JPH0477892B2 - - Google Patents

Description

[Detailed description of the invention]

[Industrial Application Field] The present invention relates to a heat-developable photosensitive material on which an image is formed by heat development, and more particularly to a heat-developable photosensitive material with improved fog (thermal fog) during heat development. [Background of the Invention] For ordinary wet-type silver halide photosensitive materials that require wet processing using a developer, etc., after image exposure,
2. Description of the Related Art Heat-developable photosensitive materials, in which images are obtained by dry processing such as heating, have many advantages in terms of processing time, cost, and concerns about pollution. Regarding such heat-developable photosensitive materials, many proposals have been made not only for monochrome use but also for heat-developable color photosensitive materials.
No. 179840, No. 57-186744, No. 57-198458, No. 179840, No. 57-186744, No. 57-198458, No.
No. 57-207250, No. 58-40551, No. 58-58543,
58-79247, 59-12431, 59-22049
No. 59-68730, No. 59-1234339, No. 59-
No. 124333, No. 59-124331, No. 59-159159, No. 124333, No. 59-124331, No. 59-159159, No.
No. 59-181345, No. 59-159161, No. 58-116537
No. 58-123533, No. 58-149046, No. 58-
There are issues such as No. 14947. The basic structure of the heat-developable color photosensitive materials proposed in these proposals consists of a photosensitive element and an image-receiving element, and the photosensitive element basically contains a photosensitive silver halide, a reducing agent (hereinafter also referred to as a developer), and a dye donor. It consists of a substance, a binder. In the present invention, only the photosensitive element is referred to as a heat-developable photosensitive material in a narrow sense. In this heat-developable photosensitive material, optical information is imparted to the photosensitive silver halide through image exposure, and during heat development, the developer that has or has not acted on the photosensitive silver halide becomes a dye-providing substance. A dye that forms an image is released or formed by reaction. The image-forming dye obtained by thermal development is transferred to an image-receiving element to form an image. However, regardless of whether it is monochrome or color, when trying to obtain an image with a sufficiently high maximum density, it has the disadvantage that fog (thermal fog) at the minimum density becomes large. This thermal fog phenomenon is thought to be due to the generation of fog nuclei on the surface of photosensitive silver halide or organic silver salt during thermal development, but the detailed mechanism is not clear. On the other hand, many of the compounds that are said to be effective as fog suppressants in photosensitive materials that do not use organic silver salts have no fog suppressing effect in photothermographic materials that contain organic silver salts, or on the contrary, Many of them have drawbacks such as increased fog or decreased sensitivity, and no effective findings as thermal fog suppressants have been provided. For example, Japanese Patent Application Laid-open No. 177550/1989 describes a compound known as an antifoggant (development inhibitor) used in ordinary silver halide photographic light-sensitive materials (hereinafter also referred to as conventional light-sensitive materials). There is also a description that the compound of 2 acts as a development accelerator in a heat-developable photosensitive material. In response, various thermal antifoggants (hereinafter also referred to as development inhibitors) for use in heat-developable photosensitive materials have been proposed. For example, the mercury compound of U.S. Pat. No. 3,589,903, the N-halogeno compound of West German Pat. No. 2,402,161, the peroxide of West German Pat.
Sulfur compounds in No. 2617907, palladium compounds in U.S. Patent No. 4102312, sulfinic acids in Japanese Patent Publication No. 53-28417, Research Disclosure No.
169077, mercaptotriazole of 169079, 1,2,4-triazole of US Pat. No. 4,137,079, and the like. However, these thermal antifoggants are either extremely harmful to the human body or have only a small antifogging effect, and the reality is that no satisfactory thermal antifoggant has yet been found. [Object of the Invention] Accordingly, an object of the present invention is to provide a heat-developable photosensitive material that has extremely low thermal fog and does not have a decrease in sensitivity or maximum density. [Structure of the Invention] The above object of the present invention is to provide at least the following on a support:
In a heat-developable light-sensitive material having a photosensitive silver halide, an organic silver salt, a reducing agent, and a binder, the heat-developable light-sensitive material further contains a compound represented by the following general formula (1). . General formula (1)
Represents a sulfinic acid group or a salt thereof. [Specific Structure of the Invention] In the general formula (1), the development inhibitor residue represented by
Chemistry of Photography (by Akira Sasai, Shashin Kogyo Publishing) 168~
169 pages or The Theory of the
In conventional photosensitive materials such as those described in Photographic Process (edited by T.H. James, Macmillan), pages 396-399, residues of organic compounds known as development inhibitors (or antifoggants) are present. The solubility product (pKsp) of the silver salt of the organic compound in water at 25°C is preferably 10 or more. Preferred examples when the residue of X in the general formula (1) is a compound represented by XH are represented by the following general formulas (2) to
Shown in (14). General formula (2) In the formula, R ₁ and R ₂ each represent a hydrogen atom, an alkyl group or an aryl group. General formula (3) In the formula, R ₄ represents a hydrogen atom, an alkyl group, or an aryl group General formula (4) In the formula, R ₅ is a hydrogen atom, an alkyl group, an aryl group, or

[Formula] is represented, and R ₆ represents a hydrogen atom or a nitro group. n represents 1 or 2. General formula (5) In the formula, R ₇ represents a hydrogen atom, an alkyl group or an aryl group. General formula (6) In the formula, R ₈ represents a hydrogen atom, an alkyl group or an aryl group, and Y is

[Formula] represents -O- or -S-. General formula (7) In the formula, R ₉ and R ₁₀ each represent a hydrogen atom, an alkyl group or an aryl group. However, R ₉ and
R ₁₀ may be combined to form a 5- to 6-membered ring.
R ₁₁ represents a thiol group or -NH-R ₁₂ (R ₁₂ represents a hydrogen atom, an alkyl group, or an aryl group), and Y represents -O-, -S-,

[expression] or

Represents [formula]. General formula (8) In the formula, R ₁₃ represents a hydrogen atom, a halogen atom, an alkyl group or a nitro group. General formula (9) In the formula, R ₁₄ , R ₁₅ and R ₁₆ each represent a hydrogen atom, an alkyl group, an amino group, an alkoxy group, a thioalkoxy group, a thiol group or a hydroxy group. General formula (10) In the formula, R ₁₇ , R ₁₈ , R ₁₉ , R ₂₀ and R ₂₁ are each a hydrogen atom, an alkyl group, an aryl group, -NH-
_R22 group ( _R22 represents a hydrogen atom, an alkyl group or an aryl group), a thiol group, an alkylthio group,
Represents a hydroxy group or an alkoxy group. General formula (11) In the formula, R ₂₃ and R ₂₄ each represent a hydrogen atom or an alkyl group. General formula (12) In the formula, _R25 represents a hydrogen atom, an amino group, an alkyl group, or an aryl group, and Y represents -O-, -S-
or

[Formula] (R ₂₆ represents a hydrogen atom, an amino group or an alkyl group). General formula (13) In the formula, R ₂₇ and R ₂₈ each represent a hydrogen atom, an acyl group, an alkyl group or an aryl group,
Y is

