JPH0934080A - Heat developable photosensitive material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a positive heat-developable color photosensitive material improved in white background by dispersing a reducible dye donor and/or a reducing agent with a polymer having a specified amount of specified structural units. SOLUTION: In the photosensitive material containing on a support a photosensitive silver halide, a binder, an electron donor and/or its precursor, and a reducible dye donor to release a diffusible dye by being reduced, the reducible dye donor and/or the reducing agent is dispersed by a polymer having the structural units in at least 5mol% represented by the formula, in which R is H or a halogen atom, or an alkyl, cycloalkyl, alkoxy, aryl, aryloxy, aryloxycarbonyl, trialkylsilyl, aralkyl, aralkoxy, alkenyl, acylamino, or alkylthio group, or the like; each optionally straight or branched; L is a divalent bonding group; and (p) is 0 or 1.

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 positive-working development color light-sensitive material having an improved white background.

[0002]

2. Description of the Related Art Photothermographic materials are known in the art. For details of the photothermographic materials and processes thereof, see, for example, "Basics of Photographic Engineering", Non-silver salt photography, ed. ２５255.

[0003] Many methods have been proposed for obtaining a color image by thermal development. For example, U.S. Patent Nos. 3,531,286, 3,761,270, and 40212
No. 40, Belgian Patent No. 802,519, Research Disclosure Magazine (hereinafter abbreviated as RD), September 31, 1975, pp. 31-32, etc., propose a method of forming a color image by combining an oxidized form of a developing agent with a coupler. Have been.

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 improve 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. 6626, No. 4483914, No. 4503137
No. 4,559,920; JP-A-59-165054).

In the above method, the developing temperature is still high, and the temporal stability of the photosensitive material is not sufficient. Thus, a method of heating and developing in the presence of a base or a base precursor and a very small amount of water to transfer the dye, thereby accelerating the development, lowering the developing temperature, and simplifying the processing is disclosed in Japanese Patent Application Laid-Open No. Sho 59-2.
No. 18443, No. 61-238056, European Patent 21
No. 0660A2.

Many methods have been proposed for obtaining a positive color image by thermal 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, U.S. Pat. No. 4,783,396 and Japanese Patent Laid-Open No. 64-13546 disclose an N-X bond (X represents an oxygen atom, a nitrogen atom or a sulfur atom) as a diffusion resistant compound that releases a diffusible dye by a similar mechanism. The heat-developable color light-sensitive material using a diffusion-resistant compound which releases a diffusible dye by reductive cleavage of (. These diffusion resistant compounds are hereinafter referred to as reducible dye donating compounds. This method comprises at least a photosensitive silver halide, a binder, an electron donor and / or its precursor (which is preferably diffusion resistant) on a support, and itself which is reduced to release a diffusible dye. A heat-developable color light-sensitive material having a multilayer structure having a diffusion-resistant compound is heated after exposure to oxidize an electron donor according to the amount of silver halide, and the above-mentioned reducible dye-donating compound is not oxidized. The residual electron donor is reduced to release a diffusible dye, which is 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.

Many studies have been made 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-mentioned problems and to make the problems of stability over time and white background and color reproducibility compatible with each other, JP-A-2-269,338 discloses that the addition amount of a hardly soluble metal compound depends on the total binder amount of a light-sensitive material. A photographic material containing 20 to 60% by weight is disclosed. But this way,
Although the effect was recognized, it was still insufficient, and further improvement in white background and color reproducibility was desired.

In the above-mentioned positive-working heat-developable color light-sensitive material, in order to improve the white background of a color image, it is necessary to accelerate silver development in the exposed area and quickly consume the electron donor. Since the electron donor is designed to have a potential suitable for reducing the reducible dye-donating compound,
The ability to reduce exposed silver halide is not necessarily high. Therefore, in many cases, a method of using a diffusible electron transfer agent to reduce exposed silver halide with this electron transfer agent and oxidizing the electron donor with an oxidized form of the electron transfer agent is often used. However, in such a case, there is a problem that the color reproducibility is deteriorated. Various studies have been made to improve color reproducibility, and for example, JP-A-2-25.
No. 9755 discloses a method of improving the spectral sensitivity characteristics of B, G, and R layers by optimizing them. JP-A-2-110557 and JP-A-2-253253 disclose positive-working heat-developable color light-sensitive materials having a specific development inhibitor releasing redox compound in the intermediate layer. JP-A-6
No. 301181 discloses a method of improving color reproducibility by using a reducible dye-donating compound that releases a plurality of dyes. Further, in JP-A-6-301179, a reducible dye-donating compound that releases a specific yellow dye and 5 g /
A method of improving color reproducibility by using a binder of m ² or less is disclosed. Although the color reproducibility was greatly improved by these methods, the white background was insufficient, and this improvement was a problem.

[0011]

SUMMARY OF THE INVENTION It is, therefore, an object of the present invention to provide a positive heat-developable color light-sensitive material having an improved white background.

[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.

A heat containing on the support at least a light-sensitive silver halide, a binder, an electron donor and / or a precursor thereof, a reducing agent, and a reducible dye-donor compound which is reduced to release a diffusible dye. In the developing color light-sensitive material, the ring-forming dye-providing compound and / or the reducing agent are dispersed by at least one polymer containing at least 5 mol% of the unit represented by the following general formula (1). Characteristic heat-developable color photosensitive material. (General formula 1)

[0014]

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In the formula, R represents a hydrogen atom, an alkyl group, a cycloalkyl group, an alkoxy group, an aryl group, an aryloxy group, an aryloxycarbonyl group, a trialkylsilyl group, an araryl group, an aralkoxy group, an alkenyl group,
It represents an acylamino group, a halogen atom, an alkylthio group, a diacylamino group, an arylthio group, an alkoxycarbonyl group, an acyloxy group, an acyl group, a sulfonamide group, a sulfonyl group, a carbamoyl group or a sulfamoyl group, which may be linear or branched. . L represents a divalent linking group. p represents 0 or 1.

