitization is by James, The Theory of Photographic Process, 4th Edition, published by Macmillan, 1977, (THJames, The
Theory of the Photographic Process, 4th ed, Macmill
an, 1977) 67-76 and using active gelatin, and Research Disclosure 120, April 1974, 12008; Research Disclosure 34, June 1975, 13452, U.S. Patent No. 2,6
42,361, 3,297,446, 3,772,031, and
3,857,711, 3,901,714, 4,266,018 and 3,904,415, and pAg 5-10, pH 5-8 and temperature 30-as described in British Patent 1,315,755.
It can be carried out at 80 ° C. with sulfur, selenium, tellurium, gold, platinum, palladium, iridium, rhodium or combinations of these sensitizers.

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.

In the present invention, two or more kinds of silver halide emulsions having different crystal habits, halogen compositions, grain sizes, grain size distributions and the like can be used in combination, and different emulsion layers and / or the same emulsion layer can be used. Can be used for

The photothermographic material used in the present invention basically contains the above-mentioned components, but may further contain an organic metal salt oxidizing agent and other additives, if necessary. In the present invention, the electron transfer agent or its precursor, the electron donor or its precursor and the reducible dye-providing compound of the general formula (I) are contained in a silver chloride content of 40 mol%.
Having the above in combination with the emulsion layer made of silver halide means that these components are added to the emulsion layer or used.
Alternatively, it means that it is used by being added to another layer (usually a non-photosensitive layer adjacent to the emulsion layer) if it is in a reactive state. 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. However, the most preferable form is to add these components to the emulsion layer.

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 light sensitivity 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. In the present invention, it is necessary that at least one of these multiple emulsion layers is an emulsion layer satisfying the requirements of the present invention, but the other emulsion layers are
It may be composed of a silver halide emulsion other than the silver halide emulsion having the silver chloride content of the present invention, or may be combined with a reducible dye-donating compound other than the general formula (I) of the present invention. May be. For the photothermographic material, a protective layer,
Various auxiliary layers such as an undercoat layer, an intermediate layer, a yellow filter layer, an antihalation layer and a back layer can be provided. 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 total of all the photosensitive layers.

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 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 reducible dye-donating compound of the general formula (I) will be described in more detail below. D ¹ is N, O,
Examples of the heterocycle formed together with D ² include a 4- to 8-membered monocycle or a heterocycle having a condensed ring, and the following rings are preferred.

[0018]

[Chemical 3]

These heterocycles may have a substituent such as an alkyl group or an aryl group. Particularly preferred among these heterocycles are the heterocycles shown in (i) and (j). In the general formula (I), EAG is an electron-accepting group, preferably a quinone residue or Hammett's σ.
_It represents an aromatic group, a heterocyclic group, an alkenyl group or an alkynyl group having a _P value of +0.09 or more. More specifically, the groups described as EAG in U.S. Pat. No. 4,783396 (JP-A-62-215270) can be mentioned.
Particularly preferred is a phenyl group in which the nitro group is substituted in the ortho or para position.

In order for the compound of the general formula (I) to remain non-diffusible in the addition layer of the heat-developable color light-sensitive material, it is desirable that a group called a ballast group be substituted. The ballast group is usually an aliphatic group having 8 or more carbon atoms or an aromatic group, and is a heterocycle or EA formed by N, O, D ¹ and D ^2.
Replaced by G. Preferred are sulfamoyl group (alkyl or arylaminosulfonyl group), carbamoyl group (alkyl or arylaminocarbonyl group), acylamino group, alkylsulfonyl group, arylsulfonyl group, alkyl group, alkylthio group and the like.

Examples of Dye of the general formula (I) include azo dyes, azomethine dyes, azopyrazolone groups, indoaniline dyes, indophenol dyes, anthraquinone dyes, triarylmethane dyes, alizanin, nitro dyes, Examples thereof include quinoline dyes, indigo dyes, and phthalocyanine dyes. In addition, those leuco bodies, those whose absorption wavelength is temporarily shifted, and dye precursors such as tetrazolium salts are also included. Further, these dyes may form chelate dyes with suitable metals. Regarding these dyes, for example, US Pat.
No. 3,880,658; No. 3,931,144; No. 3,932,380;
No. 3,932,381 and No. 3,942,987. Of these, cyan, magenta, and yellow dyes are particularly important for forming a color image density. Examples of these are given below.