[Formula] or =N- (R ₂₉ represents a hydrogen atom or an alkyl group.) However, R ₂₈ and R ₂₉ may be combined to form a 5- to 6-membered ring. General formula (14) In the formula, R ₃₀ , R ₃₁ and R ₃₂ each represent a hydrogen atom, an alkyl group or an aryl group. However, R ₃₀ and R ₃₁ may be combined to form a 5- to 6-membered ring. An represents a counter anion. In general formulas (2) to (14), compounds having a nitrogen-containing heterocycle having a thiol group are preferred, and compounds represented by general formula (3) are more preferred. In the general formula (1), L represents a divalent group, and L is preferably a divalent group represented by the following general formula (15). General formula (15) (-L ₁ -) _o In the formula, L ₁ is an alkylene group having 1 to 7 carbon atoms (e.g., methylene group, ethylene group, propylene group, etc.), an arylene group (e.g., p-phenylene group,
m-phenylene group, o-phenylene group, etc.), imino group, carbonyl group, sulfonyl group, ether group, or a combination thereof (e.g. alkylenecarbonylamino group, aralkyleneamino group,
sulfonylamino group, etc.), and n represents 0 or 1. In the general formula (1), R is a hydroxyl group,
Represents a carboxyl group or a salt thereof, a sulfo group or a salt thereof, or a sulfinic acid group or a salt thereof. The compound according to the present invention represented by the general formula (1) is preferably represented by the following general formula (16). General formula (16) In the formula, L ₁ and n have the same meanings as L ₁ and n defined in the above general formula (15), and R has the same meaning as R as defined in the above general formula (1). More preferably, the compound according to the present invention represented by the general formula (16) is a compound in which the (-L ₁ -) _o R group is substituted at the para position of the phenyl group. Representative specific examples of the compound of the present invention represented by the general formula (1) (hereinafter simply referred to as the compound of the present invention) are shown below, but the compound of the present invention is not limited thereto. Compounds of the invention may be used, for example, in British Patent No. 1275701
No., U.S. Patent No. 3266897, Japanese Patent Application Publication No. 1989-89034,
It can be synthesized by referring to the methods described in JP 53-28426, JP 55-21067, JP 56-111846, and the like. The compounds of the present invention can be used alone or in combination of two or more. The amount of the compound of the present invention added varies depending on conditions such as the type, amount, and mixing ratio of the photosensitive silver halide and organic silver salt used, but is generally 10 ^-6 to 10 ^- per mol of photosensitive silver halide. ¹ mol is preferred;
More preferably, it is 10 ^-5 to ^{10 -2} mol. The compound of the present invention may be added to any of the constituent layers of the heat-developable photosensitive material, or may be added to one or more layers, but it may be added to the photosensitive layer containing photosensitive silver halide. is preferred. In this case, the timing of addition of the compound of the present invention is such that the emulsion containing the photosensitive silver halide grains used in the photosensitive layer is coated after precipitation is formed after physical ripening of the photosensitive silver halide grains used in the photosensitive layer. The addition may be carried out at any time during the period up to the time when the compound is added, and any method commonly used for adding compounds can be applied. For example, the compound of the present invention may be added in the form of an acid or salt to water or an organic solvent such as methanol and It can be dissolved in a mixed solvent of these and added to the emulsion. Further, if it can be dissolved in an organic solvent such as ethyl acetate or cyclohexane, it can be added to the emulsion after being made into an emulsion. The heat-developable photosensitive material of the present invention contains photosensitive silver halide. Examples of the photosensitive silver halide used in the present invention include silver chloride, silver bromide, silver iodide, silver chlorobromide, silver chloroiodide, silver iodobromide, and silver chloroiodobromide. The photosensitive silver halide can be prepared by any method used in the photographic field, such as a single-jet method or a double-jet method. Photosensitive silver halide emulsions containing silver can optionally be used. The light-sensitive silver halide emulsion may be chemically sensitized by any method known in the photographic art. Such sensitization methods include various methods such as gold sensitization, sulfur sensitization, gold-sulfur sensitization, and reduction sensitization. The silver halide in the above-mentioned photosensitive emulsion may be coarse grain or fine grain, but the preferred grain size is about 0.001 μm to about 1.5 μm, more preferably about 0.01 μm to about 1.5 μm. It is approximately 0.5 μm. The photosensitive silver halide emulsion prepared as described above can most preferably be applied to the heat-developable photosensitive layer which is a constituent layer of the photosensitive material of the present invention. In the present invention, as another method for preparing photosensitive silver halide, it is also possible to allow a photosensitive silver salt-forming component to coexist with an organic silver salt described below to form photosensitive silver halide in a part of the organic silver salt. . The photosensitive silver salt-forming component used in this preparation method is an inorganic halide, for example, a halide represented by MXn (where M represents an H atom, NH ₄ group or a metal atom, and X represents Cl, Br). or represents I,
n indicates 1 when M is an H atom or an NH ₄ group, and indicates the valence when M is a metal atom. As a metal atom,
Lithium, sodium, potassium, rubidium,
cesium, copper, gold, beryllium, magnesium,
Calcium, strontium, barium, zinc,
cadmium, mercury, aluminum, indium,
Lanthanum, ruthenium, thallium, germanium, tin, lead, antimony, bismuth, chromium, molybdenum, tungsten, manganese, rhenium,
Examples include iron, cobalt, nickel, rhodium, palladium, osmium, iridium, platinum, and celium. ), halogen-containing metal complexes (e.g.
K ₂ PtCl ₆ , K ₂ PtBr ₆ , HAuCl ₄ , (NH ₄ ) ₂ IrCl ₆ ,
(NH ₄ ) ₃ IrCl ₆ , (NH ₄ ) ₂ RuCl ₆ , (NH ₄ ) ₃ RuCl ₆ ,
(NH ₄ ) ₂ RhCl ₆ , (NH ₄ ) ₃ RhBr ₆ , etc.), onium halides (e.g., tetramethylammonium bromide, trimethylphenylammonium bromide, cetylethyldimethylammonium bromide, 3-methylthiazolium bromide, trimethylbenzyl quaternary ammonium halides such as ammonium bromide, quaternary phosphonium halides such as tetraethyl phosphonium bromide, tertiary sulfonium halides such as benzylethylmethylsulfonium bromide, 1-ethylthiazolium bromide, etc.), halogenation Hydrocarbons (e.g. iodoform, bromoform, carbon tetrabromide, 2-bromo-2-methylpropane, etc.), N-halogen compounds (N-chlorosuccinimide, N-bromosuccinimide, N-
Bromophthalic acid imide, N-bromoacetamide, N-iodosuccinimide, N-bromophthalazinone, N-chlorophthalazinone, N-bromoacetanilide, N,N-dibromobenzenesulfonamide, N-bromo-N-methylbenzene sulfonamide, 1,3-dibromo-4,4-dimethylhydantoin, etc.), and other halogen-containing compounds (e.g., triphenylmethyl chloride, triphenylmethyl bromide, 2-bromobutyric acid, 2-bromoethanol, etc.). be able to. These photosensitive silver halides and photosensitive silver salt-forming components can be used in combination in various methods, and the amount used is 0.001 g per m ² per layer.
It is preferable that it is ~50g, more preferably,
The amount is 0.1g to 10g. The photosensitive silver halide used in the photothermographic material of the present invention preferably has a silver iodide content of 0 mol % to 40 mol %. More preferred photosensitive silver halides include:
It is a core/shell type with a surface latent image type shell. When silver iodide is contained as the photosensitive silver halide, there are no particular restrictions on other halogen components of the photosensitive silver halide containing silver iodide, but preferred halogen components include silver iodobromide and Silver chloroiodobromide. The photosensitive silver halide containing silver iodide that is preferably used in the present invention is described by P. Grafkides,
P. Glafkides, Chimie
et Physique Photographique, Paul Montel)
(1967), G.F. Duffin, Photographic Emulsion Chemistry (The Focal Press) (GFDuffin,
Phtographic Emulsion Chmistry, The Focal
Pressf) (1966); Making and Coating Photographic Emulsions (The Focal Pressf) (1966);
Press) (VLZelikman etal, Making and
Coating Photographic Emulsion, The Focal