In the present invention, it is unpredictable that the white background of a color image will be improved by using the compound represented by the general formula (1).

The compound represented by the general formula (1) which can be used in the present invention will be described in more detail below. Where R
Is a hydrogen atom, an alkyl group, a cycloalkyl group, an alkoxy group, an aryl group, an aryloxy group, an aryloxycarbonyl group, a trialkylsilyl group, an araryl group,
Aralkoxy group, alkenyl group, acylamino group, halogen atom, alkylthio group, diacylamino group, arylthio group, alkoxycarbonyl group, acyloxy group,
It represents an acyl group, a sulfonamide group, a sulfonyl group, a carbamoyl group or a sulfamoyl group, and may be linear or branched.

In the general formula (1), L represents a divalent linking group, and p represents 0 or 1. When p is 1, it is preferably a carbamoyl group, an arylcarbamoyl group, an alkylene group or an arylene group. L may have a substituent.

The polymer which can be used in the present invention may contain a monomer unit other than the general formula (1), and preferable monomer units include, for example, acrylic acid esters, methacrylic acid esters, acrylamides and methacrylic acid. Examples thereof include amides and styrenes. Further, JP-A-60-122940, JP-A-60-235134,
Japanese Patent Application No. 59-169042, JP-A No. 62-24403.
You may contain the comonomer described in No. 6 grade.

The molecular weight of the polymer usable in the present invention is preferably 5 × 10 ² to 1 × 10 ⁷ . If the molecular weight is too low, the polymer will be apt to move, and if the molecular weight is too high, coating may be hindered.

The preferred specific examples of the polymer used in the present invention are shown below, but the present invention is not limited thereto. Moreover, you may use 2 or more types together.

[0022]

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[0023]

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[0024]

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[0025]

[Chemical 6]

[0026]

[Chemical 7]

[0027]

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[0028]

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[0029]

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[0030]

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[0031]

[Chemical 12]

[0032]

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[0033]

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[0034]

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In the present invention, the reducible dye-donating compound and / or the reducing agent and the polymer are prepared by an oil emulsion such as dibutyl phthalate, triresyl phosphate, glyceryl triacetate or diethyl phthalate by a well-known emulsification dispersion method. It is also possible to dissolve it using an auxiliary solvent such as ethyl acetate or cyclohexanone and mechanically prepare an emulsified dispersion for use. Alternatively, a powder of the compound may be dispersed in water by a ball mill, a colloid mill, or ultrasonic waves by a method known as a solid dispersion method, and then used.

The optimum amount of the polymer used in the present invention varies depending on the amount and type of the reducible dye-donating compound and the amount and type of the reducing agent, but the usable range is a substance dispersed. 0.1 to 300% by weight, preferably 0.5 to 100% by weight.

The heat-developable color light-sensitive material of the present invention basically contains a binder, an electron donor, a reducing agent, and a reducible dye-providing compound on a support, and further, if necessary, an organic metal. A hydrochloric acid agent and the like can be included. These components are often added to the same layer,
If it can react, it can be added in separate layers. For example, the presence of a colored reducible dye-providing compound in the lower layer of a silver halide emulsion prevents a decrease in sensitivity. The electron transfer agent is preferably incorporated in the photothermographic material, but 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, at least three different spectral regions are combined with photosensitive silver halide emulsions. To use. For example, a combination of three layers of a blue layer, a green layer, and a red layer, a green layer, a red layer,
There is a three-layer combination of infrared sensitive layers. The order of arrangement of the respective photosensitive layers is arbitrary, and various arrangement orders known for ordinary type color photosensitive materials can be adopted. Further, each of these photosensitive layers may be divided into two or more layers as necessary, as described in JP-A-1-252954. 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 on the photothermographic material. Specifically, an undercoat layer as described in US Pat. No. 5,051,335, JP-A-1
No. 167,838, an intermediate layer having a solid pigment as described in JP-A No. 61-20,943, JP-A No. 1-120,
553, 5-34,884, 2-64,634.
An intermediate layer having a reducing agent or a DIR compound,
US Pat. Nos. 5,017,454 and 5,139,91
9, an intermediate layer having an electron transfer agent as described in JP-A-2-235,044, a protective layer having a reducing agent as described in JP-A-4-249,245, or a layer in which these are combined. be able to. The protective layer is preferably divided into two layers. In the case of a photothermographic material, it is often necessary to add various additives to the protective layer, so that the film strength becomes weak and scratches easily occur. Therefore, it is preferable that the protective layer is divided into two layers, and that the uppermost layer has a low content of additives (particularly oil-soluble components) to the binder and has a binder-rich composition in order to increase the film strength. When the support is polyethylene laminated paper containing a white pigment such as titanium oxide, the back layer is preferably designed to have an antistatic function and a surface resistivity of 10 ¹² Ω · cm or less.

The silver halide emulsion of the present invention (emulsion containing a photosensitive silver halide) may have various shapes. Examples thereof include regular particles having regular crystals such as cubes, octahedra, and tetradecahedrons, tabular grains, spherical grains, and grains having irregular crystal shapes such as potato grains. I can give you.
The photosensitive silver halide that can be used in each photosensitive layer of the present invention is
Any of silver chloride, silver bromide, silver iodobromide, silver chlorobromide, silver chloroiodide, and silver chloroiodobromide may be used. The silver halide emulsion may be a surface latent image type emulsion or an internal latent image type emulsion.
The internal latent image type emulsion is used as a direct reversal emulsion in combination with a 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. In particular, a method of mixing emulsions having different sensitivities for adjusting gradation (for example, JP-A-1-167744) is preferably used. The particle size is preferably 0.1 to 2 μm, particularly preferably 0.2 to 1.5 μm. The photosensitive silver halide emulsion used in the present invention is
Core shell emulsions are preferred. In addition, JP-A-3-11055
A monodisperse emulsion having a coefficient of variation of 20% or less described in No. 5 is preferable. Specifically, US Pat. No. 4,500,62
No. 6, 50th column, No. 4,628,021, Research Disclosure (hereinafter abbreviated as RD) 36544
(1994), JP-A-62-253159, JP-A-3-110555, JP-A-2-236546, 1-1.
67743, 6-332, 093, 6-30
1,129, 6-230,491, 6-19
4,768, 6-194,766, European Patent 61
Any of the silver halide emulsions described in No. 8,484A can be used.

