JPH0345820B2 - - Google Patents

Description

[Detailed description of the invention]

[Technical Field] The present invention relates to a diffusion transfer type heat-developable photosensitive material, and more particularly to a heat-developable photosensitive material that can produce high-contrast black-and-white images with little printout through simple processing. [Prior art] The conventionally known photographic method using photosensitive silver halide is superior to other photographic methods in terms of photosensitive gradation, image preservation, etc., and has been the most widely put into practical use. It is a photographic method. However, since this method uses wet processing for processing steps such as development, fixing, and water washing, processing is time-consuming and labor-intensive, and there are concerns about pollution to the human body due to processing chemicals, and There are many problems, such as the inevitable contamination of workers by the above-mentioned chemicals and the consideration of pollution caused by waste liquid. Therefore, there has been a demand for the development of a photosensitive material that uses photosensitive silver halide and can be dry processed. Many proposals have been made regarding the above-mentioned dry processing photographic method, and among them, heat-developable photosensitive materials in which the developing step can be performed by heat treatment have attracted attention as photosensitive materials that meet the above-mentioned requirements. Regarding such heat-developable photosensitive materials, for example, Japanese Patent Publication No. 43-4921 and Japanese Patent Publication No.
No. 43-4924 discloses a photosensitive material comprising an organic silver salt, silver halide, and a reducing agent. In these heat-developable photosensitive materials, a latent image is formed on silver halide by exposure, and this latent image is used as a catalyst nucleus to carry out an oxidation-reduction reaction using an organic silver salt and a reducing agent during heating, and a silver image is formed by a so-called dry physical development process. This is what you get. These heat-developable photosensitive materials are usually manufactured in such a way as to omit the fixing process to remove undeveloped silver salts, so the photo-sensitive materials after heat development are exposed to indoor light. If left for an extended period of time, the silver halide and undeveloped organic silver salt will gradually darken due to light, resulting in undesirable staining. This contamination is Post−Processing Print−out
This is called (baking out after processing).
This development significantly impairs the image quality of the heat-developable photosensitive material after processing. Therefore, many means have been proposed to reduce print-out after processing of heat-developable photosensitive materials. For example, the method using a mercury salt described in U.S. Pat. No. 3,589,903;
Publication No. 45228, U.S. Patent No. 3707377, U.S. Patent No. 3767394
No. 3874946, No. 3767394, No. 3874946,
2-tribromomethylsulfonylbenzthiazole, 2,2-dibromo-2- which is a compound described in the specifications of No. 3955982 and No. 4009039.
Phenylsulfonylacetamide, 2-bromo-
2-p-Tolylsulfonylacetamide, N-chloro-oxazolinone, 4-methyl-N-bromo-2-oxazolinone, α-bromo-p-nitrotoluene, 2-bromo-p-phenylsulfonylacetamide, 1,2,3 , 4-tetrabromobutane, tribromoquinaridine, N,N'-dichloro-1,2-ethylenebis(benzamido)-tribromoethanol, tribromoethylbenzenesulfonate, etc., a method using a compound that releases a halogen radical, United States Patent No. 3700457, same
No. 3839041, No. 3997346, No. 3893859, No.
1-hydroxy-4-(1-phenyl-5-tetrazolylthio)-2-(2'-n-tetradecyloxy)naphthanilide, 5-acetyl-4-methyl, which is a compound described in each specification of No. 4002479. -2-(3-oxobutylthio)thiazole,
5-acetyl-4-methyl-4-thiazoline-2
-thione, 1-cyclohexylcarbamoyl-4
-phenyl-2-tetrazoline-5-thione,
Methods using sulfur-containing compounds represented by mercaptans, thiones, and thioethers such as N,N'-hexamethylenebis(1-carbamoyl-4-phenyl-2-tetrazoline-5-thione) are known. No matter which method is used, it is not possible to sufficiently reduce print-out after processing, and it has not yet been possible to obtain a photothermographic material having sufficient stability after processing. [Object of the Invention] Therefore, an object of the present invention is to provide a photothermographic material having excellent storage stability after processing. [Summary of the Invention] The above object of the present invention is to provide a diffusion transfer type heat-developable photosensitive material having on a support a) a photosensitive silver halide, b) an organic silver salt, c) a diffusible black dye-providing substance, and d) a binder. This is achieved through materials. That is, by diffusively transferring the diffusible black dye released or formed by thermally developing the photosensitive material to an image-receiving layer capable of receiving the dye, a black and white image with high contrast and no printout can be obtained. [Structure of the Invention] In the present invention, "diffusivity" is not limited to the case where it sublimes or vaporizes and exhibits thermal mobility when heated, but also means that it melts by itself or dissolves in a certain substance when heated. It refers to exhibiting thermal mobility by As the substance that donates, releases or forms the diffusible black pigment used in the present invention, JP-A-54-
No. 31737, U.S. Patent No. 4126461, Japanese Patent Application Publication No. 1983-
No. 12641, No. 58-5732, No. 52-42725, No. 53-
46029, US Patent No. 3674490, UK Patent No.
