JPH0330132B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a highly sensitive heat-developable photosensitive material containing silver halide as a photocatalyst, and more particularly to a heat-developable photosensitive material containing stable, fine-grained silver halide with uniform particle size produced in an organic solvent. It is related to. Silver halide photography, which has been widely used in the past, has superior photographic properties such as photosensitivity and gradation compared to photography methods using so-called non-silver salt photosensitive materials such as diazo photography and electrophotography. It is a photographic method. However, the silver halide photographic materials used in this method require a wet processing step to obtain stable images, which is time-consuming and labor-intensive, and the handling of chemicals can be harmful to the human body. There was a problem. Therefore, a photographic method capable of obtaining stable images through dry processing while using silver halide is highly desired, and much research has been carried out to date. For example, Japanese Patent Publication No. 43-4921 or No. 43-4921
The most successful heat-developable photosensitive material is the three-component composition of a reducible organic silver salt, a reducing agent, and a photosensitive silver halide in catalytic contact with the organic silver salt, as described in Publication No. 4924. This is an example. After imagewise exposure of such a heat-developable photosensitive material, an image is formed by heating the material to usually 80° C. or higher, preferably 100° C. or higher. Since this heat-developable photosensitive material has a low content of photosensitive silver halide, which is unstable to light, it does not require any particular stabilization treatment after image formation.
Therefore, such heat-developable photosensitive materials can provide stable and high-quality images without any wet process. In such heat-developable photosensitive materials, photosensitive silver halide is important as it determines the photographic properties of the heat-developable photosensitive material, and in particular, it contains fine particles of silver chloride, silver bromide, silver chlorobromide, and silver iodine. Silver bromide is said to be preferred. The first method for preparing silver halide is to convert a part of a reducible organic silver salt into silver halide using ammonium bromide or sodium chloride, which is described in Japanese Patent Publication No. 4924/1983. How to convert and Tokuko Sho 53-40484
A method of thermally decomposing an N-halogeno compound and converting a part of the reducible organic silver salt into photosensitive silver halide, which is a so-called in-situ silver halide preparation technique, described in the above publication can be mentioned. . In this first method, a part of the reducible organic silver salt is halogenated to convert it into photosensitive silver halide, which brings about an unfavorable change in most other reducible organic silver salts. This must be avoided. The formation and sensitization methods of photosensitive silver halide that meet these requirements are naturally subject to limitations. Therefore, it is difficult to simply apply the sensitization methods used in wet silver halide photographic emulsions, especially the methods of increasing sensitivity by adding chemical sensitizers. For the above reasons, a second method, the so-called ex-situ silver halide technique, has been proposed. This heat-developable photosensitive composition containing an ex-situ silver halide is produced by forming the photosensitive silver halide in advance at a location separate from the reducible organic silver salt and then mixing it with the reducible organic silver salt. prepared. However, as is clear from Japanese Patent Publications No. 43-4921 and No. 43-4924, photosensitive silver halide prepared by a conventional silver halide photographic emulsion method is not preferred. This is because photographic emulsions using gelatin as a protective colloid have strong adsorption between silver halide and gelatin. This is because it cannot be obtained. Furthermore, silver halide prepared in the absence of a protective colloid (eg, gelatin) causes aggregation between silver halide particles, making it unsuitable for use as a photoreceptor for heat-developable photosensitive materials. Many attempts have been made to compensate for these drawbacks and to produce photosensitive silver halides that can effectively come into contact with reducible organic silver salts. For example, UK Patent No. 1362970
In the specification, an organic solvent containing an oil-soluble binder and an aqueous solution of an inorganic silver compound are emulsified by ultrasonic dispersion, an inorganic halogen compound dissolved in the organic solvent is added to this emulsion, and a photosensitive material is added to the oil-soluble binder. A method of forming a synthetic silver halide is described. However, the photosensitive silver halide prepared by this method cannot produce particles with a uniform shape and size distribution, and requires complicated operations such as ultrasonic dispersion and decantation to remove the aqueous phase. shall be.
JP-A-47-9432 and JP-B-Sho 52-17415 disclose photosensitive silver halide by reacting an inorganic silver compound soluble in a polar organic solvent (for example, acetone) with an inorganic halogen compound in an oil-soluble binder. A method for forming the is described. However, even with this method, particles with uniform particle shape and particle size distribution cannot be obtained, and agglomeration is likely to occur. JP-A-50-32926 and JP-A-54-4117 disclose that photosensitive silver halide is formed in an aqueous or water-organic solvent emulsion, and then a reducible organic silver salt is photosensitive. A method for preparing the compound by mixing it with a silver halide is described.