In the process of preparing the light-sensitive silver halide emulsion of the present invention, it is preferable to carry out so-called desalting to remove excess salt. As a means for this, a Nudel washing method performed by gelling gelatin may be used, and inorganic salts composed of polyvalent anions (eg, sodium sulfate), anionic surfactants, anionic polymers (eg, polystyrenesulfonic acid) Sodium) or a precipitation method using a gelatin derivative (for example, aliphatic acylated gelatin, aromatic acylated gelatin, aromatic carbamoylated gelatin, etc.). The sedimentation method is preferably used.

The photosensitive silver halide emulsion used in the present invention may contain heavy metals such as iridium, rhodium, platinum, cadmium, zinc, thallium, lead, iron and osmium for various purposes. These compounds may be used alone or in combination of two or more. The addition amount depends on the purpose of use, but is generally about 10 ^-9 to 10 ^-3 mol per mol of silver halide. When it is contained, it may be uniformly added to the particles, or may be localized inside or on the surface of the particles. Specifically, JP-A-2-236542, JP-A-1-116637, and JP-A-6-116637
258,755, 6-235,992, Japanese Patent Application No. 4
The emulsion described in JP-A-126629 or the like is preferably used.

In the step of forming grains of the light-sensitive silver halide emulsion of the present invention, rhodan salt, ammonia, 4-substituted thioether compound or JP-B No. 47-1 is used as a silver halide solvent.
Organic thioether derivatives described in 1386 or sulfur-containing compounds described in JP-A-53-144319 can be used.

For other conditions, see P. Graphide, "Shimmie Physics Photographic".
[Paul Montell, 1967], GF Duffin, "Photographic Emulsion Chemistry" [The Focal Press, 1966]
Year ", Bier Zerikman et al.," Making and Coating Photographic Emulsion "(published by The Focal Press, 1964). That is, any of an acidic method, a neutral method, and an ammonia method may be used, and a method of reacting a soluble silver salt with a soluble halide may be any of a one-sided mixing method, a double-mixing method, and a combination thereof. In order to obtain a monodisperse emulsion, a simultaneous mixing method is preferably used. A back mixing method in which the grains are formed in the presence of excess silver ions can also be used. As one type of the double jet method, a so-called controlled double jet method in which the pAg in a liquid phase in which silver halide is formed is kept constant can be used.

Further, in order to accelerate the grain growth, the addition concentration, the addition amount, and the addition rate of the silver salt and the halogen salt to be added may be increased (JP-A-55-142329 and JP-A-5-142329).
No. 5-158124, U.S. Pat. No. 3,650,575).
Further, the method of stirring the reaction solution may be any known stirring method. The temperature of the reaction solution during the formation of silver halide grains,
The pH may be set in any way according to the purpose. The preferred pH range is 2.2 to 7.0, more preferably 2.5 to
6.0.

The photosensitive silver halide emulsion is usually a chemically sensitized silver halide emulsion. The chemical sensitization of the light-sensitive silver halide emulsion of the present invention may be performed by a known method such as a sulfur sensitization method, a reduction sensitization method, a noble metal sensitization method and a selenium sensitization method alone or in combination with an emulsion for a conventional light-sensitive material. (For example, JP-A-3-110555 and Japanese Patent Application No. 4-75).
798). These chemical sensitizations can also be carried out in the presence of a nitrogen-containing heterocyclic compound (JP-A-62-2531).
59). The pH at the time of chemical sensitization is preferably 5.3 to 1
0.5, more preferably 5.5 to 8.5, pAg
Is preferably 6.0 to 10.5, more preferably 6.8.
９9.0. 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.

The additives used in such a process and the known photographic additives that can be used in the present invention are described in the above-mentioned RD.
No.36,544, No.18,716 and No.3
07, 105, and the corresponding portions are summarized in the following table. Type of additive RD36544 RD18716 RD307105 1. Chemical sensitizers, pages 510-511, page 648, right column, page 866. Sensitivity enhancer page 648, right column 3. 3. Spectral sensitizers 511-514 page 648 right column 866-868 supersensitizer 頁 649 right column Whitening agent Page 514 Page 648 Right column Page 868 5. Antifoggant 515 to 649, right column, 868 to 870, stabilizer, page 517 6. Light absorber 517 to 649, right column, page 873, filter dye, pages 518 to 650, left column, ultraviolet absorber 7. 7. Dye image stabilizer page 527 page 650 left column page 872 Hardener page 508 page 651 left column page 874-875 9. Binders 507 pages 651 left columns 873 to 874 10. Plasticizers and lubricants 519 pages 650 right columns 876 11. Coating aids 519 pages 650 right columns 875 to 876 Surfactants 12. Static 520 pages 650 Right column on page 876-877 page Inhibitor 13. Matting agent page 521 page 878-879

Gelatin is advantageously used as a protective colloid used in the preparation of the emulsion of the present invention and as a binder for other constituent layers of the light-sensitive material and dye fixing element, but other hydrophilic binders are also used. be able to. Examples thereof include the above-mentioned Research Disclosure and JP-A-64-13546, page (71)-
(75). Specifically, a transparent or translucent hydrophilic binder is preferable, and for example, gelatin or a protein or cellulose derivative such as a gelatin derivative, starch, gum arabic, dextran, a natural compound such as a polysaccharide 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. In particular, a combination of gelatin and the above binder is preferable.Depending on various purposes, lime-processed gelatin, acid-processed gelatin, demineralized gelatin with a reduced content of calcium, etc., and oxidized to reduce methionine residues according to various purposes. It may be selected from gelatin and the like, and it is also preferable to use them in combination.