2044474, etc., which release or form a diffusible black pigment, are advantageously used;
No. 12641, No. 56-38037, No. 57-11345, No. 57
The black pigment-forming substances described in Japanese Patent Nos. 84447 and 57-84449 can also be advantageously used. Among them, resorcinol derivatives such as those described in U.S. Pat.
Preferred are m-aminophenol derivatives such as those described in Japanese Patent Laid-Open Nos. 52-42725, 53-46029, and 54-31737, and bispyrazolone compounds such as those described in JP-A-55-105248. In addition, these black pigment-forming compounds include ordinary phenols,
Naphthols, pyrazolones, closed ketomethylene compounds, etc. For example, US Patent No. 3531286, US Patent No. 3761270
No. 4021240, Research Disclosure (hereinafter referred to as RD) No. 15108, Japanese Patent Application Publication No. 1983-
Compounds described in No. 40551 and JP-A-58-129516 by the present applicant may be used in combination. Diffusible black pigment-forming compounds and release compounds used in the present invention are shown below, but the present invention is not limited to these compounds. As the diffusible black pigment-forming substance used in the present invention, various color image-forming substances can be used as described above, but it is preferable that the color image has a substantially black tone, and D _B /D _R = 0.5~1.5 and
It is preferable that D _G /D _R be in the range of 0.5 to 1.5 (D _B , D _G , and D _R refer to blue density, green density, and red density, respectively). Among them, the black dye image-forming substances used in the present invention include JP-A-52-42725, JP-A-53-46029, and JP-A-54.
-31737, JP-A-55-105248, U.S. Patent No.
Those described in No. 4126461 and JP-A No. 58-5732 are preferably used, but specifically, the following general formula
Compounds represented by (1) are preferred. General formula (1) In the formula, R ₁ and R ₂ are a hydrogen atom, an alkyl group,
It represents an alkenyl group or an aralkyl group (each may be substituted), and either R ₁ or R ₂ is preferably a hydrogen atom. R ₃ and R ₄ are each a hydrogen atom, a halogen atom, a sulfo group, or another monovalent organic group (e.g., a hydroxy group, a substituted or unsubstituted alkyl group, an alkoxy group,
represents a monovalent group selected from amino groups, etc. X,
Y is a hydrogen atom, a halogen atom, a sulfo group, or a monovalent organic group (for example, a substituted or unsubstituted alkoxy group, an allyloxy group, an acyloxy group,
arylthio group, arylseleno group, cyclic imido group, carbamoyloxy group, phenylsulfonyloxy group, arylazo group, etc.), and X and Y represent an aromatic primary amine color developing agent. A group capable of leaving during the coupling reaction with can be arbitrarily selected. The unsubstituted alkyl group represented by R ₁ and R ₂ is preferably a linear or branched alkylalkenyl group having 1 to 12 carbon atoms, more preferably a carbon number such as methyl, ethyl, or propyl. up to 4 alkylalkenyl groups. Examples of substituted alkyl groups include alkyl having 1 to 4 carbon atoms or 4 carbon atoms.
An alkyl group having an alkyl substituent up to or substituted with an unsubstituted arylcarbamoyl group is preferable. The aralkyl group represented by R ₁ and R ₂ is preferably an unsubstituted aralkyl group, such as an aralkyl group in which the alkylene chain has 1 to 4 carbon atoms, such as a benzyl group or a phenethyl group. Other preferred black pigment-forming substances include the following general formula:
It is expressed as (2). General formula (2) In the formula, R ₅ and R ₆ are a hydrogen atom or a chain or cyclic alkyl group, and may be substituted. Examples of these include methyl, ethyl, isopropyl, t-butyl, β-cyanoethyl,
Alkyl groups having 8 or less carbon atoms, such as β-chloroethyl, benzyl, and nitrobenzyl, are preferred. moreover
R ₅ and R ₆ each represent a substituted or unsubstituted aryl group, such as phenyl, α- or β-naphthyl group, alkylalkoxy group or aryloxy group having 4 or less carbon atoms, acylamino group having 5 or less carbon atoms,
Preferred are aryl groups substituted with groups such as carbamoyl, alkylcarbamoyl having 4 or less carbon atoms, dialkylcarbamoyl, arylcarbamoyl, alkylsulfonamide having 4 or less carbon atoms, arylsulfonamide, cyano, and nitro.