However, in this method, after the photosensitive silver halide is formed, it is exposed to chemically active conditions or placed in a high temperature atmosphere. It is impossible to maintain the characteristics of the various sensitization treatments applied to sexual silver halide. JP-A-47-9171 and JP-A-47-
No. 9308 describes the formation of photosensitive silver halides in the presence of new amphiphilic copolymers, and JP-A-50-32928 describes the formation of photosensitive silver halides in the presence of surfactants. However, this method is also difficult to operate, and it is difficult to prepare silver halide with uniform grains. An object of the present invention is to provide a heat-developable photosensitive material with high image density and high contrast. In order to achieve such an objective, the present inventors have conducted various studies and found that organic fatty acid silver suspended and dispersed in an organic solvent is maintained at a predetermined temperature, and an inorganic or organic halogen compound is added to this dispersion. It has been found that when stoichiometrically added photosensitive silver halide is almost quantitatively formed. Further, the silver halide grains thus formed were fine grains with a narrow particle size distribution, and did not aggregate or settle when left for a long time. It has also been found that more favorable results can be obtained when a binder soluble in an organic solvent is co-present as a protective colloid during silver halide formation. Furthermore, by using the silver halide thus formed as a photoreceptor in a heat-developable photosensitive material, a heat-developable photosensitive material having excellent photographic properties such as sensitivity, image density, and gradation can be obtained. I understood. The photosensitive silver halide of the present invention is formed by suspending and dispersing component (a), organic fatty acid silver, in an organic solvent, and adding component (b), an inorganic or organic halogen compound, to this dispersion. The organic fatty acid silver of component (a) is poorly soluble or insoluble in organic solvents, and is preferably an organic fatty acid silver having 5 or more carbon atoms, such as silver caproate, silver caprylate, silver caprate, silver lauric acid. Silver, silver myristate, silver palmitate, silver stearate, silver alainate, silver behenate, silver lignocerate, silver oleate, silver linoleate, silver linoleate, silver hydroxystearate, silver 11-bromoundecanoate, etc. Examples include substituted or unsubstituted saturated or unsaturated fatty acid silver. Number of carbons in organic fatty acid silver is 4
If the particle diameter is less than 1, it is difficult to produce silver halide grains with a uniform shape and a narrow particle size distribution, so it is not very preferable. The preparation of such organic fatty acid silver is
A common method is to add a solution of a silver salt such as silver nitrate, ammoniacal silver nitrate, or a silver complex salt to a solution of an organic fatty acid or an alkali metal salt of an organic fatty acid dissolved in an appropriate solvent. The inorganic or organic halogen compound of component (b) is
It is capable of reacting with the organic fatty acid silver of component (a) to form silver halide. Examples of the inorganic halogen compound include compounds represented by the general formula MXn. However, in the formula, M is a hydrogen atom or a metal atom (for example, strontium, cadmium, zinc, sodium, barium, cesium, calcium, iron, nickel, magnesium, potassium, aluminum, antimony, gold, cobalt, mercury,
(lead, beryllium, lithium, indium, iridium, rhodium, palladium, platinum, bismuth, etc.), X represents a chlorine atom, a bromine atom, or an iodine atom, and n represents the valence of each cation. Examples of inorganic halogen compounds include halogen-containing metal complexes such as K ₂ PtCl ₆ , K ₂ PtBr ₆ , HAuCl ₄ ,
(HN ₄ ) ₂ IrCl ₆ , (HN ₄ ) ₃ IrCl ₆ , (HN ₄ ) ₃ RuCl ₆ ,
Examples include K ₃ RhCl ₆ . Organic halogen compounds are also effective as halogenating agents, and in particular when organic halogen compounds are used, photosensitive silver halide with uniform grain size and shape can be prepared. Preferred organic halogen compounds include compounds represented by the following general formula (1) or (2). In the formula, X represents a chlorine atom, a bromine atom, or an iodine atom, and Z represents a group of nonmetallic atoms necessary to form a 4- to 8-membered ring, and this 4- to 8-membered ring is fused with another ring. Good too. Z is preferably a 5-membered ring or a 6-membered ring
It is a membered ring, and specific examples include a pyrrole ring, a pyrroline ring, a pyrrolidine ring, an imidazoline ring, an imidazolidine ring, a pyrazoline ring, an oxazolidine ring, a piperidine ring, an oxazine ring, a piperazine ring, and an indoline ring. Furthermore, Z is 4
~8-membered lactam ring, hydantoin ring, cyanuric ring, hexahydrotriazine ring, indoline ring, etc. may be formed. Furthermore, this ring may have a substituent such as an unsubstituted or substituted alkyl group, an unsubstituted or substituted aryl group, an alkoxy group, a halogen atom, or an oxo group. A represents a carbonyl group or a sulfonyl group, and R ₁ and R ₂ represent a hydrogen atom, an unsubstituted or substituted alkyl group, an unsubstituted or substituted aryl group, or an alkoxy group. Representative examples of compounds represented by the above general formula (1) include N-bromsuccinimide, N-bromotetrafluorosuccinimide, N-bromophthalimide, N-bromglutarimide, 1,3-dibrom-5, 5-dimethyl-2,4-imidazolidinedione, N,N'-dibromo-5,5-diethylbarbituric acid, N-bromoisocyanuric acid, N,N'-dibromoisocyanuric acid, N-bromooxazolinone , N-bromphthalazinone,