Press) (1964) and others. That is, any of the acid method, neutral method, ammonia method, etc. may be used, but the ammonia method is particularly suitable. Further, as a method for reacting the soluble silver salt and the soluble halogen salt, any one of a one-sided mixing method, a simultaneous mixing method, a combination thereof, etc. may be used. It is also possible to use a back mixing method in which silver halide grains are formed in an excess of silver ions. One of the simultaneous mixing methods is to arbitrarily control the pAg of the solution in the reaction vessel in which silver halide is produced.
It is also possible to use a controlled double-jet method in which the rate of addition of the silver and halogen solutions is controlled. According to this method, a so-called monodisperse silver halide emulsion having nearly uniform crystal shape and grain size can be obtained. The term "monodisperse emulsion" as used in the present invention refers to an emulsion having a grain size distribution in which the variation in the silver halide grain size contained in the emulsion is less than a certain ratio with respect to the average grain size as shown below. Since the grain size distribution of an emulsion (hereinafter referred to as a monodisperse emulsion) consisting of a group of photosensitive silver halide grains with uniform grain morphology and small grain size variations is almost a normal distribution, the standard deviation can be easily determined. , When the width of the distribution is defined by the relational expression standard deviation/average grain size x 100 = width of distribution (%), the width of the distribution of the photosensitive silver halide grains preferably used in the present invention is 15 % or less, more preferably 10% or less. A core/shell type photosensitive silver halide emulsion which is more preferably used in the present invention can be produced by using monodisperse photosensitive silver halide grains as a core and coating the core with a shell. To make the core a monodisperse silver halide grain,
Particles of desired size can be obtained by the double jet method while keeping pAg constant. Also,
Silver halide emulsions containing highly monodisperse photosensitive silver halide can be prepared by the method described in JP-A-54-48521. A preferred embodiment of the method is a method in which a potassium iodobromide-gelatin aqueous solution and an ammoniacal silver nitrate aqueous solution are added to a gelatin aqueous solution containing silver halide seed particles while changing the addition rate as a function of time. It is manufactured by. At this time, a silver halide emulsion containing highly monodisperse core silver halide grains can be obtained by appropriately selecting the time function of the addition rate, PH, pAg, temperature, etc. Monodisperse core/shell type photosensitive silver halide, which is more preferably used in the present invention, is obtained by sequentially growing shells using monodisperse core grains as described above according to the method for producing a monodisperse emulsion. A silver halide emulsion containing the following can be obtained. The heat-developable photosensitive material of the present invention has blue light, green light,
It is also possible to have a multilayer structure including each layer having sensitivity to red light, that is, a heat-developable blue-sensitive layer, a heat-developable green-sensitive layer, and a heat-developable red-sensitive layer. In addition, two or more photosensitive layers of the same color (for example, a high-sensitivity layer and a low-sensitivity layer)
It can also be divided into two. In the above cases, the blue-sensitive silver halide emulsion, green-sensitive silver halide emulsion, and red-sensitive silver halide emulsion used, respectively, are prepared by adding various spectral sensitizing dyes to the silver halide emulsion. Obtainable. Typical spectral sensitizing dyes used in the present invention include, for example, cyanine, merocyanine, complex (trinuclear or tetranuclear) cyanine, holopolar cyanine, styryl, hemicyanine, oxonol, and the like. Among the cyanine pigments, thiazoline, oxazoline, pyrroline, pyridine, oxazole, thiazole, selenazole,
Those having a basic core such as imidazole are more preferred. Such a nucleus may contain an alkyl group, an alkylene group, a hydroxyalkyl group, a sulfoalkyl group, a carboxyalkyl group, an aminoalkyl group, or an enamine group capable of forming a fused carbocyclic or heterocyclic ring. good. Further, it may be symmetrical or asymmetrical, and the methine chain or polymethine chain may have an alkyl group, phenyl group, enamine group, or heterocyclic substituent. In addition to the above-mentioned basic nucleus, merocyanine dyes have acidic nuclei such as thiohydantoin nucleus, rhodanine nucleus, oxazolidione nucleus, thiazolidinedione nucleus, barbituric acid nucleus, thiazolinthione nucleus, malononitrile nucleus, and pyrazolone nucleus. Good too. These acidic nuclei may be further substituted with an alkyl group, an alkylene group, a phenyl group, a carboxylalkyl group, a sulfoalkyl group, a hydroxyalkyl group, an alkoxyalkyl group, an alkylamine group or a heterocyclic nucleus. If necessary, these dyes may be used in combination. Furthermore, ascorbic acid derivatives, azaindene cadmium salts,
Organic sulfonic acids, etc., such as U.S. Pat. No. 2,933,390;
A supersensitizing additive that does not absorb visible light, such as those described in the specification of No. 2937089, can be used in combination. The amount of these sensitizing dyes added is 1×10 ^-4 per mole of photosensitive silver halide or silver halide forming component.
mol to 1 mol. More preferably, 1×10 ⁻⁴
mole to 1×10 ⁻¹ mole. Examples of organic silver salts used in the heat-developable photosensitive material of the present invention include Japanese Patent Publication Nos. 43-4921 and 44-26582;
No. 45-18416, No. 45-12700, No. 45-22185,
JP-A-49-52626, JP-A No. 52-31728, JP-A No. 52-
Publications such as No. 137321, No. 52-141222, No. 53-36224, and No. 53-37610, as well as U.S. Patent No.
No. 3330633, No. 3794496, No. 4105451, No.
Silver salts of aliphatic carboxylic acids such as silver laurate, silver myristate, silver palmitate, silver stearate, silver arachidonate, behen silver aromatic carboxylates such as silver α-(1-phenyltetrazolethio)acetate, silver benzoate, silver phthalate, etc., Japanese Patent Publication No. 44-26582, No. 45
-12700, 45-18416, 45-22185, JP-A-52-31728, JP-A-52-137321, JP-A-58-
Silver salts of imino groups such as those described in publications such as No. 118638 and No. 58-118639, such as silver benzotriazole, silver 5-nitrobenzotriazole,
5-chlorobenzotriazole silver, 5-methoxybenzotriazole silver, 4-sulfobenzotriazole silver, 4-hydroxybenzotriazole silver, 5-aminobenzotriazole silver, 5-carboxybenzotriazole silver, imidazole silver,
benzimidazole silver, 6-nitrobenzimidazole silver, pyrazole silver, urazole silver, 1,
2,4-triazole silver, 1H-tetrazole silver,
3-amino-5-benzylthio-1,2,4-triazole silver, saccharin silver, phthalazinone silver,
Silver phthalimide, etc. Silver 2-mercaptobenzoxazole, silver mercaptooxadiazole, silver 2-mercaptobenzothiazole, silver 2-mercaptobenzimidazole, silver 3-mercapto-4-phenyl-1,2,4-triazole,
4-hydroxy-6-methyl-1,3,3a,7
-tetrazaindene silver and 5-methyl-7-hydroxy-1,2,3,4,6-pentazaindene silver. Among the above organic silver salts, imino group silver salts are preferred, and silver salts of bezotriazole derivatives are particularly preferred, and silver salts of sulfobenzotriazole derivatives are particularly preferred. The organic silver salts used in the present invention may be used alone or in combination of two or more, and isolated ones may be used by dispersing them in a binder by appropriate means, or they may be used in a suitable form. The silver salt may be prepared in a binder and used as is without isolation. The amount of the organic silver salt used is photosensitive silver halide 1
Preferably, it is 0.01 to 500 mol per mol,
More preferably, it is 0.1 mol to 100 mol. The present invention can of course be applied to monochrome photothermographic materials, but is preferably applied to color photothermographic materials. When the heat-developable photosensitive material of the present invention is applied to color, a dye-providing substance is used. Dye-providing substances that can be used in the present invention will be explained below. The dye-donating substance may be any substance that participates in the reduction reaction of photosensitive silver halide and/or organic silver salt and can form or release a diffusible dye as a function of the reaction, depending on the reaction form. , a negative-working dye-donor that acts on a positive function (i.e., forms a negative dye image when negative-working silver halide is used) and a positive-acting dye-donor that acts on a negative function (i.e., forms a negative dye image when using negative-working silver halide). (forms a positive dye image when using negative silver halide). Negative dye-donating substances are further classified as follows.