R ₅ and R ₆ are heterocyclic groups (nitrogen atom as a hetero atom,
5- or 6-membered heterocycles containing oxygen atoms, sulfur atoms, etc., fused heterocycles such as pyridyl, quinolyl, furyl, benzthiazolyl, oxazolyl,
(imidazolyl, etc.), or a heterocyclic group substituted with the substituents listed for the aryl group above. R ₇ and R ₈ each represent an alkyl group, a substituted alkyl group, an aryl group, a substituted aryl group, a heterocyclic group, or a substituted heterocyclic group having the same meaning as R ₅ and R ₆ above. R ₇ and R ₈ are substituted oxy groups (e.g. methoxy group, ethoxy group, phenoxy group,
tolyloxy group, etc.) or an amino group (e.g., substituted or unsubstituted N-alkylamino, cycloalkylamino, N,N-dialkylamino, N
-alkyl-N-arylamino, N-arylamino group, etc.), and these alkyl groups are preferably alkyl groups having 8 or less carbon atoms, and the aryl groups include the substituted and unsubstituted groups mentioned in R ₅ and R ₆ . Aryl groups are preferred. R ₉ represents an alkyl group, substituted alkyl group, aryl group, substituted aryl group having the same meaning as R ₅ and R ₆ described above, or an amino group having the same meaning as R ₇ and R ₈ . R ₉ can also be a halogen atom (e.g. fluorine,
(chlorine, bromine, iodine atom) or an amide group (eg, acetamide, benzamide group, etc.). R ₁₀ , R ₁₁ and R ₁₂ each represent the above-mentioned halogen atom, alkyl group, aryl group, substituted oxy group, amino group, amide group or hydrogen atom, and preferably R ₁₀ represents a halogen atom, an alkyl group, It is an aryl group, a substituted oxy group or an amino group, and R ₁₁ and R ₁₂ are hydrogen atoms. These compounds can be easily obtained by reacting aryl aldehyde and 5-pyrazolone according to the method described in JP-A-51-105820. Still another preferred black pigment-forming substance is represented by the following general formula (3). General formula (3) In the formula, _R13 is a hydroxy group, a halogen atom (fluorine, chlorine, bromine, iodine), a sulfonyl group, a nitro group, a cyano group, an amino group, an alkyl group having 1 to 20 carbon atoms (a substituted alkyl group such as haloalkyl) ), alkoxy group having 1 to 20 carbon atoms, 1 to 20 carbon atoms
phenyl and naphthyl groups, substituted or unsubstituted with groups such as 20 alkylthio groups and alkoxycarbonyl groups having 2 to 21 carbon atoms; alkyl groups having 1 to 20 carbon atoms; haloalkyl (e.g. fluorine-substituted) groups; Heterocyclic groups containing a ring system of 5 to 10 ring atoms and heteroatoms such as oxygen, nitrogen and sulfur (e.g. furyl, quinolylthienyl, etc.), especially alkyl groups having 1 to 8 carbon atoms, haloalkyl groups or A phenyl group, an alkyl group having 1 to 4 carbon atoms, an alkoxy group, or a phenyl group substituted with a halogen atom. As for L-
NHCO−, −CONH−, −NHCONH−, −
It represents NHSO ₂ - or -COO-, with -NHCO- or -COO- being particularly preferred.
Further, R ₁₄ and R ₁₆ each represent a hydrogen atom, a halogen atom, or a sulfo group, and R ₁₅ represents a relatively low molecular weight, non-bulky group, such as lower alkyl having 1 to 4 carbon atoms such as methyl, ethyl, propyl, and butyl. and halogen substituents such as chlorine and fluorine. Further, the black pigment-forming compound may be a substance that itself has reducing properties and forms a black pigment upon oxidation. Specific examples of black pigment-forming substances include the following compounds. The amount of the black pigment-forming substance used is 1 part organic silver salt.
The amount per mole is 0.1 to 10 mol, preferably 0.2 to 1 mol. These dye-providing substances such as black dye-forming compounds can be added to the heat-developable photosensitive material of the present invention by various methods. For example, it can be mixed and dissolved as it is in the composition for a heat-developable photosensitive layer, for example, it can be dissolved in water or various organic solvents and then mixed, or it can be pulverized and dispersed by a mechanical pulverization means such as a ball mill, a sand mill, or an ultrasonic wave. There are methods such as post-mixing. It is possible to adopt the method of dispersing the protect in a hydrophilic binder as described in Japanese Patent Application No. 57-229673 filed by the present applicant, or the method of adding it by a fissure dispersion as described in Japanese Patent Application No. 58-129516. , and various other methods known in the art can be used. 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-
No. 137321, No. 52-141222, No. 53-36224, No.
53-37610, U.S. Patent No. 3330633, U.S. Patent No. 3794496
No. 4105451, No. 4123274, No. 4168980 and other publications and specifications, i.e., silver salts of aliphatic carboxylic acids such as silver laurate, silver myristate, silver palmitate, stearin. Silver acid, silver arachidonic acid, silver behenate, α-
(1-phenyltetrazolethio)silver acetate, etc.
Silver salts of aromatic carboxylic acids, such as silver benzoate and silver phthalate; silver salts of organic compounds having imino groups, such as silver benzotriazole, silver nitrobenztriazole, silver chlorbenztriazole, silver methylbenzotriazole, and silver hydroxybenztriazole; , carboxybenztriazole silver,
Silver salts of compounds having mercapto or thione groups, such as aminobenztriazole silver, sulfobenztriazole silver, saccharin silver, phthalazinone silver, phthalimide silver, etc., such as 2-mercaptobenzoxazole silver, mercaptooxadiazole silver, 2-mercaptobenzothiazole silver, 2-mercaptobenzimidazole silver, 3-mercapto-4-phenyl-1,2,4-triazole silver,
Others 4-hydroxy-6-methyl-1,3,
3a,7-tetrazaindene silver, 5-methyl-7
-Hydroxy-1,2,3,4,6-pentazaindene silver and the like. Among the above organic silver salts, silver salts and imino silver salts of aliphatic carboxylic acids are preferred, particularly those having 18 to 18 carbon atoms.