When a system in which a small amount of water is supplied for thermal development is adopted, it is possible to quickly absorb water by using the above superabsorbent polymer. Further, when a superabsorbent polymer, polyvinyl alcohol, or a polysaccharide is used in the dye fixing layer or its protective layer as described in Japanese Patent Application No. 5-181,413, the dye may be removed from the dye fixing element after transfer. It is possible to prevent the retransfer to the thing. 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,
Further, it is appropriate that the weight be 7 g or less.

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-described organic silver salt oxidizing agents include US Pat.
There are benzotriazoles, fatty acids and other compounds described in No. 0,626, columns 52 to 53 and the like. In addition, JP
Silver salts of carboxylic acids having an alkynyl group, such as silver phenylpropiolate described in JP-A-113235;
The acetylene silver described in No. 1-249044 is also useful.
Two or more 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 suitably from 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 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. Especially,
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.
Nos. 49-50, No. 4,483,914, No. 30
Columns 31, 31 and 4,330,617, 4,590,1
No. 52, No. (17) of JP-A-60-140335
(18), pp. 57-40245, pp. 56-1387
No. 36, No. 59-178458, No. 59-53831
Nos. 59-182449 and 59-182450
No. 60, No. 60-119555, No. 60-138436 to No. 60-128439, No. 60-19854.
No. 0, No. 60-181742, No. 61-259253
Nos. 62-244444, 62-131253 to 62-131256, European Patent No. 220,
746A2, pages 78 to 96, and the like, for example, electron donors and electron donor precursors. US Patent 3,03
Various electron donor combinations such as those disclosed in US Pat. No. 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 is from 0.01 to 20 mol, particularly preferably from 0.1 to 10 mol, per mol of silver.

The reducible dye-donating compound used in the present invention is a compound which, when silver ions are reduced to silver under a high temperature condition, produces a mobile dye in response to this reaction or releases it. Is. Examples of dye-donor compounds include
Examples thereof include compounds having a function of releasing or diffusing a diffusible dye in an image form. This type of compound can be represented by the following general formula [LI]. (Dye-Y) nZ [LI] Dye represents a dye group, a temporarily shortened dye group or a dye precursor group, Y represents a simple bond or linking group, and Z represents an image latent image. Corresponding to or opposite to the photosensitive silver salt having a difference in the diffusivity of the compound represented by (Dye-Y) nZ, or releasing Dye and releasing Dye and (Dye- Y) represents a group having a property of causing a difference in diffusibility with nZ, n represents 1 or 2, and when n is 2, two Dy
e-Y may be the same or different. General formula [LI]
The following compounds may be mentioned as specific examples of the dye-donating compound represented by. The following compounds form a diffusible dye image (positive dye image), which corresponds to the development of silver halide.

US Pat. No. 4,559,290, European Patent 220,746A2, US Pat. No. 4,783,3
As described in No. 96, Kokai Giho 6-6199, etc., a non-diffusible compound which releases a diffusible dye by reacting with a reducing agent remaining unoxidized by development can be used.
Examples thereof include U.S. Pat. Nos. 4,139,389 and 4,139,379, JP-A-59-185333,
Compounds which release a diffusible dye by a nucleophilic substitution reaction in the molecule after reduction described in US Pat. No. 4,232,107, JP-A-59-84453.
No. 101649, No. 61-99257, RD240
25 (1984), which releases a diffusible dye by an intramolecular electron transfer reaction after reduction, West German Patent No. 3,008,588A, JP-A-56-
No. 142530, U.S. Pat. Nos. 4,343,893, 4,619,884, and the like, compounds which release a diffusible dye by cleavage of a single bond after reduction, U.S. Pat. Examples thereof include nitro compounds described in U.S. Pat. No. 223, which release a diffusible dye after electron acceptance, compounds described in U.S. Pat. No. 4,609,610 which release a diffusible dye after electron acceptance, and the like.

Further, as more preferable ones, European Patent No. 220,746A2, Open Technical Report 87-6199, US Pat. No. 4,783,396, Japanese Patent Laid-Open No. 63-2016.
No. 53, 63-2016654 and the like, compounds having an N—X bond (X represents oxygen, sulfur or nitrogen atom) and an electron-withdrawing group in one molecule, JP-A-1-268.
No. 42, a compound having SO ₂ —X (where X is as defined above) and an electron-withdrawing group in one molecule, JP-A-63-2
No. 71344, a PO-X bond (X
Has the same meaning as above) and a compound having an electron-withdrawing group, C-X 'in one molecule described in JP-A-63-271341.
Compounds having a bond (X ′ has the same meaning as X or represents —SO ₂ —) and an electron-withdrawing group are exemplified. In addition, JP-A-1
Compounds described in JP-A-161237 and JP-A-1-161342, which release a diffusible dye by cleaving 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. No. 4,783,3.
96-compounds (1)-(3), (7)-
(10), (12), (13), (15), (23)-
(26), (31), (32), (35), (36),
(40), (41), (44), (53) to (59),
(64), (70), compounds (11) to (23) described in JP-A-87-6199, JP-A-6-301,1.
Compounds (I-1) to (I-10) described in No. 81.

In the present invention, the development inhibitor releasing redox compound can be used as described above. For example, 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-
213,847, 62-260,153, U.S. Pat. No. 4,684,604, JP-A-1-269936.
Nos. 3,379,529 and 3,620,
746, 4,377,634, 4,332,8
78, JP-A-49-129,536 and JP-A-56-15.
3,336, 56-153,342 and the like.