Examples of yellow dyes: US Pat. No. 3,597,220
No., No. 3,309,199, No. 4,013,633, No. 4,245,028
No., No. 4,156,609, No. 4,139,383, No. 4,195,992
No. 4,148,641, No. 4,148,643, No. 4,336,322
Issue: JP-A-51-114930, JP-A-56-71072, Research Dis
Those described in closure 17,630 (1978) and 16,475 (1977). Examples of magenta dyes: U.S. Patents 3,453,107 and 3,544,545
No. 3,932,380, No. 3,931,144, No. 3,932,308
No., No. 3,954,476, No. 4,233,237, No. 4,255,509
Issue 4,250,246, Issue 4,142,891, Issue 4,207,104
Nos. 4,287,292: JP-A-52-106727, 53-23628.
No. 55, No. 55-36804, No. 56-73057, No. 56-71060, No. 55
-Those listed in No. 134. Examples of cyan dyes: U.S. Patents 3,482,972 and 3,929,760
No., No. 4,013,635, No. 4,268,625, No. 4,171,220
No. 4,242,435, 4,142,891, 4,195,994
Nos. 4,147,544 and 4,148,642: British Patent 1,551,
138: JP 54-99431, JP 52-8827, JP 53-47823
No. 53-143323, No. 54-99431, No. 56-71061: European Patent (EPC) 53,037, No. 53,040, Research D
Those described in isclosure 17,630 (1978) and 16475 (1977).

Further, as a kind of the dye precursor part, specific examples of the dye whose light absorption is temporarily shifted in the light-sensitive material element are described in US Pat. Nos. 4,310,612 and T-999,003,
Nos. 3,336,287, 3,579,334, 3,982,946, British Patent 1,467,317, and Japanese Patent Laid-Open No. 57-158638.

Specific examples of the dye-donating compound represented by the general formula (I) used in the color light-sensitive material used in the present invention are shown below, but the present invention is not limited thereto.

[0025]

[Chemical 4]

[0026]

[Chemical 5]

[0027]

[Chemical 6]

[0028]

[Chemical 7]

[0029]

[Chemical 8]

The coating amount of the general formula (I) dye-providing compound represented by the present invention is preferably ^{0.08mmol / m 2 ~0.40mmol / m 2} , 0.12mmol / m 2 ~0.30mmol / m 2 more preferable. A hydrophilic binder is preferably used as the binder of the constituent layers of the light-sensitive material and the dye fixing element. As an example, Japanese Patent Laid-Open No. Sho 6
The thing described in pages (26)-(28) of 2-253159 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. Also, JP-A-62-245
Superabsorbent polymer described in No. 260, etc., that is, -CO
OM or -SO ₃ M (M is a hydrogen atom or an alkali metal) copolymer of homopolymer or a vinyl monomer together or with other vinyl monomers of the vinyl monomer having a (e.g. sodium methacrylate, ammonium methacrylate, Sumitomo Chemical (Sumikagel L-5H manufactured by Co., Ltd.)
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 used, it is 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 layer (including the back layer) of the light-sensitive material or the dye-fixing element is used for the purpose of improving physical properties of the film such as dimensional stabilization, curl prevention, adhesion prevention, film cracking prevention and pressure increase / decrease prevention. Various polymer latices can be included. Specifically, any of the polymer latexes described in JP-A Nos. 62-245258, 62-136648, 62-110066 and the like can be used. In particular,
When a polymer latex having a low glass transition point (40 ° C. or less) is used in the mordant layer, cracking of the mordant layer can be prevented, and when a polymer latex having a high glass transition point is used in the back layer, a curl preventing effect can be obtained. .

As the 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, a development inhibitor releasing redox compound can be used. For example, JP-A-61-21
3,847, 62-260,153, JP-A-2-
68,547, 2-110,557, 2-25
Those described in Nos. 3,253 and 1-150,135 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-61-161.
213,847, 62-260,153, U.S. Pat. No. 4,684,604, JP-A-1-269936.
U.S. Pat. Nos. 3,379,529 and 3,620,
No. 746, No. 4,377, 634, No. 4,332, 8
78, JP-A-49-129,536 and JP-A-56-15.
3, 336, 56-153, 342, etc.

The development inhibitor-releasing redox compound of the present invention contains 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 a well-known emulsification dispersion method, dibutyl phthalate, tricresyl phosphate, oil such as glyceryl triacetate or diethyl phthalate, and an auxiliary solvent such as ethyl acetate or cyclohexanone are dissolved and mechanically emulsified and dispersed. It is also possible to create and use things. Alternatively, by a method known as a solid dispersion method, a powder of a development inhibitor-releasing redox compound is ball milled in water, a colloid mill,
Alternatively, they can be dispersed by ultrasonic waves and used.