Silver salts of long-chain aliphatic carboxylic acids of 33, triazoles and benztriazoles are preferred. The amount of the organic silver salt used is 0.05 g to 1 m ² of support.
The amount is 10.0 g, preferably 0.2 g to 2.0 g. The photosensitive silver halide used in the present invention includes silver chloride, silver bromide, silver iodide, silver chlorobromide, silver chloroiodide, silver iodobromide, silver chlorobromoiodide, and mixtures thereof. can give. The photosensitive silver halide can be prepared by any method known in the photographic field, such as a single-jet method or a double-jet method, but in particular, in the present invention, a silver halide gelatin emulsion is prepared. Light-sensitive silver halide emulsions prepared according to techniques including the following give favorable results. The light-sensitive silver halide emulsion may be chemically sensitized by any method known in the photographic art. Such sensitization methods include gold sensitization, sulfur sensitization, gold-
Various methods such as sulfur sensitization and reduction sensitization can be used. The silver halide in the above photosensitive emulsion may have coarse or fine grains, but the preferred grain size is about 1.5 to about 0.001 μm, more preferably about 0.5 to about 0.05 μm. It is. The light-sensitive silver halide emulsion prepared as described above can be applied to a layer containing light-sensitive silver halide, which is a constituent layer of the light-sensitive material of the present invention. Furthermore, as another method for preparing photosensitive silver halide,
It is also possible to cause a photosensitive silver salt-forming component to coexist with an organic silver salt to form a photosensitive silver halide in a portion of the organic silver salt. The photosensitive silver salt-forming component used in this preparation method includes inorganic halides, such as
Halide represented by MXn (where M represents an H atom, _NH4 group or a metal atom, and X is
Cl, Br or 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.
Metal atoms include lithium, sodium, potassium, rubidium, cesium, copper, gold, beryllium, magnesium, calcium, strontium, barium, zinc, cadmium, mercury, aluminum, potassium, indium, lanthanum, ruthenium, thallium, germanium, and tin. , lead, antimony, bismuth, chromium, molybdenum, tungsten, manganese, rhenium, iron, cobalt, nickel, ruthenium, rhodium, palladium, osmium, iridium, platinum, cerium, and the like. 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 ) ₃ RhCl ₆ , (NH ₄ ) ₃ RhBr ₆ , etc.), onium halides (e.g. tetramethylammonium bromide, trimethylphenylammonium bromide, cetylethyldimethylammonium bromide, 3-methylthiazolium bromide, trimethylbenzylammonium) (e.g., quaternary ammonium halides such as bromide, quaternary phosphonium halides such as tetraethyl phosphonium bromide, tertiary sulfonium halides such as benzylethylmethyl bromide, 1-ethylthiazolium bromide, etc.), halogenated hydrocarbons (e.g. iodoform, bromoform, carbon tetrabromide, 2-bromo-2-methylpropane, etc.), N-halogen compounds (N-chlorosuccinimide, N-bromosuccinimide, N-bromphthalimide, N-bromoacetamide, N-iodosuccinimide, N-bromphthalazinone, N
-chlorophthalazinone, N-bromoacetanilide, N,N-dibromobenzenesulfonamide,
N-bromo-N-methylbenzenesulfonamide, 1,3-dibromo-4,4-dimethylhydantoin, etc.), other halogen-containing compounds (e.g. triphenylmethyl chloride, triphenylmethyl bromide, 2-bromobutyric acid, -bromoethanol, etc.). 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 to 1.0 per mol of organic silver salt.
mol, preferably 0.01 to 0.3 mol. As the reducing agent used in the present invention, when a substance that releases a diffusible black dye is used as a dye-donating substance, the diffusible black dye-releasing compound is used alone or in combination with the following reducing agent. Typical reducing agents include phenols (e.g. p-phenylphenol, p-methoxyphenol, 2,6-di-tert-butyl-p-cresol, N-methyl-p-aminophenol, etc.), sulfonamides. Phenols (e.g. 4-benzenesulfonamidophenol, 2-benzenesulfonamidophenol, 2,6-dichloro-4
-benzenesulfonamidophenol, 2,6-
Dibromo-4-(p-toluenesulfonamide)
phenol, etc.), di- or polyhydroxybenzenes (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, 4-aminonaphthol, 4-aminonaphthol, -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, pyrazolines, pyrazolones, hydrazones and paraphenylenediamines. The above-mentioned reducing agents may be used alone or in combination of two or more. Next, when a substance that forms a diffusible black pigment is used as the dye-donating substance of the present invention, hydrazones or parafluorophores whose oxidized product couples with the diffusible black pigment-forming substance to form a diffusible black pigment. It is preferable to use enylene diamines and p-aminophenols. These reducing agents include U.S. Patent Nos. 3,531,286, 3,764,328,
No. 3761270, RD12146, RD15108, RD15127,
Reducing agents such as those described in JP-A-56-27132 and JP-A-56-146133 are effective, and representative examples thereof are listed below. [Exemplary compounds] N,N-diethylelene-p-phenylenediamine N,N-diethylamino-2-methylaniline N,N-diethylamino-3-methoxyaniline N-ethyl-N-2-methoxyethylamino-
2-Methylaniline 4-morpholinoaniline 4-N,N-diethylamino-2-methylphenylsulfamic acid sodium 4-N,N-di-iso-propylamino-2-
Sodium methylphenylsulfamate 4-N,N-di-ethylamino-2-chlorophenylsulfamate 4-benzenesulfonamide-N,N-diethylaniline 4-methanesulfonamide-3-methyl-N ，
N-diethylaniline 4-benzenesulfonamidophenol 4-benzenesulfonamido-2,6-dichlorophenol N-methyl-2-hydrazono-benzthiazoline N-methyl-2-benzenesulfonylhydrazono-benzthiazoline These reducing agents can be used alone or in combination of two or more, and the amount used depends on the type of organic silver salt used, the type of photosensitive silver salt, the type of other additives, etc., but usually Organic silver salt 1
It ranges from 0.05 to 10 mol, preferably from 0.1 to 3 mol. As the binder used in the present invention, any hydrophilic or hydrophobic binder can be used depending on the purpose. Examples of hydrophilic binders include gelatin, gelatin derivatives, casein, sodium caseinate, proteins such as albumin, cellulose derivatives such as ethylcellulose, polysaccharites such as dextran, polysaccharides such as agar, natural substances such as gum arabic, gum tragacanth, etc. , polyvinyl alcohol, polyvinylpyrrolidone, and also water-soluble polyvinyl acetals, preferably those with a degree of acetalization of less than 20%, such as synthetic polymers such as polyvinyl butyral, and latex-like vinyl compounds that increase the dimensional stability of photographic materials. and synthetic polymers such as those described below. Suitable synthetic polymers include U.S. Pat.