[Table] Coupling dyes Coupling dyes Release type compounds Formation type compounds Each dye-donating substance will be further explained. Examples of the reducible dye-releasing compound include compounds represented by general formula (17). General formula (17) Car−NHSO ₂ −Dye In the formula, Car is a reducing substrate (so-called carrier) that is oxidized and releases a dye upon reduction of photosensitive silver halide and/or organic silver salt used as necessary. ), and Dye is a diffusible dye residue. Specific examples of the above-mentioned reducing dye-releasing compounds include JP-A-57-179840, JP-A-58-116537, and JP-A-59.
−60434, No. 59-65839, No. 59-71046, No.
No. 59-87450, No. 59-88730, No. 59-123837,
They are described in the specifications of No. 59-165054 and No. 59-165055, and include, for example, the following compounds. Examples of other reducible dye-releasing compounds include compounds represented by general formula (18). General formula (18) In the formula, A ₁ and A ₂ each represent a hydrogen atom, a hydroxy group, or an amino group, and Dye has the same meaning as Dye shown in general formula (17). Specific examples of the above compounds are shown in JP-A-59-124329. Examples of coupling dye-releasing compounds include compounds represented by general formula (19). General formula (19) Cp ₁ (-J-) _o1 Dye In the formula, Cp ₁ is an organic group (so-called coupler residue) that can react with the oxidized form of the reducing agent to release a diffusible dye, J is a divalent bonding group, and the bond between Cp ₁ and J is cleaved by reaction with the oxidized form of the reducing agent. n ₁ represents 0 or 1, and Dye has the same meaning as defined in general formula (17). In addition, Cp ₁ is preferably substituted with various ballast groups in order to make the coupling dye-releasing compound non-diffusible, and the ballast group has 8 or more carbon atoms ( (more preferably 12 or more) organic groups, or hydrophilic groups such as sulfo groups and carboxy groups, or 8 or more (more preferably 12 or more) carbon atoms and hydrophilic groups such as sulfo groups and carboxy groups. It is a group that both have. Another particularly preferred ballast group can include polymer chains. Specific examples of the compound represented by the above general formula (19) include JP-A-57-186744 and JP-A-57-122596.
No. 57-160698, No. 59-174834, No. 57-
They are described in the specifications of No. 224883, No. 59-159159, and Japanese Patent Application No. 59-104901, and include, for example, the following compounds. Examples of the coupling dye-forming compound include compounds represented by general formula (20). General formula (20) Cp ₂ (-F)-(-B) In the formula, Cp ₂ is an organic group (so-called coupler) that can react with the oxidized form of the reducing agent (coupling reaction) to form a diffusible dye. residue), and F
represents a divalent bonding group, and B represents a ballast group. The coupler residue represented by Cp ₂ preferably has a molecular weight of 700 or less, more preferably 500 or less, in view of the diffusibility of the dye formed. In addition, the ballast group is preferably the same as the ballast group defined in general formula (19), especially 8
A group having at least 12 carbon atoms (more preferably 12 or more) and a hydrophilic group such as a sulfo group or a carboxy group is preferable, and a polymer chain is more preferable. The coupling dye-forming compound having a polymer chain is preferably a polymer having a repeating unit derived from a monomer represented by general formula (21). General formula (21) Cp ₂ (-F)-(-Y) _l ---(-Z)-(-L) In the formula, Cp ₂ and F have the same meaning as defined in general formula (20). , Y represents an alkylene group, arylene group, or aralkylene group, and l is 0 or 1
, Z represents a divalent organic group, and L represents an ethylenically unsaturated group or a group having an ethylenically unsaturated group. Specific examples of coupling dye-forming compounds represented by general formulas (20) and (21) include
No. 59-124339, No. 59-181345, special eye 1987-
No. 109293, No. 59-179657, No. 59-181604, No. 109293, No. 59-179657, No. 59-181604, No.
It is described in the specifications of No. 59-18250b and No. 59-182507, and includes, for example, the following compounds. In more detail, the coupler residue defined by Cp ₁ or Cp ₂ in the above general formulas (19), (20) and (21) is preferably a group represented by the following general formula. In the formula, R ₃₃ , R ₃₄ , R ₃₅ and R ₃₆ are each a hydrogen atom, a halogen atom, an alkyl group, a cycloalkyl group, an aryl group, an acyl group, an alkyloxycarbonyl group, an aryloxycarbonyl group, an alkylsulfonyl group, or an aryl group. represents a sulfonyl group, a carbamoyl group, a sulfamoyl group, an acyloxy group, an amino group, an alkoxy group, an aryloxy group, a cyano group, a ureido group, an alkylthio group, an arylthio group, a carboxy group, a sulfo group, or a heterocyclic residue; Substituted with hydroxyl group, carboxy group, sulfo group, alkoxy group, cyano group, nitro group, alkyl group, aryl group, aryloxy group, acyloxy group, acyl group, sulfamoyl group, carbamoyl group, imide group, halogen atom, etc. Good too. These substituents are selected depending on the purpose of Cp ₁ and Cp ₂ , and as mentioned above, in Cp ₁ , one of the substituents is preferably a ballast group, and in Cp ₂ , it is preferable that one of the substituents is a ballast group. In order to increase the molecular weight, the substituents are preferably selected so that the molecular weight is 700 or less, more preferably 500 or less. Examples of positive dye-providing substances include oxidizable dye-releasing compounds represented by the following general formula (32). General formula (32) In the formula, W ₁ represents a collection of atoms necessary to form a quinone ring (which may have a substituent on this ring), R ₃₇ represents an alkyl group or a hydrogen atom, and E represents