The development inhibitor-releasing redox compound of the present invention is 1 × 10 ^{-6 to} 5 × 10 ^-2 per mol of silver halide.
Mole, more preferably in the range of 1 × 10 ^-5 to 1 × 10 ^-2 mole. The development inhibitor releasing redox compound used in the present invention may be any suitable water-miscible organic solvent, for example, alcohols (methanol, ethanol, propanol, fluorinated alcohol), ketones (acetone, methyl ethyl ketone), dimethylformamide, dimethyl sulfoxide. And methylcellosolve. In addition, by an already well-known emulsification dispersion method, dissolution is performed using an oil such as dibutyl phthalate, tricresyl phosphate, glyceryl triacetate or diethyl phthalate, and an auxiliary solvent such as ethyl acetate or cyclohexanone, and mechanically emulsified and dispersed. Objects can also be created and used. Alternatively, by a method known as a solid dispersion method, a powder of a development inhibitor-releasing redox compound is placed in water with a ball mill, a colloid mill,
Alternatively, they can be used by being dispersed by ultrasonic waves.

The heat-developable color light-sensitive material of the present invention may contain one or more 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,
In particular, 100,000 to 800,000 are preferable. The pullulan is preferably 20,000 to 2,000,000. 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 use amount of dextran, pullulan and / or their derivatives is 0.01 to 10 g / m ² ,
It is preferably in the range of 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 it exceeds 10 g / m ² , the film quality deteriorates.

Hydrophobic additives such as dye-donor compounds, antidiffusive 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, based on 1 g of the dye-donor compound used. Further, 1 cc or less, more preferably 0.5 cc or less, particularly 0.3 cc or less is suitable for 1 g of the binder. A 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 the hydrophobic compound in the hydrophilic colloid, various surfactants can be used. For example, JP-A-59-
The surfactants described in Research Disclosure, pages 37 to 38 of 157636, can be used. Further, a so-called polymer dispersant can be used. In the present invention, a compound capable of activating development and simultaneously stabilizing an image can be used in the light-sensitive material. The specific compounds preferably used are described in US Pat. No. 4,500,626, columns 51 to 52.

In a system for forming an image by diffusion transfer of a dye, a dye fixing element is used together with a light-sensitive material. The dye-fixing element may be in the form of being separately coated on a support separate from the light-sensitive material, or in the form of being coated on the same support as the light-sensitive material. The relationship between the photosensitive material and the dye fixing element, the relationship with the support, and the relationship with the white reflective layer described in US Pat. No. 4,500,626, column 57, can be applied to the present invention. 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 58-59 and JP-A-61-8825.
No. 6, pages (32) to (41);
Nos. 2-244043 and 62-244036. Also, US Pat.
A dye-accepting polymer compound as described in JP-A-63,079 may be used. The dye-fixing element may be provided with an auxiliary layer such as a protective layer, a release layer, and an anti-curl layer, if necessary. In particular, it is useful to provide a protective layer.

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 between the light-sensitive material and the dye-fixing element. A specific example is (2) in JP-A-62-253159.
5), pages 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 sample 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. Anti-fading agents include, for example, antioxidants, ultraviolet absorbers, or certain metal complexes.
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 27-29), 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). An anti-fading agent for preventing fading of the dye transferred to the dye-fixing element may be contained in the dye-fixing element in advance, or may be supplied to the dye-fixing element from the outside such as a photosensitive material. . The above antioxidants, ultraviolet absorbers, and metal complexes may be used in combination with each other. A fluorescent whitening agent may be used for the light-sensitive material and the dye fixing element. In particular, whether the dye-fixing element contains a fluorescent whitening agent,
It is preferably supplied from the outside such as a photosensitive material. For example, see “The Chemistry of K. Veenkataraman”.
Synthetic Dyes ", Volume V, Chapter 8, JP-A-61-143
No. 752 and the like. More specifically, stilbene compounds, coumarin compounds, biphenyl compounds, benzoxazolyl compounds, naphthalimide compounds, pyrazolidone 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 for 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 and the like. 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 preferred is JP-A-Hei 3
The vinyl sulfone type hardener described in No. 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 releasability, improvement of slipperiness, prevention of electrification, acceleration of development and the like. Specific examples of the surfactant are disclosed in JP-A-62-173463.
And No. 62-183457. 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. Representative examples of organic fluoro compounds include JP-B-57-9053, columns 8-17, and JP-A-61-20.
No. 944, No. 62-135826 or the like, or a hydrophobic fluorine compound such as an oily fluorine compound such as fluorine oil or a solid fluorine compound resin such as ethylene tetrafluoride resin. No.

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 heat solvent, an antifoaming agent, an antibacterial and antibacterial agent, colloidal silica and the like. Specific examples of these additives are disclosed in JP-A-61-8.
No. 8256, pages (26) to (32).
Further, as a preferable antibacterial / antifungal agent, JP-A-3-11338 is used.
The number one is used.