Examples include those described in the specifications of No. 3220844, No. 3287289, and No. 3411911. Useful polymers include water-insoluble polymers based on alkyl acrylates, methacrylates, acrylic acid, sulfoalkyl acrylates or methacrylates. Suitable polymeric substances include polyvinyl butyral, polyacrylamide, cellulose acetate butyrate, cellulose acetate propionate, polymethyl methacrylate, polyvinylpyrrolidone, polystyrene, ethyl cellulose, polyvinyl chloride,
Chlorinated rubber polyisobutylene, butadiene styrene copolymer, vinyl chloride-vinyl acetate copolymer vinyl acetate-vinyl chloride-maleic acid copolymer, polyvinyl alcohol, polyvinyl acetate, benzyl cellulose, cellulose acetate, cellulose propionate, cellulose acetate phthalate can give. If necessary, two or more types may be used in combination.
The amount of binder is 1/10 to 10 parts by weight, preferably 1/4 to 1 part of organic silver salt for each exposure dose.
~4 parts. In the present invention, when the black pigment formed or released is a diffusible hydrophobic pigment, it is preferable to use a hydrophilic binder. Hydrophilic binders include proteins such as gelatin, cellulose derivatives such as ethylcellulose, and water-soluble synthetic polymers such as polyvinyl alcohol, polyvinylpyrrolidone, or water-soluble polyvinyl acetal, and these may be used alone or in combination of two or more. I can do it. A toning agent can be used in the heat-developable photosensitive material of the present invention for the purpose of accelerating development. As the above-mentioned color toning agent, for example, JP-A-46-4928
No. 46-6077, No. 49-5019, No. 49-5020
No. 49-91215, No. 49-107727, No. 50-
No. 2524, No. 50-67132, No. 50-67641, No. 50-
No. 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. 54-156525, No. 54-156526, No. 55-4060
No. 55-4061, No. 55-32015, and West German Patent No. 2140406, West German Patent No. 2147063, West German Patent No.
2220618, U.S. Patent No. 3080254, U.S. Patent No. 3847612,
Same No. 3782941, No. 3994732, No. 4123282, Same No.
Phthalimide, pyrazolone, quinazolinone, N-hydroxynaphthalimide, benzoxazine, naphthoxazinedione, 2,3-dihydro-phthalazinedione, 2,3-dihydro- which are compounds described in specifications such as No. 4201582.
1,3-oxazine-2,4-dione, oxypyridine, aminopyridine, hydroxyquinoline,
Aminoquinoline, isocarbostyryl, sulfonamide, 2H-1,3-benzothiazine-2,4
-(3H) dione, benzotriazine, mercaptotriazole, dimercaptotetrazapentalene, phthalic acid, naphthalic acid, phthalamic acid, phthalazinone and other derivatives. Furthermore, an antifoggant can be used to prevent thermal fog in the photothermographic material of the present invention. As an antifoggant, for example,
11113, JP-A No. 49-90118, JP-A No. 49-10724,
No. 49-97613, No. 50-101019, No. 49-130720
No. 50-123331, No. 51-47419, No. 51-
No. 57435, No. 51-78227, No. 51-104338, No. 53
−19825, No. 53-20923, No. 51-50725, No.
No. 51-3223, No. 51-42529, No. 51-81124, No.