[Formula] (In the formula, R ₃₈ represents an alkyl group or a hydrogen atom, and R ₃₉ represents an oxygen atom or

Represents [formula]. ) or _-SO2- , r represents 0 or 1, and Dye is the same as that defined in general formula (17). Specific examples of this compound are described in the specifications of JP-A-59-166954 and JP-A-59-154445, and include the following compounds. Another positive type dye-providing substance is a compound represented by the following general formula (33), which loses its dye-releasing ability when oxidized. General formula (33) In the formula, W ₂ represents a group of atoms necessary to form a benzene ring (which may have a substituent on the ring), and R ₃₇ , r, E, and Dye are defined by general formula (32). It is similar to what was done. Specific examples of this compound are described in the specifications of JP-A-59-124329 and JP-A-59-154445, and include the following compounds. Further examples of other positive dye-providing substances include compounds represented by the following general formula (34). General formula (34) In the above formula, W ₂ , R ₃₇ and Dye are the general formula (33)
It is the same as that defined in . Specific examples of this compound are described in JP-A-59-154445, etc., and include the following compounds. The above general formulas (17), (18), (19), (32), (33
)
In (34), the residue of the diffusible dye represented by Dye will be described in further detail. The residue of the diffusible dye preferably has a molecular weight of 800 or less, more preferably 600 or less for the sake of dye diffusivity, and includes azo dyes, azomethine dyes, anthraquinone dyes, naphthoquinone dyes, styryl dyes, nitro dyes, Examples include residues such as quinoline dye, carbonyl dye, and phthalocyanine dye. These dye residues may be in a temporary short-waveform form capable of multiple colors during thermal development or transfer. In addition, these dye residues are used for the purpose of increasing the light resistance of images, for example, in JP-A-59-48765 and JP-A-59-48765.
The chelatable dye residues described in No. 124337 are also a preferred form. These dye-providing substances may be used alone or in combination of two or more. The amount used is not limited and depends on the type of dye-providing substance, whether it is used alone or in combination, or whether the photographic constituent layer of the light-sensitive material of the present invention is a single layer or a multilayer of two or more layers. You can decide accordingly, but for example, the usage amount is 1 m ²
It can be used in an amount of 0.005g to 50g, preferably 0.1g to 10g. Any method can be used to incorporate the dye-providing substance used in the present invention into the photographic constituent layer of the heat-developable photosensitive material.
For example, after dissolving in a low boiling point solvent (methanol, ethanol, ethyl acetate, etc.) or a high boiling point solvent (dibutyl phthalate, dioctyl phthalate, tricresyl phosphate, etc.), ultrasonic dispersion,
Alternatively, after dissolving in an alkaline aqueous solution (e.g., 10% aqueous sodium hydroxide solution, etc.), it can be used by neutralizing it with a mineral acid (e.g., hydrochloric acid or nitric acid, etc.);
Alternatively, it can be used after being dispersed with a suitable polymer aqueous solution (eg, gelatin, polyvinyl butyral, polyvinyl pyrrolidone, etc.) using a ball mill. As the reducing agent used in the heat-developable photosensitive material of the present invention, those commonly used in the field of heat-developable photosensitive materials can be used, such as those disclosed in US Pat.
p-phenylenediamine type and Examples include p-aminophenol type developing agents, phosphoroamide phenol type and sulfonamide phenol type developing agents, and hydrazone type color developing agents. Also, U.S. Patent No. 3342599, U.S. Patent No. 3719492, and JP-A-53-
Color developing agent precursors described in No. 135628, No. 54-79035, etc. can also be advantageously used. As a particularly preferable reducing agent, JP-A-56-146133
Examples include reducing agents represented by the following general formula (35) described in the specification of No. General formula (35) In the formula, R ₄₀ and R ₄₁ represent a hydrogen atom or an alkyl group having 1 to 30 carbon atoms (preferably 1 to 4) that may have a substituent, and R ₄₀ and R ₄₁ represent a closed ring. May form a heterocycle. _R42 , _R43 ,
R ₄₄ and R ₄₅ each have 1 to 1 carbon atoms, which may have a hydrogen atom, a halogen atom, a hydroxy group, an amino group, an alkoxy group, an acylamido group, a sulfonamide group, an alkylsulfonamide group, or a substituent.
represents an alkyl group of 30 (preferably 1 to 4),
R ₄₂ and R ₄₀ and R ₄₄ and R ₄₁ may each be closed to form a heterocycle. M is an alkali metal atom,
Represents a compound containing an ammonium group, a nitrogen-containing organic base, or a quaternary nitrogen atom. The nitrogen-containing organic base in the above general formula (35) is an organic compound containing a basic nitrogen atom capable of forming a salt with an inorganic acid, and particularly important organic bases include amine compounds. Examples of chain amine compounds include primary amines, secondary amines, and tertiary amines, and examples of cyclic amine compounds include pyridine, quinoline, and piperidine, which are well-known examples of typical heterocyclic organic bases. , imidazole and the like. In addition, compounds such as hydroxylamine, hydrazine, and amidine are also useful as chain amines. In addition, as the salt of the nitrogen-containing organic base, inorganic acid salts of the organic base (eg, hydrochloride, sulfate, nitrate, etc.) as described above are preferably used. On the other hand, examples of the compound containing quaternary nitrogen in the above general formula include salts or hydroxides of nitrogen compounds having a tetravalent covalent bond. Next, preferred specific examples of the reducing agent represented by the general formula (35) are shown below. The reducing agent represented by the above general formula (35) can be prepared by a known method such as Heuben-Beil, Methodden,
Dell Organizien Hemy, Band XI/
2 (Houben-Weyl, Methoden der
Organischen Chemie, Band XI/2) 645−703
It can be synthesized according to the method described on p. Other reducing agents as described below can also be used. For example, phenols (e.g. p-phenylphenol, p-methoxyphenol, 2,6-di-tert-butyl-p-cresol, N-methyl-
p-aminophenol, etc.), sulfonamidophenols [e.g. 4-benzenesulfonamidophenol, 2-benzenesulfonamidophenol, 2,6-dichloro-4-benzenesulfonamidophenol, 2,6-dibromo-4-(p-aminophenol, etc.) −
toluenesulfonamido)phenol group], or polyhydroxybenzene group (e.g. hydroquinone, tert-butylhydroquinone, 2,6-dimethylhydroquinone, chlorohydroquinone,
carboxyhydroquinone, catechol, 3-carboxycatechol, etc.), naphthols (e.g. α-naphthol, β-naphthol, 4-aminonaphthol, 4-methoxynaphthol, etc.), hydroxybinaphthyls and methylene bisnaphthols [e.g. 1,1′ -dihydroxy-2,2'-binaphthyl, 6,6'-dibromo-2,2'-dihydroxy-1,1'-binaphthyl, 6,6-dinitro-
2,2'-dihydroxy-1,1'-binaphthyl,
4,4'-dimethoxy-1,1'-dihydroxy-
2,2'-binaphthyl, bis(2-hydroxy-1
-naphthyl)methane, etc.], methylenebisphenols [e.g. 1,1-bis(2-hydroxy-
3,5-dimethylphenyl)-3,5,5-trimethylhexane, 1,1-bis(2-hydroxy-3-tert-butyl-5-methylphenyl)methane, 1,1-bis(2-hydroxy- 3,5-di-tert-butylphenyl)methane, 2,6-methylenebis(2-hydroxy-3-tert-butyl-
5-methylphenyl)-4-methylphenol,
α-phenyl-α,α-bis(2-hydroxy-
3,5-di-tert-butylphenyl)methane, α
-phenyl-α,α-bis(2-hydroxy-3
-tert-butyl-5-methylphenyl)methane,
1,1-bis(2-hydroxy-3,5-dimethylphenyl)-2-methylpropane, 1,1,5,
5-tetrakis(2-hydroxy-3,5-dimethylphenyl)-2,4-ethylpentane, 2,
2-bis(4-hydroxy-3,5-dimethylphenyl)propane, 2,2-bis(4-hydroxy-3-methyl-5-tert-butylphenyl)propane, 2,2-bis(4-hydroxy- 3,5
-di-tert-butylphenyl)propane, etc.], ascorbic acids, 3-pyrazolidones, pyrazolones, hydrazones, and paraphenylenediamines. These reducing agents can be used alone or in combination of two or more. The amount of reducing agent used depends on the type of photosensitive silver halide used, the type of organic acid silver salt, and the types of other additives, but it is usually per mol of photosensitive silver halide.
It ranges from 0.01 to 1500 mol, preferably from 0.1 to 1500 mol.
It is 200 moles. Examples of the binder used in the heat-developable photosensitive material of the present invention include synthetic or natural polymers such as polyvinyl butyral, polyvinyl acetate, ethyl cellulose, polymethyl methacrylate, cellulose acetate butyrate, polyvinyl alcohol, polyvinylpyrrolidone, gelatin, and phthalated gelatin. One or more molecular substances can be used in combination. In particular, it is preferable to use gelatin or a derivative thereof in combination with a hydrophilic polymer such as polyvinylpyrrolidone or polyvinyl alcohol, and more preferably the following binder described in Japanese Patent Application No. 104249/1982. This binder includes gelatin and vinylpyrrolidone polymer. The vinylpyrrolidone polymer may be polyvinylpyrrolidone, which is a homopolymer of vinylpyrrolidone, or one or two of other monomers copolymerizable with vinylpyrrolidone.
Copolymers with the above (including graft copolymers)
It may be. These polymers can be used regardless of their degree of polymerization. The polyvinylpyrrolidone may be a substituted polyvinylpyrrolidone, with preferred polyvinylpyrrolidone having a molecular weight of 1000
~400,000. Other monomers copolymerizable with vinylpyrrolidone include (meth)acrylic acid esters such as acrylic acid, methacrylic acid and alkyl esters thereof, vinyl alcohols, vinyl imadazoles, (meth)acrylamides, and vinyl carbinol. and vinyl alkyl ethers, but it is preferable that polyvinylpyrrolidone accounts for at least 20% (by weight, the same hereinafter) of the composition. Preferred examples of such copolymers have a molecular weight of