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, EP 210,660, U.S. Pat.
Use is made of a combination of the hardly soluble metal compound described in No. 45 and a compound capable of forming a complex with a metal ion constituting the hardly soluble metal compound (referred to as a complex forming compound). Specifically, JP-A-2-269,338 (2)-
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 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 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 (especially syndiotactic polystyrene is preferable),
Polypropylene, polyimide, celluloses (for example, triacetyl cellulose) or those films containing a pigment such as titanium oxide, synthetic film made of polypropylene or the like, synthetic resin pulp such as polyethylene and natural pulp Blended paper made from, 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), JP-A-2-272543, and JP-A-2-2
The support described in No. 2651 can be preferably 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, natural light, tungsten lamps, light emitting diodes, laser light sources, CRT light sources, etc., US Pat. No. 4,500,626, column 56, JP-A-2-53,37.
The light sources and exposure methods described in No. 8 and No. 2-54,672 can be used. Further, a blue light emitting diode, which has been remarkably developed recently, can be used, and a light source combined with a green light emitting diode and a red light emitting diode can be used.
In particular, Japanese Patent Application Nos. 6-40,164 and 6-40,012
No. 6, No. 6-42, 732, No. 6-86,919, No. 6-86,920, No. 6-93,421, No. 6-9.
4,820, 6-96,628, 6-149,
The exposure apparatus described in No. 609 can be preferably used. Also, image exposure can 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 non-linear optical material is a material capable of exhibiting non-linearity between polarization and an electric field, which appears when a strong optical electric field such as laser light is applied, such as lithium niobate and potassium dihydrogen phosphate (KDP). ), An inorganic compound represented by lithium iodate, BaB ₂ O ₄ or the like, a urea derivative, a nitroaniline derivative, for example, nitropyridine-N-such as 3-methyl-4-nitropyridine-N-oxide (POM). Oxide derivative, JP-A-6
Compounds described in 1-53462 and 62-210432 are preferably used. As a 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. Further, the image information is
Image signals obtained from video cameras, electronic still cameras, etc., television signals represented by the Nippon Television Signal Standard (NTSC), image signals obtained by dividing an original image into a large number of pixels such as a scanner, CG, CAD, etc. An image signal created by using a computer 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.
No. 45544 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., but development at 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 transfer of the dye is caused 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 not lower than 50 ° C. and not higher than the boiling point of the solvent. For example, when the solvent is water, the temperature is preferably 50 ° C. or more and 100 ° C. or less. 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, a fungicide and a fungicide may be contained in the solvent. Water is preferably used as the solvent in these steps of heat development and diffusion transfer, but any commonly used water may be used. Specifically, distilled water, tap water, well water, mineral water, and the like can be used. Further, in the heat developing apparatus using the light-sensitive material and the image-receiving material of the present invention, water may be used up, or may be circulated for repeated use. And JP-A-63-144,354 and JP-A-63-144,3.
55, 62-38,460, JP-A-3-310,
No. 555 or the like or water may be used.

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 the methods described in JP-A-62-253,159, page (5) and JP-A-63-85,544. Further, the solvent can be used by being incorporated in advance in the light-sensitive material or the dye-fixing element or both in the form of enclosing the solvent in microcapsules.

In order to promote dye transfer, a system in which a hydrophilic thermal solvent which 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 adopted. The hydrophilic thermal solvent may be incorporated in either the photosensitive 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 is preferably incorporated in the dye-fixing layer and / or an adjacent layer. Examples of hydrophilic thermal solvents include ureas, pyridines, amides, sulfonamides, imides, alcohols, oximes and other heterocycles. In order to promote dye transfer, a high-boiling organic solvent may be contained in the light-sensitive material and / or the dye-fixing element.

As the heating method in the developing and / or transferring step, a heated block or plate may be contacted, or a hot plate, a hot presser, a heat roller, a halogen lamp heater, an infrared or far infrared lamp heater, etc. may be 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.
No. 47244, page 27, can be applied.

For processing the photographic element of the present invention, any of various heat developing apparatuses can be used. For example, JP-A-59-7
No. 5247, No. 59-177547, No. 59-181.
No. 353, No. 60-18951, No. 62-259.
No. 44, JP-A-3-131856 and JP-A-3-13185
No. 1, Japanese Patent Application Nos. 4-277,517 and 4-243,0
No. 27, No. 4-244, 693, No. 6-164, 42
No. 1 and No. 6-164,422, etc. are preferably used. As a specific device, Fuji Photo Pictrostat 100, Fuji Pictostat 200, Pictrostat 300, and the like manufactured by Fuji Photo Film Co., Ltd. are preferably used.

[0081]

EXAMPLES The present invention will be described below with reference to 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 a mill was used to obtain an average particle size of 0.75 mm. 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, 0.4 g of carboxymethylcellulose (trade name: Serogen 6A manufactured by Daiichi Kogyo Co., Ltd.) as a dispersant, and 0.2 g of the following anionic surfactant were added to a 5% aqueous gelatin solution. , Milled with glass beads having an average particle size of 0.75 mm for 60 minutes. Separate glass beads, average particle size 0.35μm
Was obtained.

[0086]

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[0087]

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

The following polymer latex (solid content 13
%) 108 ml, the following surfactant 20 g, water 1232 ml
While stirring this mixture, 600 ml of a 5% aqueous solution of the following anionic surfactant was added over 10 minutes. Using the ultrafiltration module, the dispersion made in this way is
It was concentrated and desalted to 500 ml. 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.

[0090]

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[0091]

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[0092]

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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 heated and dissolved at about 60 ° C. to form a uniform solution. This solution and the aqueous phase component heated at about 60 ° C. were added, mixed with stirring, and dispersed with a homogenizer for 13 minutes at 12,000 rpm. Add water to this,
Stirring yielded a uniform dispersion. For the gelatin dispersion of the magenta and cyan dye-donor compounds, the ultrafiltration module (Asahi Kasei Ultrafiltration Module ACV
-3050) using water to repeat dilution and concentration,
Ethyl acetate and methyl ethyl ketone in Table 1 were reduced to 1/6.

[0095]

[Table 1]

[0096]

[Chemical 21]

[0097]

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[0098]

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[0099]

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[0100]

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[0101]

[Chemical formula 26]

[0102]

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[0103]

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[0104]

[Chemical 29]

[0105]

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[0106]

[Chemical 31]

[0107]

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[0108]

[Chemical 33]

[0109]

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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 (in 700 ml of water, 20 g of gelatin, 0.5 g of potassium bromide, 2.5 g of sodium chloride and the following chemicals) (A) Add 15mg and 42 ℃
Solution (I) and solution (II) in Table 2 were simultaneously added at a constant flow rate for 8 minutes. Then, 8 minutes after the completion of the addition of the liquids (I) and (II), an aqueous solution of a gelatin dispersion of a dye (water 1) was added.
1.9 g of gelatin in 60 ml, the following pigment (a) 127
mg, the following pigment (b) 253 mg, the following pigment (c) 8 mg
Containing 35 ° C. and kept at 35 ° C.). Two minutes later, solution (III) and solution (IV) shown in Table 2 were simultaneously added at the same flow rate for 32 minutes.