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 reducible dye-donating compounds and electron donors can be incorporated into the layer of the light-sensitive material by a known method such as the method described in US Pat. No. 2,322,027. . In this case, JP-A-59-831
No. 54, No. 59-178451, No. 59-17845
No. 2, No. 59-178453, No. 59-178454.
No. 59-178455, No. 59-178457 and the like, a high-boiling point organic solvent 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 per 1 g of the dye-donor compound used.
It is the following. Also, 1 cc or less for 1 g of binder,
Furthermore, 0.5 cc or less, particularly 0.3 cc or less is suitable.
The dispersion method using a polymer described in JP-B-51-39853 and JP-A-51-59943 can also be used. In the case of a compound which is substantially insoluble in water, fine particles can be dispersed and contained in a binder in addition to the above method. When dispersing a hydrophobic compound in a 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. 4,500,62.
No. 6, 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 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. No. 4,500,626.
Nos. 58-59 and JP-A-61-88256 (3)
2) to (41), the mordants described in JP-A-62-244.
No. 043, No. 62-244036, etc. can be mentioned. Also, U.S. Pat. No. 4,463,07
A dye-accepting high molecular compound as described in No. 9 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 plasticizer, a slipping agent, or a high boiling point organic solvent can be used as 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, coumarans 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. For example, see “The Chemistry of S” edited by K. Veenkataraman.
Synthetic Dyes ", Volume V, Chapter 8, JP-A-61-1437
The compounds described in No. 52 and the like can be mentioned. More specifically, stilbene compounds, coumarin compounds, biphenyl compounds, benzoxazolyl compounds, naphthalimide compounds, pyrazoline compounds,
Examples thereof include carbostyryl compounds. The fluorescent whitening agent can be used in combination with an anti-fading agent.

As a 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 base precursor to the dye fixing element in order to enhance the storability 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 stoppers can be used in the light-sensitive material and / or the dye-fixing element 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 after proper development to lower the concentration of the base in the film to stop the 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, the support for the light-sensitive material and the dye-fixing element is one that can withstand the processing temperature. 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, and polypropylene are used. Film-processed synthetic papers, mixed papers made of synthetic resin pulp such as polyethylene and natural pulp, Yankee papers, baryta papers, coated papers (particularly cast coated papers), metals, cloths and glasses 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 with a camera or the like, a method of exposing through a reversal film or a negative film with a printer or an enlarger, A method of scanning and exposing an original image through a slit or the like using an exposure device of a copying machine, a method of exposing image information by emitting light from a light emitting diode or various lasers through an electric signal, a CRT, a liquid crystal display of image information, There is a method of outputting to an image display device such as an electroluminescence display and a plasma display, and exposing directly or through an optical system.

As a light source for recording an image on a photosensitive material,
As described above, the 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.

In order to promote dye transfer, a method in which a hydrophilic thermal solvent that is solid at room temperature and dissolves at high temperature is incorporated in the light-sensitive material or the dye fixing element can also be used. 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 thermal development 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.

[0059]

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.

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 and 0.5 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.

[0064]

[Chemical 9]

Next, the method for preparing the 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.

[0067]

[Chemical 10]

[0068]

[Chemical 11]

[0069]

[Chemical 12]

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 water phase component heated at about 60 ° C were added, and the mixture was stirred and mixed and then homogenized with a homogenizer.
Dispersed for 3 minutes at 12000 rpm. Water was added to this and stirred to obtain a uniform dispersion.

[0072]

[Table 1]

[0073]

[Chemical 13]

[0074]

[Chemical 14]

[0075]

[Chemical 15]

[0076]

[Chemical 16]

[0077]

[Chemical 17]

[0078]

[Chemical 18]

[0079]

[Chemical 19]

[0080]

[Chemical 20]

[0081]

[Chemical 21]

[0082]

[Chemical formula 22]

[0083]

[Chemical formula 23]

[0084]

[Chemical formula 24]

[0085]

[Chemical 25]

[0086]

[Chemical formula 26]

Next, a method for preparing a gelatin dispersion of the hydrophobic additive of the present invention will be described. The above-mentioned dye-donor compound
Dye donating compounds (4) and (5) were prepared in the same manner except that the compounds I-1 and I-3 of the present invention were used instead of (3).

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 and 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.