5,000 to 400,000. Gelatin may be treated with lime or acid, and may be ossein gelatin, pigskin gelatin, hydrogelatin, or modified gelatin obtained by esterifying or phenylcarbamoylating these gelatins. In the above binder, gelatin preferably accounts for 10 to 90%, more preferably 20 to 60%, and vinylpyrrolidone accounts for 5 to 90%, more preferably 10 to 80% of the total binder amount. %. The binder may contain other polymeric substances, such as gelatin and a mixture of polyvinylpyrrolidone with a molecular weight of 1,000 to 400,000 and one or more other polymeric substances, gelatin and a polymer with a molecular weight of 5,000 to 400,000.
A mixture of the vinyl pyrrolidone copolymer and one or more other polymeric substances is preferred. Other polymeric substances that can be used include polyvinyl alcohol, polyacrylamide, polymethacrylamide, polyvinyl butyral, polyethylene glycol, polyethylene glycol ester, or proteins such as cellulose derivatives, and polysaccharides such as starch and gum arabic. Examples include natural substances. These range from 0 to 85%, preferably from 0 to 85%.
It may contain 70%. Note that the vinyl pyrrolidone polymer may be a crosslinked polymer, but in this case, it is preferable to crosslink it after coating it on the support (including the case where the crosslinking reaction progresses by leaving it naturally). The amount of binder used is usually 0.05g to 50g per square ^meter per layer, preferably 0.1g to 10g.
It is g. Examples of the support used in the heat-developable photosensitive material of the present invention include polyethylene film, cellulose acetate film, polyethylene terephthalate film, synthetic plastic film such as polyvinyl chloride, and photographic base paper, printing paper, baryta paper, and resin coated paper. Examples include paper supports such as the above, and supports prepared by providing the above-mentioned synthetic plastic film with a reflective layer. In particular, it is preferable that various thermal materials are added to the heat-developable photosensitive material of the present invention. The heat-melting material of the present invention may be any substance that promotes thermal development and/or thermal transfer, and is preferably solid, semi-solid, or liquid at room temperature (preferably, with a boiling point of 100°C at normal pressure).
(more preferably 150°C or higher) and dissolves or melts in the binder by heating, preferably urea derivatives (e.g., dimethylurea, diethylurea, phenylurea, etc.), amide derivatives ( (e.g., acetamide, benzamide, etc.), polyhydric alcohols (e.g., 1,5-pentanediol, 1,6-pentanediol, 1,2-cyclohexanediol,
pentaerythritol, trimethylolethane, etc.), or polyethylene glycols. A detailed example is described in Japanese Patent Application No. 58-104249. These thermal solvents may be used alone or in combination of two or more. In addition to the above-mentioned components, various additives may be added to the heat-developable photosensitive material of the present invention, if necessary. For example, as a development accelerator, US Pat.
3220840, 3531285, 4012260, 4060420, 4088496, 4207392 specifications, RD No. 15733, RD No. 15734, RD No. 15776,
Alkali release agents such as urea and guanidiim trichloroacetate described in JP-A-56-130745 and JP-A-56-132332, organic acids as described in JP-A-45-12700, - as described in U.S. Pat. No. 3,667,959 CO−,−
Non-aqueous polar solvent compounds having SO ₂ -, -SO- groups, melt formers described in U.S. Patent No. 3,438,776, polyalkylene glycols described in U.S. Pat. . In addition, as a color toning agent, for example, JP-A No. 46-4928,
No. 46-6077, No. 49-5019, No. 49-5020, No. 49
−91215, No. 49-107727, No. 50-2524, No.
No. 50-67132, No. 50-67641, No. 50-114217,
No. 52-33722, No. 52-99813, No. 53-1020,
No. 53-55115, No. 53-76020, No. 53-125014
No. 54-156523, No. 54-156524, No. 54-
No. 15625, No. 54-156526, No. 55-4060, No. 55
Publications such as -4061 and 55-32015, as well as West German Patent Nos. 2140406, 2147063, 2220618,
U.S. Patent No. 3080254, U.S. Patent No. 3847612, U.S. Patent No.
Phthalazinone, phthalimide, pyrazolone, quinazolinone, N-hydroxynaphthalimide, benzoxazine, naphthoxazinedione, which is a compound described in the specifications of No. 3782941, No. 3994732, No. 4123282, No. 4201582, etc. , 2,3-dihydro-phthalazinedione, 2,
3-dihydro-1,3-oxazine-2,4-dione, oxypyridine, aminopyridine, hydroxyquinoline, aminoquinoline, isocarbostyryl, sulfonamide, 2H-1,3-benzothiazine-2,4-(3H) dione, benzotriazine, mercaptotriazole, dimethylcaptotetrazapentalene, phthalic acid, naphthalic acid, phthalamic acid, etc., mixtures of one or more of these with imidazole compounds, and phthalic acid, naphthalic acid, etc. Examples include mixtures of at least one acid or acid anhydride and a phthalazine compound, and combinations of phthalazine and maleic acid, itaconic acid, quinolinic acid, gentisic acid, and the like. In addition, 3-amino-5-mercapto-
1,2,4-triazoles and 3-acylamino-5-mercapto-1,2,4-triazoles are also effective. In addition, as a stabilizer, a printout preventive agent may be used at the same time, especially after processing.
No. 45528, No. 50119624, No. 50-120328, No. 53
-Halogenated hydrocarbons described in Publication No. 46020, etc.
Specifically, tetrabromobutane, tribromoethanol, 2-bromo-2-tolylacetamide,
2-bromo 2-trisulfonylacetamide, 2
-tribromomethylsulfonylbenzothiazole, 2,4-bis(tribromomethyl)-6-methyltriazine, and the like. Also, JP-A-46-5393, JP-A-50-54329,
Post-treatment may be carried out using a sulfur-containing compound as described in each publication of No. 50-77034. Furthermore, U.S. Patent No. 3301678, U.S. Patent No. 3506444
The isothiuronium stabilizer precursor described in the specifications of U.S. Pat. No. 3,824,103 and U.S. Pat. No. 3,844,788;
It may also contain activator stabilizer precursors and the like as described in No. 4,060,420 and the like. In addition, a water release agent such as sucrose, NH ₄ Fe ₂ (SO ₄ ) _{2.12H 2} O, etc. may be used.
Heat development may be carried out by supplying water as in No. 132332. In addition to the above-mentioned components, the heat-developable photosensitive material of the present invention may further contain various additives such as spectral sensitizers, antihalation dyes, optical brighteners, hardeners, antistatic agents, plasticizers, and spreading agents. agents, coating aids, etc. are added. The heat-developable photosensitive material of the present invention basically includes (1) photosensitive silver halide, (2) reducing agent, (3) organic silver salt, (4) binder, and ( 5) It is preferable to contain a dye-providing substance. However, these do not necessarily need to be contained in a single constituent layer; for example, the photosensitive layer is divided into two layers, and the components (1), (2), (3), and (4) are placed on one side. It is contained separately in two or more photographic constituent layers as long as they are in a state where they can react with each other, such as by containing the dye-providing substance (5) in the photosensitive layer of the photosensitive layer and containing the dye-providing substance (5) in the other layer adjacent to this photosensitive layer. You can let it happen. In addition, the photosensitive layer may be divided into two or more layers, such as a high-sensitivity layer and a low-sensitivity layer, and may further include one or more photosensitive layers having different color sensitivities. It may also have various photographic constituent layers such as an overcoat layer, an undercoat layer, a backing layer, and an intermediate layer. Similar to the heat-developable photosensitive layer of the present invention, coating solutions are prepared for the protective layer, intermediate layer, undercoat layer, back layer, and other photographic constituent layers, using the dipping method, air knife method, curtain coating method, or Patent No.
Photosensitive materials can be prepared by various coating methods such as the hopper coating method described in No. 3681294. Furthermore, if desired, two or more layers can be applied simultaneously by the methods described in US Pat. No. 2,761,791 and British Patent No. 837,095. The above-mentioned components used in the photographic constituent layer of the photothermographic material of the present invention are coated on a support, and the coating thickness after drying is preferably 1 to 1000 μm, more preferably 3 to 20 μm. After the heat-developable photosensitive material of the present invention is imagewise exposed as it is, it is usually 80°C to 200°C, preferably 120°C to
Color development can be carried out by simply heating in a temperature range of 170° C. for 1 second to 180 seconds, preferably 1.5 seconds to 120 seconds. In addition, if necessary, it may be developed with a water-impermeable material in close contact with it, or it may be heated at 70°C to 70°C before exposure.
Preheating may be performed in the temperature range of 180°C. Various exposure means can be used for the photothermographic material according to the present invention. The latent image is obtained by imagewise exposure to radiation, including visible light. Light sources commonly used for regular color printing, such as tungsten lamps, mercury lamps, xenon lamps,
Laser beams, CRT beams, etc. can be used as light sources. As the heating means, all methods applicable to ordinary photothermographic materials can be used, such as contacting with a heated block or plate, contacting with a heated roller or drum, passing through a high-temperature atmosphere, etc. Alternatively, it is also possible to use high frequency heating, or furthermore, to provide a conductive layer in the photosensitive material of the present invention or in the image receiving layer (element) for thermal transfer, and to utilize the Joule heat generated by electricity or a strong magnetic field. The heating pattern is not particularly limited;