After washing with water and desalting by a conventional method, 22 g of lime-treated ossein gelatin and 50 mg of the following chemical (B) were added to adjust pH to 6.2 and pAg to 7.8, and 4-hydroxy-6- Methyl-1,3,3a, 7-tetrazaindene was added, and then sodium thiosulfate and chloroauric acid were added for optimum chemical sensitization at 68 ° C., and then the following antifoggant (1), chemical (C ) 80 mg and 3 g of the chemical (D) were added and then cooled. Thus, the average particle size is 0.21 μm
635 g of a monodispersed cubic silver chlorobromide emulsion was obtained.

[0113]

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[0114]

[Table 2]

[0115]

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[0116]

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[0117]

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Photosensitive silver halide emulsion (2) [for red-sensitive emulsion layer] Well-stirred aqueous gelatin solution (20 g of gelatin, 0.3 g of potassium bromide, 9 g of sodium chloride in 700 ml of water).
g) and 15 mg of the above-mentioned chemical (A) were added thereto, and the mixture was kept at 53 ° C.). Solution (I) and solution (II) in Table 3 were simultaneously added at an equal flow rate for 10 minutes. Then, 6 minutes after the completion of the addition of the liquids (I) and (II), an aqueous solution of a gelatin dispersion of the dye (115 ml of water) was added.
Including 1.2 g of gelatin, 77 mg of the above dye (a), 153 mg of the above dye (b), and 5 mg of the above dye (c).
(Preserved at 5 ° C.). After 4 minutes, Solution (III) and Solution (IV) in Table 2 were simultaneously added at an equal flow rate for 30 minutes.

After washing with water and desalting by a conventional method, 33 g of lime-treated ossein gelatin and 50 mg of the above-mentioned chemical (B) were added to adjust pH to 6.2 and pAg to 7.8, and then 4-hydroxy-6-. Methyl-1,3,3a, 7-tetrazaindene was added, and then sodium thiosulfate and chloroauric acid were added to optimally perform chemical sensitization at 68 ° C., followed by the antifoggant (1), the chemical (C ) 80 mg and 3 g of the chemical (D) were added and then cooled. Thus, the average particle size is 0.45 μm
635 g of a monodispersed cubic silver chlorobromide emulsion was obtained.

[0120]

[Table 3]

Photosensitive Silver Halide Emulsion (3) [For Green Sensitive Emulsion Layer] Well stirred gelatin aqueous solution (20 g of gelatin, 0.5 g of potassium bromide, 5 g of sodium chloride in 690 ml of water).
g) and 15 mg of the above-mentioned chemical (A) were added thereto, and the mixture was kept at 41 ° C.). Solution (I) and solution (II) in Table 4 were simultaneously added at a constant flow rate for 8 minutes. After 10 minutes, solutions (III) and (IV) shown in Table 4 were simultaneously added at the same flow rate for 32 minutes. (II
One minute after completion of the addition of the liquids (I) and (IV), a methanol solution of the dye (containing 280 mg of the following dye (d) in 47 ml of methanol and kept at 30 ° C.) was added all at once.

After washing with water and desalting by a conventional method, 22 g of lime-treated ossein gelatin, 50 mg of the above-mentioned chemical (B) and 3 g of chemical (D) were added to adjust pH to 6.0 and pAg to 7.1. 4-hydroxy-6-methyl-1,3,3a, 7
-Tetrazaindene was added, and then sodium thiosulfate was added for optimal chemical sensitization at 60 ° C. Then, the following antifoggant (1) was added, followed by cooling. Thus, a monodisperse cubic silver chlorobromide emulsion 63 having an average grain size of 0.23 μm was prepared.
5 g was obtained.

[0123]

[Table 4]

[0124]

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Photosensitive Silver Halide Emulsion (4) [For Green Sensitive Emulsion Layer] Well stirred gelatin aqueous solution (20 g of gelatin, 0.3 g of potassium bromide and 9 g of sodium chloride in 710 ml of water).
g) and 7.5 mg of the above-mentioned chemical (A) were added, and the mixture was kept at 63 ° C.).
It was added at an equal flow rate for 0 minutes. After 10 minutes, (III) in Table 5
Solution and Solution (IV) were added simultaneously in equal amounts for 20 minutes. Also
One minute after the completion of the addition of the liquids (III) and (IV), a methanol solution of the dye (170 mg of the above-mentioned dye (d) in 35 ml of methanol)
Which was kept at 46 ° C.).

After washing with water and desalting in the usual way, 33 g of lime-treated ossein gelatin, 50 mg of the above-mentioned chemical (B) and 3 g of chemical (D) were added to adjust pH to 6.0 and pAg to 7.2. 4-hydroxy-6-methyl-1,3,3a, 7
-Tetrazaindene was added, sodium thiosulfate and chloroauric acid were added, and the mixture was optimally chemically sensitized at 60 ° C. Then, the following antifoggant (1) was added, followed by cooling. Thus, 635 g of a monodisperse cubic silver chlorobromide emulsion having an average grain size of 0.45 μm was obtained.