Examples include N-chlorsuccinimide, N-iodosuccinimide, N-chlorphthalimide, N-bromusactucalin, N-bromocaprolactam, N-bromobutyrolactam, N,N'-dibromothiohydantoin, and the like. . Representative examples of compounds represented by the above general formula (2) include N-bromoacetamide, N-bromoacetanilide, N-bromobenzenesulfonylanilide, N-bromobenzamide, N-chloroacetamide, N-bromonaphthamide, -Brom-
P-hydroxybenzamide and the like can be mentioned. Further, halogenated melamine can also be used as the organic halogen compound, and specific examples include tribromemelamine, trichloromelamine, and the like. Furthermore, as an organic halogen compound, a C-halogen compound represented by the following general formula (3) is also effective. In the formula, X represents a chlorine atom, a bromine atom, or an iodine atom, and R ₃ , R ₄ , and R ₅ may be the same or different from each other, and represent a hydrogen atom, an unsubstituted or substituted alkyl group, an unsubstituted or substituted alkyl group, Aryl group, nitro group, acyl group, unsubstituted or substituted amide group,
It represents a sulfonyl group bonded to an unsubstituted or substituted aryl group or alkyl group, or a halogen atom. However, at least one of R ₃ , R ₄ , and R ₅ helps release a halogen atom, and represents, for example, a nitro group, an unsubstituted or substituted aryl group, an alkenyl group, an acyl group, an amide group, a sulfonyl group, etc. . As the compound represented by the above general formula (3), α
Examples include -haloketone compounds, α-haloamide compounds, halosulfonyl compounds, halonitro lower alkane compounds, and compounds having an unsaturated bond at the carbon β position relative to the halogen atom. Specific examples of the compound represented by general formula (3) include α-bromoacetophenone, α-chloroacetophenone, α-bromo-α-phenylacetophenone, α-bromo-1,3-diphenyl -1,
3-propanedione, α-bromo-2,5-dimethoxyacetophenone, α-bromomethylsulfonylbenzene, α-bromo-α-benzenesulfonylacetamide, α-chloro-α-(P-tolylsulfonyl)acetamide , α-bromo-γ
-Nitro-β-phenylbutyrophenone, α-iodo-γ-nitro-β-phenylbutyrophenone, 2-bromo-2-nitro-1,3-propanediol, 2-bromo-2-nitrotri Methylene-1,3-bis(phenyl carbonate), α-
Bromotoluene, α,P-dibromotoluene,
α, α′-dibromo-m-xylene, α, α, α′,
Examples include α'-tetrabromo-P-xylene and 3-bromopropene. Among the above-mentioned compound examples, compounds in which the carbon at the β-position of the halogen atom has an unsaturated bond, such as α-bromotoluene and 3-bromopropene, are particularly useful. Onium halide compounds are also useful as halogenating agents in the present invention; specific examples include ammonium bromide, trimethylphenylammonium chloride, cetylethyldimethylammonium bromide, trimethylbenzylammonium bromide, tetraethylphosphonium bromide, and trimethylsulfonium chloride. etc. can be mentioned. The present invention provides the above-mentioned components.
The organic fatty acid silver of (a) and the inorganic or organic halogen compound of component (b) are mixed, and a reaction for converting all or most of the organic fatty acid silver of component (a) into photosensitive silver halide is carried out in an organic solvent. Therefore, the amount of halogen compound used in component (b) is the same as that in component (a).
The amount may be stoichiometric with respect to the organic fatty acid silver.
However, it is preferable to use the halogen compound of component (b) in an excess amount, that is, in the range of about 1.0 mol to about 3.0 mol per 1 mol of organic fatty acid silver of component (a). In the present invention, component (a) organic fatty acid silver and component
The organic solvent used in the reaction of the halogen compound (b) is liquid at the reaction temperature and is capable of uniformly dispersing the organic fatty acid silver of component (a) and dissolving a certain amount of the halogen compound of component (b). If possible, there are no particular limitations. Specifically, alcohols, ketones, aliphatic hydrocarbons, aromatic hydrocarbons, alcohols, ethers, acid amides, and the like can be used alone or as a mixture. Specific examples of alcohols include fatty alcohols such as methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, isobutyl alcohol, sec-butyl alcohol, n-amyl alcohol, isoamyl alcohol, and n-hexyl alcohol. Aliphatic unsaturated alcohols such as group saturated alcohols, allyl alcohol and propargyl alcohol, alicyclic alcohols such as cyclopentanol and cyclohexanol, aralkyl alcohols such as benzyl alcohol and cinnamyl alcohol, polyhydric alcohols such as ethylene glycol and glycerin. etc. can be mentioned. Specific examples of ketones include aliphatic saturated ketones such as acetone, methyl ethyl ketone, methyl propyl ketone, isopropyl methyl ketone, butyl methyl ketone, and isobutyl methyl ketone; unsaturated aliphatic ketones such as methyl vinyl ketone and methyl heptene ketone; Examples include alicyclic ketones such as cyclobutanone and cyclohexanone, and aromatic ketones such as acetophenone, propiophenone and butylphenone. Specific examples of esters include methyl formate, propyl formate, amyl formate, ethyl acetate, methyl acetate, butyl acetate, isobutyl acetate, methyl propionate, ethyl propionate, isopropyl propionate, methyl butyrate, ethyl butyrate, and ethyl isobutyrate. , methyl isovalerate, isopropyl isovalerate, methyl benzoate, ethyl phthalate, and the like. Specific examples of ethers include dimethyl ether, dipropyl ether, diisopropyl ether, dibutyl ether, methyl butyl ether,