Although it is possible to preheat in advance and then reheat it, to heat it at a high temperature for a short time, or at a low temperature for a long time, continuously raising, lowering, or repeating it, and even discontinuously heating, there is a simple pattern. preferable. Alternatively, a method in which exposure and heating proceed simultaneously may be used. The image-receiving member used in the present invention only needs to have the function of receiving the dye released or formed by thermal development, and can be used as a mordant used in dye diffusion transfer type light-sensitive materials or as described in JP-A No. 57-207250. It is preferable to use a heat-resistant organic polymer material having a glass transition temperature of 40° C. or higher and 250° C. or lower. Specific examples of the mordant include nitrogen-containing secondary and tertiary amines, nitrogen-containing heterocyclic compounds, quaternary cationic compounds thereof, US Pat. No. 2,548,564,
Vinylpyridine polymers and vinylpyridinium cationic polymers disclosed in US Pat.
Polymers containing dialkylamino groups disclosed in U.S. Pat. No. 2,675,316; aminoguanidine derivatives disclosed in U.S. Pat. No. 2,882,156;
covalently reactive polymers as described in No. 137333;
US Patent No. 3625694, US Patent No. 3859096, British Patent No.
Mordant capable of crosslinking with gelatin etc. disclosed in No. 1277453 and No. 2011012, US Patent No. 3958995
No. 2721852 and No. 2798063; water-insoluble mordants disclosed in JP-A-50-61228; U.S. Patent No. 3788855;
West German Patent Application (OLS) No. 2843320, JP-A-53-
No. 30328, No. 52-155528, No. 53-125, No. 53-
No. 1024, No. 54-74430, No. 54-124726, No. 54-124726, No. 54-74430, No. 54-124726, No.
55-22776, U.S. Patent No. 3642482, U.S. Patent No. 3488706
No. 3557066, No. 3271147, No. 3271148,
Special Publication No. 55-29418, No. 56-36414, No. 57-
Various mordants disclosed in No. 12139 and RD12045 (1974) can be mentioned. Particularly useful mordants are polymers containing ammonium salts, such as those containing quaternary amino groups as described in US Pat. No. 3,709,690. Polymers containing ammonium salts include, for example, polystyrene copolymer.
In N,N,N-tri-n-hexyl-N-vinylbenzylammonium chloride, the ratio of styrene and vinylbenzylammonium chloride is:
The ratio is 1:4 to 4:1, preferably 1:1. A typical image-receiving layer for dye diffusion transfer is obtained by coating a polymer containing an ammonium salt mixed with gelatin on a support. Examples of the heat-resistant organic polymer substances include polystyrene with a molecular weight of 2,000 to 85,000, polystyrene derivatives having a substituent having 4 or less carbon atoms, polyvinylcyclohexane, polyvinylbenzene, polyvinylpyrrolidone, polyvinylcarbazole, polyallylbenzene, and polyvinyl alcohol. , polyacetals such as polyvinyl formal and polyvinyl butyral, polyvinyl chloride, chlorinated polyethylene, polytrichlorinated fluorinated ethylene, polyacrylonitrile, poly-N,N-dimethylacrylamide, p-cyanophenyl group, pentachlorophenyl group, and 2, Polyacrylate with 4-dichlorophenyl group, polyacryl chloroacrylate, polymethyl methacrylate, polyethyl methacrylate, polypropyl methacrylate, polyisopropyl methacrylate, polyisobutyl methacrylate, poly-tert-butyl methacrylate,
Polyesters such as polycyclohexyl methacrylate, polyethylene glycol dimethacrylate, poly-2-cyano-ethyl methacrylate, polyethylene terephthalate, polysulfone,
Examples include polycarbonates such as bisphenol A polycarbonate, polyanhydrides, polyamides, and cellulose acetates.
Also, Polymer Handbook 2nd Edition (Polymer Handbook 2nd Edition)
Handbook 2nd ed.), J. Brandlap,
Edited by E.H. Inmargt (J.Brandrup,
EHImmergut), John Willie &
Synthetic polymers with glass transition temperatures of 40° C. or higher, such as those described in John Wiley & Sons, are also useful. These polymeric substances may be used alone, or may be used in combination of two or more or as a copolymer. Particularly useful polymers include cellulose acetate, such as triacetate and diacetate;
Polyamides made from combinations such as heptamethylene diamine and terephthalic acid, fluorene dipropylamine and adipic acid, hexamethylene diamine and diphenic acid, hexamethylene diamine and isophthalic acid, diethylene glycol and diphenylcarboxylic acid, bis-p-carboxyphenoxybutane Examples include polyester, polyethylene terephthalate, polycarbonate, and vinyl chloride made of a combination of ethylene glycol and ethylene glycol. These polymers may be modified. For example, cyclohexanedimethanol, isophthalic acid, methoxypolyethylene-glycol, 1,2
Polyethylene terephthalate using -dicarbomethoxy-4-benzenesulfonic acid or the like as a modifier is also effective. Among these, particularly preferred are the layer made of polyvinyl chloride described in Japanese Patent Application No. 58-97907, and the layer made of polycarbonate and a plasticizer described in Japanese Patent Application No. 128600-1982. The above polymer is used by dissolving it in a suitable solvent and coating it on a support to form an image receiving layer, or by laminating a film-like image receiving layer made of the above polymer on a support, or by coating it on a support. It is also possible to constitute the image-receiving layer by a member (for example, a film) made of the above-mentioned polymer alone (also used as an image-receiving layer support). Furthermore, the image-receiving layer may be constructed by providing an opaque layer (reflective layer) containing titanium dioxide or the like dispersed in gelatin on the image-receiving layer on a transparent support. This opaque layer provides a reflective color image when the transferred color image is viewed from the transparent support side of the image-receiving layer. [Specific Examples of the Invention] Hereinafter, the present invention will be specifically explained using Examples, but the embodiments of the present invention are not limited to these. Example 1 [Preparation of Emulsion A] Emulsion A was prepared by the following method. Unexamined Japanese Patent Publication 1987
-92523 and 57-92524 using the mixer shown in the specifications, ossein gelatin 20
g, A in which 1000 ml of distilled water and ammonia were dissolved
To the solution, 500 ml of an aqueous solution B containing 130.9 g of potassium bromide and 500 ml of an aqueous solution C containing 1 mol of silver nitrate and ammonia were simultaneously added while keeping the pAg constant. The shape and size of the emulsion grains to be prepared were adjusted by controlling the pH, pAg, and addition rate of solutions B and C to obtain a silver bromide emulsion. The silver halide grains of the silver bromide emulsion obtained were octahedral grains with an average grain size of 0.3 μm and a monodispersity of 8%. This emulsion was washed with water and desalted. Emulsion yield is 800
It was hot in ml. [Preparation of emulsions B and C] Two types of emulsions B and C with different silver iodide contents
was prepared by the following method. Add potassium iodide and potassium bromide to a specified concentration (for emulsion B, potassium iodide 6.64 g, Potassium bromide 130.9g,
For Emulsion C, Solution B consists of an aqueous solution containing 11.62 g of potassium iodide and 130.9 g of potassium bromide.
500 ml and 500 ml of solution C consisting of an aqueous solution containing 1 mol of silver nitrate and ammonia were simultaneously added while keeping the pAg constant. The shape and size of the emulsion grains to be prepared were adjusted by controlling the pH, pAg, and addition rates of solutions B and C to obtain a silver iodobromide emulsion.
In this way, emulsions B and C, which had the same regular octahedral shape but differed only in silver iodide content, were prepared.
(The monodispersity of each emulsion was 9%) These emulsions were washed with water and desalted. The yield of each emulsion was 800ml. [Preparation of Emulsions D, E and F] Three types of core/shell type emulsions having different silver iodide contents and grain sizes were prepared by the following method. At 50℃, JP-A-57-92523, JP-A No. 57-92523;
Using the mixing agitator shown in specification No. 92524,
Add potassium iodide and potassium bromide to a solution A in which 20 g of ossein gelatin, 1000 ml of distilled water and ammonia are dissolved (potassium iodide for emulsion D).
11.62g, potassium bromide 130.9g, potassium iodide 11.62g, potassium bromide 130.9g for emulsion E, potassium iodide 33.2g, potassium bromide for emulsion F
119.0g) of an aqueous solution containing 500ml of solution B, an aqueous solution containing 1 mole of silver nitrate, and ammonia.
500 ml of Solution C was added at the same time while keeping the pAg constant. The shape and size of the particles of the core emulsion to be prepared were adjusted by controlling the pH, pHg, and the addition rate of Solutions B and C. In this way, core emulsions having the same regular octahedral shape but different grain sizes and silver iodide contents were prepared. (The monodispersity of each core emulsion was 8%.) Next, the silver halide grains obtained above were used as cores and coated with a silver halide shell in the same manner as described above. Core/shell type emulsions D to F having the same regular octahedral shape but different grain sizes and silver iodide contents were prepared. Wash each of these emulsions with water, desalt them, and add 800ml.
And so. Table 1 summarizes the properties of the six types of emulsions A to F prepared in this manner.