[0127]

[Table 5]

Photosensitive silver halide (5) [For blue-sensitive emulsion layer] Well-stirred aqueous gelatin solution (20 g of gelatin, 0.5 g of potassium bromide, 5 g of sodium chloride in 690 ml of water).
g) and 15 mg of the above-mentioned chemical (A) were added thereto, and the mixture was kept at 46 ° C.). Solution (I) and solution (II) in Table 6 were simultaneously added at the same flow rate for 8 minutes. After 10 minutes, solutions (III) and (IV) shown in Table 6 were simultaneously added at the same flow rate for 18 minutes. (II
One minute after the completion of the addition of the liquids (I) and (IV), an aqueous solution of the dye (water 9
225 mg of the following dye (e) in 5 ml and 5 ml of methanol
And the following dye (f) containing 225 mg and kept at 30 ° C.) were added all at once.

After washing with water and desalting by a conventional method, 22 g of lime-treated ossein gelatin, 50 mg of the above-mentioned chemical (B) and 3 g of chemical (D) were added to adjust pH to 6.0 and pAg to 7.7. 4-hydroxy-6-methyl-1,3,3a, 7
-Addition of tetrazaindene, then sodium thiosulfate, optimal chemical sensitization at 65 ° C, then addition of the following antifoggant (1) followed by cooling. Thus, a monodisperse cubic silver chlorobromide emulsion 63 having an average grain size of 0.27 μm was prepared.
5 g was obtained.

[0130]

[Table 6]

[0131]

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[0132]

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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 710 ml of water).
g) and 15 mg of the above-mentioned chemical (A) were added thereto, and the mixture was kept at 59 ° C.). Liquids (I) and (II) in Table 7 were simultaneously added at a constant flow rate for 8 minutes. After 10 minutes, solutions (III) and (IV) in Table 7 were simultaneously added at the same flow rate for 18 minutes. (II
One minute after the completion of the addition of the liquids (I) and (IV), an aqueous solution of the dye (water 8
113 mg of the above dye (e) in 2 ml and 6 ml of methanol
And the above-mentioned dye (f) containing 113 mg and kept at 40 ° C.) were added all at once.

After washing with water and desalting in a conventional manner, 33 g of lime-treated ossein gelatin, 50 mg of the above-mentioned chemical (B) and 3 g of chemical (D) were added to adjust pH to 6.0 and pAg to 7.7. 4-hydroxy-6-methyl-1,3,3a, 7
-Tetrazaindene was added, sodium thiosulfate and chloroauric acid were added, and the mixture was optimally chemically sensitized at 65 ° C. Then, the following antifoggant (1) was added, followed by cooling. Thus, 635 g of a monodisperse cubic silver chlorobromide emulsion having an average grain size of 0.47 μm was obtained.

[0135]

[Table 7]

A light-sensitive material 101 shown in Table 8 was prepared using the above.

[0137]

[Table 8]

[0138]

[Table 9]

[0139]

[Table 10]

[0140]

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[0141]

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[0142]

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[0143]

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[0144]

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[0145]

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[0146]

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Next, a method for preparing a dispersion containing the polymer of the present invention will be described. A dispersion of the present invention was prepared in exactly the same manner as in the dispersion of the dye-donor compound shown in Table 1 above, except that a polymer was added as shown in Table 9 to adjust the addition amount of the high boiling point organic solvent. .

[0148]

[Table 11]

As shown in Table 10 from the photographic material 101,
The light-sensitive material 102 shown in Table 11 was prepared in the same manner as the light-sensitive material 101 except that the same amounts of these dispersions were used in the light-sensitive layer.
I made ~ 110.

[0150]

[Table 12]

Next, a method for producing an image receiving material will be described. An image receiving material G101 having a constitution as shown in Table 11 was prepared.

[0152]

[Table 13]

[0153]

[Table 14]

[0154]

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[0155]

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[0156]

[Chemical 51]

[0157]

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[0158]

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Using the photosensitive materials 101 to 110 and the image receiving material G101 described above, processing was performed using Pictrostat 300 manufactured by Fuji Photo Film Co., Ltd. That is, the original image [Tetos chart obtained by photographing a Macbeth color checker chart and printing it on color paper] was placed on the original plate of Pictrostat 300, and the standard processing of Pictrostat was performed. At this time, Graystep Neutral 5
The concentration of 0.7 (X-light 40
The exposure amount of each layer was adjusted so as to meet the above (measured using No. 4). The light-sensitive materials 101 to 110 were processed as described above, and the white background of the obtained image was measured with an X light 404. The results are shown in Table 12.

[0160]

[Table 15]

In Table 12, the density of the photosensitive materials 102 to 110 of the present invention is lower than that of the photosensitive material 101.
It can be seen that the white background has been improved.

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[Procedure amendment]

[Submission date] September 21, 1995

[Procedure amendment 1]

[Document name to be amended] Statement

[Correction target item name] 0008

[Correction method] Change

[Correction contents]

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 complex formation reaction of the sparingly soluble metal compound with 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.

[Procedure amendment 2]

[Document name to be amended] Statement

[Correction target item name] 0150

[Correction method] Change

[Correction contents]

[0150]

[Table 12]

Claims (1)

[Claims] 1. A support containing at least a photosensitive silver halide, a binder, an electron donor and / or a precursor thereof, a reducing agent, and a reducible dye-donating compound which is reduced to release a diffusible dye. In the heat-developable color light-sensitive material, the reducible dye-donating compound and / or the reducing agent are dispersed by at least one polymer containing at least 5 mol% of the unit represented by the following general formula (1). A heat-developable color photosensitive material characterized by: (General formula 1) In the formula, R represents a hydrogen atom, an alkyl group, a cycloalkyl group, an alkoxy group, an aryl group, an aryloxy group, an aryloxycarbonyl group, a trialkylsilyl group, an araryl group, an aralkoxy group, an alkenyl group, an acylamino group, a halogen atom. Represents an alkylthio group, a diacylamino group, an arylthio group, an alkoxycarbonyl group, an acyloxy group, an acyl group, a sulfonamide group, a sulfonyl group, a carbamoyl group or a sulfamoyl group, and may be linear or branched. L represents a divalent linking group.
p represents 0 or 1.