Saturated aliphatic ethers such as ethyl propyl ether and ethyl isoamyl ether, unsaturated aliphatic ethers such as diallyl ether and ethyl allyl ether, aromatic ethers such as anisole and phenyl ether, and cyclic ethers such as tetrahydrofuran and dioxane. can be mentioned. Specific examples of aliphatic hydrocarbons include n-heptane, n-hexane, 3-methylpentane, 2,3
- Saturated aliphatic hydrocarbons such as dimethylbutane, cyclohexane, cycloheptane, cyclohexene,
Unsaturated aliphatic hydrocarbons such as cyclopentadiene and cyclopentene can be mentioned. Specific examples of aromatic hydrocarbons include benzene, toluene, xylene, chlorobenzene, indene, and tetralin. In addition, solvents containing nitrogen atoms or sulfur atoms, such as dimethylacetamide, dimethylformamide, and dimethyl sulfoxide, can also be used. Particularly preferred among the above organic solvents are alcohols or ketones alone or in mixtures with the other solvents mentioned above. Mixed systems of water-alcohols and water-ketones can also be used. In preparing the photosensitive silver halide of the present invention, the ingredients
The organic fatty acid silver (a) is suspended and dispersed in the above-mentioned organic solvent using a well-known dispersion technique such as a homomixer, ball mill, sand mill, ultrasonic disperser, etc.
This suspension is referred to as a liquid (A), and a liquid in which an inorganic or organic halogen compound as a component (b) is dispersed, preferably dissolved, in the above-mentioned organic solvent is referred to as a liquid (B). Liquid (A) and liquid (B)
Although the concentration can be set arbitrarily, it is preferably in the range of 0.5% by weight to 50% by weight. The method of mixing liquid (A) and liquid (B) is a technique known in the field of photographic technology.
For example, a forward flow method, a reverse flow method, a simultaneous mixing method, etc. can be used. However, a simple and preferred method is to add liquid (B) to liquid (A) which is being stirred. liquid
Regarding the addition method of (B), photosensitive silver halide can be formed by any of the methods of adding at once, adding intermittently, and adding gradually continuously. However, in order to make the grain size and shape of the silver halide grains uniform and to grow the grains, a method of adding intermittently or gradually and continuously is preferred. Furthermore, the method of addition under control of the oxidation-reduction potential described in Japanese Patent Publication No. 54-24012 can also be applied to the above-mentioned addition method. The time required for addition of liquid (B) cannot be set uniquely because it changes depending on reaction conditions, such as stirring speed and reaction temperature. However, for operational reasons, it is preferable to set the time to 30 minutes to 5 hours. The reaction time from the start of the reaction to the end of the reaction can be set to the end of addition of liquid (B), but generally speaking
It is preferable to continue the reaction for an additional 30 minutes to 24 hours after the addition of (B) is complete. In the method for forming photosensitive silver halide of the present invention, dissociation of silver ions of organic fatty acid silver as component (a),
In order to help generate halogen ions from the halogen compound of component (b), the reaction temperature is 0°C or higher, especially about 20°C.
It is preferable to set the temperature above 100°C.
The reaction temperature is determined by the organic fatty acid silver used as component (a), the halogen compound used as component (b), and the reaction solvent used. Generally, the longer the alkyl chain of the silver organic fatty acid of component (a), the more preferably the temperature is set. Furthermore, when an inorganic halogen compound is used as component (b), the reaction temperature can be set to a slightly lower temperature than when an organic halogen compound is used. Furthermore, when alcohols are mainly used as the reaction solvent, the temperature can be set lower than that of other solvents. When forming the photosensitive silver halide of the present invention, in addition to heating, a reaction accelerator,
For example, an acidic substance such as trifluoroacetic acid or a basic substance such as pyridine may be added to form coarse silver halide grains that are stable in an organic solvent. In the present invention, a polymer soluble in the reaction solvent, preferably in the dispersion solvent of liquid (A), can be added thereto. The addition of a polymer soluble in an organic solvent improves the dispersibility of the organic fatty acid silver of component (a), allows uniform reaction of the organic fatty acid silver of component (a) and the halogen compound of component (b), It is also possible to prevent irregular growth and aggregation of the photosensitive silver halide formed. Polymers that can be used for this purpose are, for example, polyvinyl acetate, polyvinyl propionate, polymethyl methacrylate, ethyl cellulose, cellulose acetate, nitrocellulose, polyethylene, ethylene-vinyl acetate copolymers, chlorinated polyethylene, polyvinyl chloride, Vinyl chloride-vinyl acetate copolymer, chlorinated polypropylene, polyvinyl acetal, acrylic resin, polystyrene, epoxy resin, modified melamine resin, alkyd resin, polyamide, chlorinated rubber,
Examples include acrylonitrile-butadiene-styrene terpolymer, silicone block copolymer, polyvinylpyrrolidone, polyethylene oxide, high molecular weight paraffin, and the vinyl copolymer described in JP-A-47-9432.