Publications such as No. 54-51821 and No. 55-93149, as well as British Patent No. 1455271, U.S. Patent No. 3885968,
3700457, 4137079, 4138265, West German Patent No. 2617907, etc.; oxidizing agents (e.g. N-halogenoacetamide, N-halogenoacetamide,
-halogenosuccinimides, perchloric acid and its salts, inorganic peroxides, persulfates, etc.), acids and their salts (e.g. sulfinic acid, lithium laurate, rosin, diterpenic acid, thiosulfonic acid, etc.), sulfur-containing compounds (For example, mercapto compound-releasing compounds, thiouracil, disulfide, simple sulfur, mercapto-1,2,4-triazole, thiazolinthione, polysulfide compounds, etc.), and other compounds such as oxazoline, 1,2,4-triazole, phthalimide, etc. can give. The photothermographic material of the present invention may contain a compound that releases water upon heating, that is, a water-releasing agent. Such water release agents include, for example, phosphoric acid 3
Sodium dodecahydrate, sodium sulfate decahydrate, ferrous ammonium sulfate hexahydrate, ammonium alum 24hydrate, potassium alum 24hydrate, magnesium acetate tetrahydrate,
Examples include compounds containing water of crystallization such as manganese acetate tetrahydrate. Further, the heat-developable photosensitive material of the present invention may contain a water-retentive compound for the purpose of keeping the water content in the photosensitive material constant. Examples of such water-retentive compounds include polyalkylene oxide (polyglycol), hydroxyethyl cellulose, carboxymethyl cellulose, etc., which are described in US Pat. No. 3,347,675. A development accelerator can be added to the heat-developable photosensitive material of the present invention, if necessary. As the development accelerator used in the present invention, for example, US Pat.
No. 3220846, No. 3531285, No. 4012260, No. 3220846, No. 3531285, No. 4012260, No.
Alkali release agents described in the specifications of No. 4060420, No. 4088496, No. 4207392 or RD15733, No. 15734, No. 157776, organic acids described in Japanese Patent Publication No. 45-12700, -CO described in U.S. Patent No. 3667959 −，−
Non-aqueous polar solvent compounds having SO ₂ -, -SO- groups, melt formers described in U.S. Pat. No. 3,438,776, polyalkylene glycols described in U.S. Pat. . In addition to the above-mentioned components, the heat-developable photosensitive material of the present invention may optionally contain various known additives such as spectral sensitizing dyes, antihalation dyes, printout inhibitors, and non-mercury-based antifoggants. be able to. The above-mentioned spectral sensitizing dye is effective for silver halide emulsions, such as cyanine, merocyanine,
Rhodacyanine, styryls, etc. can be used. Printout inhibitors include tetrabromobutane, tribromoethanol, 2-bromo-2-tolylacetamide, 2-bromo-2-tolylsulfonylacetamide, 2-tribromomethylsulfonylbenzothiazole, 2,4-bis( Examples include tribromomethyl)-6-methyltriazine. Examples of the support used in the heat-developable photosensitive material of the present invention include synthetic plastic films such as cellulose nitrate film, polyvinyl acetal film, polyethylene film, cellulose acetate film, polyethylene terephthalate film, and polycarbonate film, as well as photographic base paper and printing paper. Examples include paper, baryta paper, resin coated paper, and the like. Each component used in the photosensitive material is coated on the support together with a binder dissolved in water or a mixture of water and an organic solvent. The thickness of the coating layer after drying is 1 to 1000 μm, preferably 3 to 20 μm.
It is m. Furthermore, an overcoat layer may be formed on the photosensitive material, if necessary. The image-receiving layer used in the present invention may be formed of a substance that receives the diffusible black dye released or formed by thermal development, and may be made of a mordant used in a diffusion transfer type light-sensitive material, or the like of JP-A No. 57-207250, etc. 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 as described in . As specific examples of the mordant, nitrogen-containing secondary and tertiary amines, nitrogen-containing heterocyclic compounds, and quaternary cationic compounds thereof are widely known, and these can also be effectively used in the present invention. . U.S. Patent No. 2548564, U.S. Patent No. 2484430, U.S. Patent No.
No. 3148061 and No. 3756814 disclose vinylpyridine polymers and vinylpyridinium cationic polymers. US Pat. No. 2,675,316 discloses the use of polymers containing dialkylamino groups as mordants. Aminoguanidine derivatives are disclosed in US Pat. No. 2,882,156. U.S. Patent No. 3625694, U.S. Patent No. 3859096, British Patent No. 1277453, U.S. Patent No. 2011012, gelatin, etc.
A crosslinkable mordant is disclosed. U.S. Patent No. 3958995, U.S. Patent No. 2721852, U.S. Patent No.
No. 2798063 discloses an aqueous sol type mordant. Further, JP-A-50-61228 discloses a water-insoluble mordant. In addition, U.S. Patent No. 3709690, 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. 55
−22766, 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. 57-12139,
Various mordants are disclosed in RD12045 (1974). 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, polydivinylbenzene, 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-dimethylallylamide, p-cyanophenyl group, pentachlorophenyl group, and Polyacrylate with 2,4-dichlorophenyl group, polyacryl chloroacrylate, polymethyl methacrylate, polyethyl methacrylate, polypropyl methacrylate, polyisopropyl methacrylate, polyisobutyl methacrylate, poly-tert-butyl methacrylate, polycyclohexyl methacrylate, polyethylene Glycol dimethacrylate, poly-2-
Examples include polyesters such as cyano-ethyl methacrylate and polyethylene terephthalate, polycarbonates such as polysulfone and bisphenol A polycarbonate, polyanhydrides, polyamides, and cellulose acetates. Also, Polymer Handbook 2nd CD.