[0091]

[Table 2]

[0092]

[Chemical 27]

[0093]

[Chemical 28]

[0094]

[Chemical 29]

[0095]

[Chemical 30]

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 800 ml of water).
g and 30 mg of the following chemical (A) were added and kept at 65 ° C.), the solutions (I) and (II) in Table 3 were added over 30 minutes. After 5 minutes, solution (III) and solution (IV) in Table 3 were further added over 15 minutes. Two minutes after the addition of the solutions (III) and (IV) is started, an aqueous solution of the gelatin dispersion of the dye (water 9
1.1 g gelatin in 5 ml, 76 mg dye (a) above,
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 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.

[0098]

[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.

[0101]

[Table 4]

[0102]

[Chemical 31]

Photosensitive Silver Halide Emulsion (4) [For Green Sensitive Emulsion Layer] Well stirred aqueous gelatin solution (20 g of gelatin, 0.3 g of potassium bromide, 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 end of the addition of the (IV) solution, 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 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 0.45 μm was obtained.

[0105]

[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 kept at 51 ° C.), the solutions (I) and (II) shown 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.

[0108]

[Table 6]

[0109]

[Chemical 32]

[0110]

[Chemical 33]

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.

[0113]

[Table 7]

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

[0115]

[Table 8]

[0116]

[Table 9]

[0117]

[Table 10]

[0118]

[Chemical 34]

[0119]

[Chemical 35]

[0120]

[Chemical 36]

[0121]

[Chemical 37]

[0122]

[Chemical 38]

[0123]

[Chemical Formula 39]

[0124]

[Chemical 40]

Next, the method for preparing the emulsion of the present invention will be described. In the above method for preparing photosensitive silver halide, Table 11 was used instead of the liquids (I) and (III) described in Tables 5 and 6.
Photosensitive silver halides (7) to (14) were prepared in the same manner except that the solutions (I) and (III) shown in Table 12 were used.

[0126]

[Table 11]

[0127]

[Table 12]

A light-sensitive material 1 was prepared by using the above emulsion of the present invention.
No. 01 photosensitive layer 102 and the dye-donor compound were changed as shown in Table 13, respectively.
I made 109.

[0129]

[Table 13]

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

Image-receiving material R10 having a constitution as shown in Table 14
Made one.

[0132]

[Table 14]

[0133]

[Table 15]

[0134]

[Chemical 41]

[0135]

[Chemical 42]

[0136]

[Chemical 43]

Using the above-mentioned photosensitive materials 101 to 109 and image receiving material R101, processing was carried out using the image recording apparatus described in FIG. 2 of JP-A-2-84634. 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. After dipping for 2.5 seconds, 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. Next, using a heat drum whose temperature was adjusted so that the water-absorbed film surface temperature was 80 ° C., each photosensitive material was heated for 12 seconds, 17 seconds, and 22 seconds, and the photosensitive material was peeled from the image receiving material. A clear color image corresponding to the original image was obtained.

With respect to these color images, the density of the gray wedge portion was measured using a density measuring instrument X light 404 manufactured by X light company. Table 16 shows the results of the maximum density (Dmax) and the minimum density (Dmin) of yellow, magenta, and cyan for the light-sensitive materials 101 to 109.

[0139]

[Table 16]

[0140]

According to the present invention, a heat-developable color light-sensitive material having a low minimum density and excellent suitability for short-time processing can be obtained.

Claims (1)

[Claims] 1. A photosensitive silver halide emulsion layer comprising silver halide having a silver chloride content of 40 mol% or more on a support, an electron transfer agent or a precursor thereof, an electron donor or a precursor thereof and the following: A heat-developable color light-sensitive material having a reducing dye-providing compound represented by formula (I) in combination. General formula (I) In the formula, EAG represents a group that receives an electron from a reducing substance. N and O respectively represent a nitrogen atom and an oxygen atom,
This single bond is cleaved after the EAG receives the electron. D ² represents -CO- or -SO _2, D ¹ is N,
Represents a group having the property of forming a heterocycle containing O and D ² and having the property of cleaving the D ¹ -G bond following the cleavage of the N—O bond, and G itself has the timing ability of further decomposition. May be. Dye represents a diffusible dye group, X represents a benzene ring, a naphthalene ring, a 5- to 8-membered heterocyclic ring containing 1 or 2 nitrogen atoms, or a chain or cyclic alkyl group having 2 to 10 carbon atoms. , These may have a substituent, other saturated or unsaturated rings may be condensed, and some of the constituent carbon atoms may be replaced by oxygen atoms or sulfur atoms. good. L represents a linking group. m is a natural number of 1 or more and n is 2 or more, and n L- (Dye)
_m may be the same, and when m is 2 or more, m D
Ye may be the same or different.