Among the above polymers, preferred are those that can be dissolved in alcohols or ketones alone or in a mixed solvent with other organic solvents, and particularly preferred polymers are polyvinyl acetals. The amount of the polymer soluble in the organic solvent used is about 0.05 g to about 20 g per 1 g of the organic fatty acid silver salt of component (a).
Preferably it ranges from about 0.1 g to about 10 g. Next, preferred embodiments of the procedure for preparing the photosensitive silver halide of the present invention will be described. Organic fatty acid silver is uniformly dispersed in an organic solvent (e.g. n-butanol), a polymer soluble in the organic solvent (e.g. polyvinyl butyral) is added and stirred to dissolve it, and the organic fatty acid silver containing the polymer is suspended and dispersed. Prepare the liquid. This dispersion is maintained at a constant temperature while stirring under a safe light, and an inorganic or organic halogen compound dissolved in a suitable organic solvent (for example, acetone) is added thereto for about 30 minutes to about 5 hours, preferably about 30 minutes to about 5 hours. Add intermittently or gradually continuously over 3 hours. After the addition is completed, the reaction temperature is maintained and the reaction is continued for about 30 minutes to about 24 hours, preferably about 30 minutes to 8 hours. This can be determined by measuring the redox potential. When an N-halogeno compound is used as the halogen compound, it can also be determined by decolorizing a merocyanine dye as described in Japanese Patent Publication No. 40484/1984). After the reaction is completed, the reaction solution is returned to room temperature to obtain a mixed dispersion of photosensitive silver halide and a by-product organic fatty acid or an organic fatty acid that does not use silver as a cation. The photosensitive silver halides prepared according to the invention are silver chloride, silver iodide, silver bromide, silver chlorobromide, silver iodobromide, silver iodochloride and silver chloroiodobromide. The photosensitive silver halide prepared according to the present invention can be subjected to known chemical sensitization methods used in conventional wet silver halide emulsions, such as sulfur sensitization, gold sensitization, reduction sensitization, etc., to increase the inherent sensitivity. be able to. Furthermore, the photosensitive silver halide prepared according to the present invention can be processed by known spectral sensitization methods, such as cyanine dyes, styryl dyes, hemicyanine dyes, triphenylmethane dyes, xanthene dyes, oxonol dyes, merocyanine dyes, especially "product licensing". Index, Volume 92, Pages 107-110 (published December 1971), or Belgian Patent No.
Spectral sensitization can be performed as described in No. 772371. The photosensitive silver halide prepared according to the present invention is an oxidized silver halide comprising a reducible organic silver salt and a reducing agent.
It has extremely favorable properties as a photosensitive component for a reduced image forming component, and therefore, by using the photosensitive silver halide prepared according to the present invention, a heat-developable photosensitive material with excellent photographic properties can be provided. can do. That is, at least (c) an oxidation-reduction image forming component comprising a reducible organic silver salt and a reducing agent, (d)
In a heat-developable photosensitive material having at least one layer of a photosensitive composition consisting of a photosensitive silver halide and (e) a binder, as (d) a photosensitive silver halide, a photosensitive composition prepared according to the present invention; Silver halide can be suitably used. As a result of many years of research on such photosensitive silver halide, the present inventors found that it is effective when the silver halide has fine grains of around 0.1μ, and in particular, when the silver halide is a normal crystal of [1.0.0], The present inventors have discovered that silver particles are effective, and furthermore, the present inventors have discovered that photosensitive silver halide particles formed by the reaction of organic fatty acid silver suspended and dispersed in the above-mentioned organic solvent and an inorganic or organic halide compound. However, it has been found that the above-mentioned conditions are satisfied and it is preferable for the production of heat-developable photosensitive materials. The reason why these conditions are satisfied is that the photosensitive silver halide prepared by the present invention has a narrow and fine particle size distribution, and can provide a heat-developable photosensitive material with high image density and high contrast. can. The photosensitive silver halide prepared according to the present invention is easily and stably dispersed in an organic solvent, and is therefore advantageous in the production of heat-developable photosensitive materials. The photosensitive silver halide dispersion prepared according to the present invention can be used to produce a heat-developable photosensitive material without washing operations such as reprecipitation, decantation, and centrifugation, without causing fogging during heat development. Not a cause. The following points can be mentioned. As mentioned above, the heat-developable photosensitive material of the present invention has the following features:
The above three components (c), (d), and (e) are present as essential components in at least one layer provided on the support. In the oxidation-reduction image forming component consisting of a reducible organic silver salt and a reducing agent as component (c), the reducible organic silver salt is a colorless, white, or light-colored silver salt that is relatively stable to light. The coexisting silver halide is exposed to light, and the metallic silver produced as a core is heated at a temperature of 80°C.
When heated at a temperature of 100° C. or higher, preferably 100° C. or higher, it reacts with a reducing agent to form a silver image. Specifically, Japanese Patent Publication No. 43-4924 and Japanese Patent Publication No.