Brandrup, EHImmergut (ed.) John Wiley &
Glass transition temperature listed in Sons Publishing, 40
Synthetic polymers below 0 C are also useful. These polymeric substances may be used alone or in combination of two or more as a copolymer. Particularly useful polymers include cellulose acetate, such as triacetate and diacetate;
Polyamides made from combinations such as terephthalic acid with heptamethylene diamine, fluorene dipropylamine and adipic acid, hexamethylene diamine and diphenic acid, hexamethylene diamine and isophthalic acid, diethylene glycol and diphenylcarboxylic acid, bis-p-carboxyphenoxib Examples include polyester made from a combination of tan and ethylene glycol, polyethylene terephthalate, and polycarbonate. These polymers may be modified. For example, polyethylene terephthalate using cyclohexanedimethanol, isophthalic acid, methoxypolyethylene glycol, 1,2-dicarbomethoxy-4-benzenesulfonic acid, etc. as a modifier is also effective. These polymers may be coated on another support such as paper, glass, metal, etc. to form an image-receiving layer, or they may be made into a film sheet so that it also functions as a support by itself. It's okay. When these polymers are used as supports, the supports may be formed from a single layer or from multiple layers. A white reflective layer may be formed by having a portion or layer containing titanium white in or outside the support. Further, the above-mentioned compounds used as mordants may be used alone or mixed with other polymers and coated on a suitable support. The heat-developable photosensitive material of the present invention comprises at least one heat-developable photosensitive layer containing each of the following components: a) photosensitive silver halide, b) organic silver salt, c) a diffusible black dye-providing substance, and d) a binder. These components a) to d) are not necessarily contained in one layer, but as long as they can react with each other. 2
It may be contained separately in the above layers. Furthermore, the photosensitive material of the present invention may have two or more heat-developable photosensitive layers, for example, a separate layer may contain a dye-providing substance that releases or forms diffusible black dyes with different tones. . For the heat-developable photosensitive layer according to the present invention, as well as for the protective layer, intermediate layer, undercoat layer, back layer, and other layers, respective coating solutions are prepared and coated using the dipping method, air knife method, curtain coating method or the U.S. Pat.
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. Various exposure means can be used for the heat-developable photosensitive material of the present invention. The latent image is obtained by imagewise exposure to radiation, including visible light. In general, light sources used for ordinary color printing, such as tungsten lamps, mercury lamps, xenon lamps, laser beams, CRT beams, etc., can be used as the light source. The original drawing may be a line image such as a technical drawing, or a photographic image with steps. Furthermore, the printing from the original drawing may be either contact printing or projection printing. In addition, images projected by video cameras, etc., and image information sent from television stations can be directly transmitted to CRT or
It is also possible to expose the image to a FOT, form the image on a heat-developable photosensitive material using a contact lens or a lens, and then print the image. Furthermore, LEDs (light emitting diodes), which have recently seen significant progress, can also be used as exposure means in various devices. In addition to the above method of directly attaching or projecting the original image, the original image illuminated by a light source can be
After being read by a light-receiving element such as a CCD, stored in the memory of a computer, etc., and subjected to so-called image processing that processes this information as necessary, this image information is reproduced on a CRT and used as an image-like light source. Another method is to emit light from an LED or laser based on the processed information. After exposure of the heat-developable color photosensitive material of the present invention, the resulting latent image is, for example, 0.3 to
Development and transfer can be carried out by heating the entire surface of the photosensitive material for 120 seconds. As long as the temperature falls within the above range, both high and low temperatures can be used by increasing or shortening the heating time. Especially about 110
A range of 0.degree. C. to 200.degree. C. is useful, and the heating means may be a hot plate, iron, hot roller or the like. The light-sensitive material according to the present invention is imagewise exposed and then thermally developed to release or form an imagewise distribution of a thermal diffusion transferable black dye or a thermal diffusion transferable dye precursor from the dye-providing substance, At least a portion of the imagewise distribution is thermally transferred to an image receiving layer in a stacked relationship with the photothermographic material. In the present invention, one specific method for forming a black dye image by development is thermal diffusion transfer of a mobile black dye, and for this purpose, the heat-developable photosensitive material has at least silver halide, It is composed of a photosensitive layer containing an organic silver salt, a dye-donating substance that releases or forms a diffusible black dye, and a binder, and an image-receiving layer that can receive the mobile black dye formed in the photosensitive layer. The above-mentioned photosensitive layer and image-receiving layer may be formed on the same support, or may be formed on separate supports. The image receiving layer can be peeled off from the photosensitive layer. For example, after imagewise exposure of the heat-developable photosensitive material, an image-receiving layer can be superimposed on the photosensitive layer and uniformly heat-developed. Further, after the photothermographic material of the present invention is subjected to imagewise exposure and uniform heat development, an image-receiving layer may be placed thereon and the black dye may be transferred by heating at a temperature lower than the development temperature. A transfer solvent can also be used to transfer the black dye from the heat-developable photosensitive layer to the image-receiving layer. The transfer solvent includes low boiling point solvents such as methanol, ethyl acetate, diisobutyl ketone, tri-n-cresyl phosphate, tri-n-nonyl phosphate,
A high boiling point solvent such as di-n-butyl phthalate can be used, and in the case of a high boiling point solvent, it can be emulsified in gelatin using a suitable emulsifier and added to the image-receiving layer. [Example] Next, the present invention will be specifically explained with reference to Examples, but the present invention is not limited to the illustrative Examples. Example 1 400 ml of methyl alcohol and 500 ml of an 8% poly-vinyl alcohol (Gohsenol AL-02) aqueous solution were added to 22.7 g of silver benztriazole and dispersed in a ball mill for 24 hours to prepare a dispersion. Next, while stirring this dispersion, a silver iodobromide emulsion (silver iodide 5
Mol%, 60 g of gelatin and 0.353 silver in 1 kg of emulsion
Cubic particles with an average particle size of 0.06μm (including moles) 28ml
added. Additionally, 812 g of p-amino-N,N-diethylaniline and 6.8 g of exemplified compounds (1), 7.6 g of (3), and (23) as diffusible black pigment-forming compounds, respectively.