【table】

[Table] Thickness
Emulsion Core Shell (μm) (μm)
D 7 2 0.04 0.3
E 7 2 0.05 0.5
F 20 4 0.04 0.3
[Preparation of photosensitive silver halide dispersion] The six types of silver halide emulsions prepared above were mixed with the following sensitizing dye (1) and 4-hydroxy-6-methyl-1,3,3a,7-tetrazaindene. A photosensitive silver halide dispersion having the following composition was prepared by sulfur sensitization treatment with sodium thiosulfate in the presence of . Silver halide (converted to silver) 381g Gelatin 85g/2820ml [Preparation of organic silver salt dispersion] - Obtained by reacting 5-methylbenzotriazole and silver nitrate in a water-alcohol mixed solvent.
28.8 g of 5-methylbenzotriazole silver, 16.0 g of poly(N-vinylpyrrolidone) and 1.33 g of 4-sulfobenzotriazole sodium salt were dispersed in an alumina ball mill to adjust the pH to 5.5 to prepare 200 ml of an organic silver salt dispersion. [Preparation of dye-providing substance dispersion] Add 35.5 g of the exemplary dye-providing substance to 200 ml of ethyl acetate.
The mixture was mixed with 720 ml of an aqueous gelatin solution containing 124 ml of a 5% by weight aqueous solution of Alkanol PH after distillation
5.5 and the volume was adjusted to 795 ml to prepare a dye-providing substance dispersion (1). [Preparation of developer dispersion] 23.3 g of exemplary reducing agent (R-11), the following development accelerator
1.10g, poly(N-vinylpyrrolidone) 14.6g,
Dissolve 0.50g of the following fluorine-based surfactant in water and adjust the pH.
5.5 and the volume was adjusted to 250 ml to prepare a developer dispersion. [Preparation of heat-developable photosensitive material] 6.00 ml of the three photosensitive silver halide dispersions A, C, and D prepared above, 12.5 ml of the organic silver salt dispersion,
Dye-donor dispersion 39.8ml, developer dispersion 12.5ml
A 2×10 ^-2 molar aqueous solution of the compound shown in Table 2 below was mixed as an antifoggant, and a hardening agent {tetra(vinylsulfonylmethyl)methane and taurine at 1:1 (weight ratio) 2.50 ml of a hardening agent solution in which tetra(vinylsulfonylmethyl)methane is 3% by weight by dissolving it in a 1% aqueous solution of phenylcarbamoylated gelatin, and using polyethylene glycol 300 (Kanto) as a hot solvent. After adding 3.80g of (manufactured by Kagakusha),
The amount of silver is 1.76g/180μm thick undercoated photographic polyethylene terephthalate film.
^m2 , and a protective layer made of a mixture of the phenylcarbamoylated gelatin and poly(N-vinylpyrrolidone) was provided thereon to obtain heat-developable photosensitive material samples 1 to 15 shown in Table 2. Ta. [Preparation of image-receiving element] Polyvinyl chloride (n=
An image receiving element was prepared by applying a tetrahydrofuran solution of 1100 (Wako Pure Chemical Industries, Ltd.) to give a polyvinyl chloride content of 12 g/m ² . The heat-developable photosensitive material prepared above was exposed to 1600C.MS through a step wedge, and then exposed to light at 150C.MS for 1 minute together with the image-receiving element in a heat development machine (Developer Module 277, manufactured by 3M). After thermal development, the photosensitive material and image receiving element were immediately separated, and a magenta step wedge negative image was obtained on the polyvinyl chloride surface of the image receiving element. The green reflection density of the obtained negative image was measured using a densitometer (PDA-65, manufactured by Konishiroku Photo Industry Co., Ltd.). The maximum density, relative sensitivity and minimum density (fog) obtained are shown in Table 2 below.

[Table] However, the structural formula of the comparative antifoggant (a) used in Table 2 is as follows. In addition, in Table 2, relative sensitivity refers to fog +
It is the reciprocal of the exposure amount that gives a density of 0.3, and is expressed as a relative value with the value of sample No. 1 as 100. From the results in Table 2, the minimum density (fog) is lower in the comparison samples to which antifoggant was added (Nos. 4 to 5) compared to the samples to which no antifoggant was added (Nos. 1 to 3). On the other hand, in the samples to which the compound of the present invention was added (Nos. 6 to 15), the minimum concentration was lowered without reducing the maximum concentration much (especially in Nos. 9 to 15, there was no effect). It can be seen that the compounds of the present invention function as effective antifoggants. It can also be seen that the sensitivity is also better than that of the comparison sample. Furthermore, focusing on the characteristics of the emulsion, the sample of the present invention (No. 10) using a silver bromide emulsion was compared to the sample of the present invention using a silver iodobromide emulsion containing silver iodide. (No. 11) showed a significant increase in sensitivity, and samples of the present invention (Nos. 12 to 15) using silver iodobromide core/shell emulsions showed further improvement in sensitivity. It can be seen that the compounds of this invention act as effective antifoggants. Example 2 [Preparation of photosensitive silver halide dispersion] To the emulsions A, B and F prepared in Example 1, the following image-sensitive dye (2) and 4-hydroxy-6-
A photosensitive silver halide dispersion having the following composition was prepared by sulfur sensitization treatment with sodium thiosulfate in the presence of methyl-1,3,3a,7-tetrazaindene. Silver halide (in terms of silver) 381g Gelatin 85g/2820ml [Preparation of dye-donor dispersion] 30.0g of the exemplary dye-donor substance was dissolved in 30.0g of tricresyl phosphate and 90.0ml of ethyl acetate, and the same as in Example 1 was prepared. , gelatin aqueous solution containing surfactant
After mixing with 460 ml and dispersing with an ultrasonic homogenizer, ethyl acetate was distilled off, and water was added to make 500 ml to prepare a dye-providing substance dispersion (2). [Preparation of heat-developable photosensitive material] Photosensitive silver halide dispersion prepared above 40.0
ml, 25.0 ml of the organic silver salt dispersion prepared in Example 1,
50.0 ml of the dye-providing substance dispersion prepared above and an antifoggant were mixed as shown in Table 3, and 4.20 g of polyethylene glycol 300 (manufactured by Kanto Kagaku Co., Ltd.) was added as a heat solvent, and the same hardening agent as in Example 1 was added. solution
3.00 ml and 20.0 ml of a 10 wt.% water-alcoholic solution of guanidine trichloroacetic acid and 20.0 ml of a 10 wt.% methanol solution of 2,6-dichloro-p-aminophenol to form an undercoat with a thickness of 180 μm.
The photothermographic materials Samples 16 to 33 shown in Table 3 below were obtained by coating the photothermographic materials onto a photographic polyethylene terephthalate film at a silver content of 2.50 g/m ² . [Preparation of image-receiving element] The following layers were sequentially coated on a transparent polyethylene terephthalate film having a thickness of 100 μm to prepare an image-receiving element. (1) A layer made of polyacrylic acid. (7.00g/m ² ) (2) A layer made of cellulose acetate. (4.00 g/m ² ) (3) A layer consisting of a 1:1 copolymer of styrene and N-benzyl-N,N-dimethyl-N-(3-maleimidopropyl) ammonium chloride and gelatin. Copolymer 3.00 g/m ² Gelatin 3.00 g/m ² ) The photothermographic material samples 16 to 33 were exposed to 1600 C.MS through a step wedge;
After heating on a heat block at 150℃ for 1 minute,
The image-receiving element of Example 2 which had been immersed in water was laminated together, pressure bonded at 50° C. and 500 g/cm 2 to 800 g/cm ² for 30 seconds, and then quickly peeled off. The transmission density of the yellow transparent image obtained on the surface of the image-receiving element is calculated using the density system (PDA
-65 (manufactured by Konishiroku Photo Industry Co., Ltd.). The maximum and minimum densities (fog) and relative sensitivities obtained are shown in Table 3 below. The antifoggant (a) used in Table 3 is the same as that used in Example 1. Further, the relative sensitivity is expressed as a relative value with the value of sample No. 16 as 100, which is the reciprocal of the exposure amount that gives a density of fog + 0.3.

[Table] As is clear from the results in Table 3, even when using a dye-donating substance, which is a dye-releasing compound that releases a hydrophilic dye by reacting with photosensitive silver halide upon heating, the same results as in Example 1 were obtained. It can be seen that the following can be obtained. That is, the sample without antifoggant added (No.
16-19), the sample (No. 20) to which the comparative antifoggant was added showed almost no effect of lowering the minimum density (fog), whereas the sample (No. 20) to which the compound of the present invention was added showed almost no effect in lowering the minimum density (fog) Nos. 21 to 23), the minimum concentration was lowered without reducing the maximum concentration too much, and (especially No.
26 to 33) It can be seen that the compound of the present invention works as an effective antifoggant. Furthermore, it can be seen that the sensitivity is also better than that of the comparative sample. Furthermore, focusing on the characteristics of the emulsion, the sample of the present invention using a silver iodobromide emulsion containing silver iodide was compared to the sample of the present invention using a silver bromide emulsion (No. 27). (Nos. 28, 29, 32, 33) showed a significant increase in sensitivity, and the samples of the present invention (Nos. 30, 31) using silver iodobromide core/shell emulsions had even higher sensitivity. It can be seen that the compound of the present invention functions as an effective antifoggant.

Claims (1)

[Scope of Claims] 1. A heat-developable photosensitive material having at least a photosensitive silver halide, an organic silver salt, a reducing agent, and a binder on a support, wherein the photosensitive silver halide is a core/shell type photosensitive halogenated material. silver, and the heat-developable photosensitive material further contains a compound represented by the following general formula (1), and the compound represented by the general formula (1) is added after completion of chemical sensitization of the photosensitive silver halide. A heat-developable photosensitive material characterized by: General formula (1) Represents an acid group or its salt. 2 In the compound represented by the general formula (1), X
2. The photothermographic material according to claim 1, wherein the development inhibitor residue is a compound having an -SH group. 3 In the compound represented by the general formula (1), X
2. The photothermographic material according to claim 1, wherein the development inhibitor residue is a nitrogen-containing heterocyclic residue, and R is a sulfo group or a salt thereof.