46-6074, or a silver salt of an organic compound having an imino group or a mercapto group. In particular, a silver salt of a long chain fatty acid having 12 to 24 carbon atoms is This is preferable because it is less susceptible to undesirable changes such as darkening. Specifically, silver behenate, silver stearate, silver palmitate, silver myristate, silver laurate, silver oleate or silver hydroxystearate can be mentioned,
Among them, silver behenate is particularly effective. In addition, a part of the above-mentioned reducible organic silver salt has been converted to silver halide by the method described in Japanese Patent Publication No. 43-4924, Japanese Patent Publication No. 53-40484, etc. You can also use things. Various reducing agents can be used in the above-mentioned oxidation-reduction image forming component. In general, developers used in conventional silver halide photosensitive materials, specifically hydroquinone, methylhydroquinone, chlorohydroquinone, methylhydroxynaphthalene, N,N'-diethyl-P-phenylenediamine, aminophenol, Examples include ascorbic acid, 1-phenyl-3-pyrazolidone, etc. In addition to these, 2,2'-methylenebis(6-t-butyl-4-methylphenol), 4,4'-butylidenebis(6- t-butyl-3-methylphenol), 4,4'-thiobis(6-t-butyl-3-methylphenol), etc.
Furthermore, bisnaphthol-based reducing compounds described in JP-A No. 46-6074 or Belgian Patent No.
Examples include sulfonamidophenol compounds such as 4-benzenesulfonamidophenol described in No. 802519. Furthermore, two or more of the above reducing agents may be used in combination. The amount of such reducing agent ranges from about 0.05 mole to about 5 mole, preferably from about 0.2 mole to about 3 mole per mole of reducible organic silver salt. The photosensitive silver halide of component (d) in the present invention is prepared by the method described above, and includes silver chloride, silver bromide, silver iodide, silver chlorobromide, silver iodochloride, silver iodobromide. It is one or a mixture of two or more selected from silver and silver chloroiodobromide, preferably prepared from organic fatty acid silver having 16 or more carbon atoms, and containing 30% silver bromide.
It contains mol% or more. The photosensitive silver halide of component (d) is produced either while containing by-products or after being subjected to washing operations such as reprecipitation, decantation, and centrifugation.
It is redispersed and mixed with a dispersion containing a reducible organic silver salt. Component (d), the photosensitive silver halide, may be added at any time during the manufacturing process of the heat-developable photosensitive material as long as it is contained in the same layer where it can come into contact with the reducible organic silver salt. Further, the preparation of a uniform dispersion of photosensitive silver halide and reducible organic silver salt can be easily achieved using a conventional stirrer, ball mill dispersion, ultrasonic dispersion, or the like. The amount of photosensitive silver halide added as component (d) is in the range of about 0.01 mol to about 0.5 mol per mol of reducible organic silver salt,
Preferably it ranges from about 0.05 mole to about 0.3 mole. If the amount used is outside this range, i.e. 0.01 mol or less, practical photographic properties cannot be obtained, and
If the amount is 0.5 mol or more, the background color changes significantly after image formation. The binder component (e) of the present invention can be used alone or in combination of two or more. Suitable materials for the binder can be hydrophobic or hydrophilic, and transparent or translucent.
Specifically, polyvinyl butyral, cellulose acetate butyrate, polymethyl methacrylate, polyvinylpyrrolidone, ethyl cellulose, cellulose acetate, polyvinyl acetate, polyvinyl alcohol, gelatin, and the sulfobetaine repeating unit described in Canadian Patent No. 774054. Among them, polyvinyl butyral is particularly preferred. The amount of the binder to be used is preferably about 10:1 to 1:10, more preferably about 4:1 to 1:2, based on the weight ratio of the reducible organic silver salt. The heat-developable photosensitive material of the present invention preferably contains one or more toning agents in order to obtain a black image. Examples include phthalazinone and its derivatives as described in US Pat. No. 3,080,254, cyclic imides as described in JP-A No. 46-6074, and phthalazinedione compounds as described in JP-A-50-32927. be able to. In the heat-developable photosensitive material of the present invention, a known antifoggant can be used for the purpose of preventing thermal fog during development. For example, mercury compounds described in Japanese Patent Publication No. 47-11113, Japanese Patent Publication No. 49-10724, Japanese Patent Publication No. 1977-10724,
N described in each publication No. 25808 and No. 54-23813
- Halogeno compounds, higher fatty acids such as stearic acid and behenic acid described in U.S. Patent No. 3,645,739 and JP-A-48-89720, and acids such as salicylic acid, tetrabromobenzoic acid, phthalic acid, trimellitic acid, etc. Stabilizers and the like can be mentioned. The heat-developable photosensitive material of the present invention may contain a suitable spectral sensitizer. Useful sensitizing dyes include cyanine dyes, merocyanine dyes, and xanthene dyes, especially "Product Licensing Index" Vol. 92, pp. 107-110 (published December 1971)
Or Belgian Patent No. 772371, JP-A-Sho
No. 47-6329, JP-A No. 105127-1987, JP-A-51-
127719, JP-A-52-80829, etc. are useful. Furthermore, it may contain a compound that prevents photodiscoloration after image formation. For example, U.S. Pat.
Azole thioethers and blocked azolethiones described in US Patent No. 3839041, tetrazolylthione compounds described in US Patent No. 3700457, and halogen-containing organic oxidations described in US Patent No. 3707377. Agent, U.S. Patent No.