11.1 g, (25) 11.5 g, and (17) 14.1 g were dissolved in 100 ml of methyl alcohol, and then 2 of 3-amino-4-allyl-5-mercaptotriazole was added.
% methanol solution and 50 g of acetamide were added and stirred thoroughly. The coating solution thus prepared was coated as a photosensitive layer on a polyethylene terephthalate base coated with gelatin (3 μm dry film thickness) (coated silver amount: 5.2 mg/dm ² ), and a photosensitive element was prepared.
, and obtained. Separately, an image-receiving paper was prepared by applying a 5% solution of polyvinyl chloride in tetrahydrofuran (containing 10% by weight of dibutyl phthalate to the polymer) onto photographic baryta paper so that the amount of polyvinyl chloride was 1.20 g per 1 m ² . . After each of the photosensitive elements, . When the image-receiving layer was peeled off after development, a blue-black dye image was obtained on the image-receiving layer. The measurement results of the transmitted density are shown in Table 1.

[Table] The black dye transfer image thus obtained on the image-receiving layer was separated from the organic silver salt and silver halide, and no discoloration was observed in the unexposed areas after processing. Example 2 p-amino-N,N-diethylaniline in Example 1 was replaced with 10.0 g of 4-(N,N-diethylamino)-2-methylphenylsulfamic acid sodium,
Similar samples were created (sample, , and). The same process was carried out except that the developing temperature was changed to 160°C to obtain a black to blue-black transferred image. The measurement results of the transmitted density are shown in Table 2.

[Table] Example 3 Exemplified compound (16) 16.3g, Exemplified compound (17)
14.1 g of each was added to a mixture of 10 ml of dibutyl phthalate and 30 ml of ethyl acetate and heated at 60°C to completely dissolve. This solution was mixed with a 6% aqueous solution of Alkanol B (alkylnaphthalene sulfonic acid, DuPont).
ml and 100 ml of a 5% gelatin aqueous solution and dispersed in a colloid mill to obtain dispersions A and B, respectively.
Separately, 400 ml of methyl alcohol and 500 ml of an 8% polyvinyl alcohol (Gohsenol AL-02) aqueous solution were added to 22.7 g of benztriazole silver and dispersed in a ball mill for 24 hours to prepare a dispersion. Next, 28 ml of a silver iodobromide emulsion (cubic grains with an average grain size of 0.06 μm containing 5 mol % of silver iodide, 60 g of gelatin and 0.353 mol of silver in 1 kg of the emulsion) was added to this dispersion. The above coupler dispersions A and B were added to the organic silver salt and silver halide dispersions, and to each was added 9 ml of a 2% methanol solution of 3-amino-4-allyl-5-mercaptotriazole, p-
Amino-N,N-diethylaniline 8.2g, 50g
of acetamide was added and stirred well. The coating solution thus prepared was coated on the same support as in Example 1 to produce photosensitive elements (Samples Nos. XI and XII).
After each of the photosensitive elements was exposed to tungsten light through a step wedge, the image-receiving layer of the image-receiving paper prepared in Example 1 was combined and developed at 150° C. for 20 seconds. When the image-receiving layer was peeled off after development, a black image was obtained on the surface of the image-receiving layer. Table 3 shows the measurement results of the transmitted density.

[Table] Example 4 As the diffusible black pigment forming substance of Example 1 (1),
Instead of using (3), (23), (25), and (17), use 8.0 g each of compounds (44) and (45), omit p-amino-N,N-diethylaniline, and repeat the same procedure. Two types of photosensitive elements (No.) were obtained by coating. After each of the photosensitive elements was exposed to tungsten light through a step wedge, the coated surface of each element was combined with the receiver paper prepared in Example 1 and developed at 150 DEG C. for 20 seconds. When the image-receiving layer was peeled off after development, a black dye image was obtained on the image-receiving layer. The measurement results of transmission density are shown in Table 4.

【table】

Claims (1)

[Claims] 1 A diffusion transfer type heat-developable photosensitive layer having on a support at least one heat-developable photosensitive layer containing a) a photosensitive silver halide, b) an organic silver salt, c) a diffusible black dye-providing substance, and d) a binder. material.