1-carbamoyl-2-tetrazoline-5-thiones described in No. 3893859 can be used. Other suitable additives, such as development accelerators, curing agents, antistatic agents (layers), ultraviolet absorbers, optical brighteners, filter dyes (layers), may also be added.
etc. can also be used. The heat-developable photosensitive material of the present invention comprises component (c) a reducible organic silver salt and a reducing agent, component (d) a photosensitive silver halide, component (e) a binder, and the various additives mentioned above in a suitable solvent. It can be obtained by dispersing or dissolving the solution in water and coating it on a support in a single layer or in multiple layers. Furthermore, an overcoat polymer layer can be provided on the heat-developable photosensitive layer formed of a single layer or multiple layers. Suitable polymer layers include, for example:
Examples include polyvinyl butyral, polystyrene, polymethyl methacrylate, polyurethane rubber, chlorinated rubber, ethyl cellulose, cellulose acetate butyrate, cellulose acetate, polyvinyl chloride, polyvinylidene chloride, polycarbonate, and polyvinylpyrrolidone. Alternatively, the above polymer may be provided as an undercoat layer on a support, and the heat-developable photosensitive layer of the present invention may be laminated thereon. The support used in the present invention can be selected from a wide variety of supports. Typical supports include synthetic resin films such as polyethylene, polypropylene, polyethylene terephthalate, polycarbonate, and cellulose acetate, synthetic papers, papers coated with resin films such as polyethylene, papers such as art paper, and photographic baryta paper. , metal plates (foils) such as aluminum, synthetic resin films having metal vapor-deposited films by ordinary methods, glass plates, and the like. Application methods include roll coating method, air knife method,
Known methods such as a kiss coating method, a curtain coating method, a bar coating method, and a hopper coating method can be used. The heat-developable photosensitive material of the present invention is exposed to light from a light source such as a xenon lamp, a mercury lamp, a tungsten lamp, or a CRT laser beam, and then heated at 80°C to 180°C.
It is preferably developed at a heating temperature range of 110°C to 150°C. Although development can be carried out outside the above-mentioned temperature range by extending or shortening the heating time, it is preferable that the developing time is usually in the range of about 1 second to 60 seconds. The usual method for heat development is to bring the material into contact with a heating plate or heating drum, but other means for temporarily holding the material in a heated atmosphere may also be used, or high frequency heating or infrared light may be used. It is also possible to employ heating means such as Hereinafter, the present invention will be explained in more detail based on examples. Production Example 1 3.9 g of silver stearate was added to 100 ml of isopropyl alcohol and dispersed using a homomixer.
After this dispersion, add 3g of polyvinyl butyral,
A polymer suspension dispersion of silver salt was prepared by stirring and dissolving. This dispersion was heated to 50℃ under a red safety light, and lithium bromide was dissolved in 30ml of acetone while stirring.
0.9 g was added dropwise over 1 hour. After the dropwise addition, the reaction temperature was maintained for 2 hours and stirring was continued, and then the dispersion was cooled to room temperature to obtain a photosensitive silver halide dispersion (1). The obtained dispersion (1) did not precipitate even after being left for a long time. A part of this dispersion was added to xylene/n-
Diluted approximately 5 times with a solution of butanol (50/50 by volume), centrifuged (6000 RPM), removed the supernatant in which polyvinyl butyral was dissolved by decantation, and placed the residue on a glass plate. It was dried and used as sample (1). Electron microscopy of this sample (1) using the replica method (1000x, 10000x, and 30000x)
The type and particle size distribution of the silver halide grains were observed (measurements were also carried out in the same manner in the production series and comparative production examples described later). Table 1 shows the results obtained.

[Table] From the results in Table 1, it can be seen that the silver halide prepared by this method is extremely fine silver halide grains with a well-organized crystal type and narrow particle size distribution. Comparative Production Example 1 Silver halide was prepared according to British Patent No. 1362970. 2.35 molar silver nitrate aqueous solution 5
ml and a solution of acetone/toluene (50/100 by volume) in which 7.5 g of polyvinyl butyral is dissolved.
150ml was mixed and emulsified by ultrasonic dispersion. While maintaining the liquid temperature of this emulsion at 25℃ and continuing ultrasonic dispersion, 50 ml of an acetone solution of 0.23 molar lithium bromide was added dropwise over 2 minutes to form a dispersion of silver bromide.
(a) was prepared. A portion of this dispersion (A) was diluted with ethanol, and polyvinyl butyral was removed by centrifugation to prepare a sample (A). Table 2 shows the results obtained.

[Table] *Removed during preparation of sample for electron microscopy From the results in Table 2, it can be seen that the photosensitive silver halide prepared by this method has an irregular crystal type and a wide particle size distribution. Comparative Production Example 2 Silver halide was prepared according to the description in Japanese Patent Publication No. 52-17415. 40ml of acetone solution containing 1.2g of lithium bromide and 2.4g of polyvinyl butyral
Silver trifluoroacetate 3.0 synthesized from trifluoroacetic acid and silver oxide was added to this solution while stirring at 30°C.
A dispersion (b) was prepared by adding 40 ml of an acetone solution containing g dissolved therein dropwise over 2 minutes. 40 ml of the obtained dispersion (b) was immediately poured into 400 ml of water under stirring to obtain a precipitate. After filtering and drying this, silver bromide-
A polyvinyl butyral solid (b)' was obtained. This solid was mixed with xylene/n-butanol (volume ratio: 50/
50) A sample for electron microscopy (b) was prepared by redissolving in 100 ml and performing the same procedure as in Production Example 1. Separately, the above silver halide dispersion in which trifluoroacetic acid anions and lithium cations coexisted was allowed to stand for 2 hours to obtain a dispersion (c) in which some precipitation had occurred. Dispersion (c)
was processed in the same manner as in Production Example 1 to prepare a sample for electron microscopy.
(c) was created. Table 3 shows the results obtained.

[Table] From the results in Table 3, the grain size of the photosensitive silver halide prepared by this method is irregular;
It can also be seen that the particle size tends to increase due to standing. Production Example 2 4.5 g of silver behenate was placed in 100 ml of ethanol and dispersed using a homomixer, and 3 g of polyvinyl butyral was added to the resulting dispersion and dissolved with stirring to prepare a polymer dispersion of silver salt. This dispersion was heated to 45°C under a red safety light, and stirred with methanol 30°C.
ml of ammonium bromide was added dropwise over 30 minutes. After the dropwise addition, the temperature was maintained for 1 hour and stirring was continued, and then the dispersion was cooled to room temperature to prepare a dispersion (2). This dispersion (2) showed no precipitation of silver halide even after being left for a long time. Production example 1 from this dispersion (2)
Sample (2) was prepared in the same manner as above. Dispersion (3) was prepared in the same manner as dispersion (2) except that the reaction temperature was changed to 60° C., and sample (3) was prepared from dispersion (3). Further, a dispersion (4) was prepared under the same conditions as dispersion (3) except that 0.56 g of ammonium chloride was used instead of ammonium bromide, and a sample (4) was prepared from the dispersion (4). Table 4 shows the measurement results of the obtained sample using an electron microscope.

[Table] From the results in Table 4, it can be seen that fine silver halide grains with a narrow particle size distribution can be obtained by this method. Production Example 3 In the dispersion (2) of Production Example 2, 1.25 g of potassium bromide-30 ml of ethanol/glycerin (volume ratio 50/50) was used instead of ammonium bromide-methanol. A dispersion (5) was obtained in the same manner as in 2). This dispersion (5) causes precipitation at room temperature, but when the precipitate was separated by decantation and 3 g of polyvinyl butyral was dissolved in 100 ml of a xylene/n-butanol mixture and redispersed in the solution, good dispersion was observed. It became a thing. Sample (5) was prepared from this dispersion. In addition, dispersion (6) was prepared in the same manner as dispersion (2) using a solution of 3.8 g of mercuric bromide and 30 ml of methanol instead of ammonium bromide-methanol in dispersion (2) of Production Example 2. Sample (6) was prepared from dispersion (6).
Table 5 shows the measurement results of samples (5) and (6) obtained using an electron microscope.

[Table] From the results in Table 5, it can be seen that the photosensitive silver halide grains obtained by this method are fine and have a narrow particle size distribution. Production Example 4 Using the same procedure as Production Example 1, add 2.5 g of silver caprate.
and xylene/n containing 6 g of polyvinyl butyral
- 100 ml of a butanol (50/50 by volume) dispersion was prepared. This dispersion was divided into two parts and kept at 20℃ and 45℃ under red safety light, respectively, and 15ml of acetone was added under stirring.
0.93 g of N-bromosuccinimide dissolved in
It dripped over time. After the dropwise addition, the reaction continued for 12 hours for those reacted at 20°C, and for 2 hours for those reacted at 45°C, and then returned to room temperature to form dispersions (7), (8).
I got it. The resulting dispersion was extremely stable.
Samples (7) and (8) were prepared from this dispersion. In the same manner, 3.6 g of silver palmitate and 4.5 g of silver behenate were reacted to prepare samples (9), (10), (11), and (12). Table 6 shows the reaction conditions and the results of measurement using an electron microscope.

[Table] From the results in Table 6, it can be seen that when an N-halogen compound is used as the organic halogen compound, a fine silver halide with a uniform grain shape and a narrow particle size distribution can be obtained. Production Example 5 Polyvinyl butyral 3
A polymer dispersion of silver salt containing g was maintained at 60 °C and dissolved in 30 ml of acetone under red safety light with stirring.
2.4 g of iodosuccinimide was divided into 15 equal parts and added dropwise at 5 minute intervals. After the dropwise addition was completed, the reaction was continued for another 3 hours, and then the mixture was allowed to return to room temperature to obtain a strong yellow dispersion (13). Sample (13) from this dispersion (13)
It was created. Table 7 shows the measurement results using an electron microscope.
Shown below.

[Table] From the results in Table 7, it can be seen that even when silver halide is silver iodide, silver halide grains with uniform shapes can be obtained. Production Example 6 A silver iodobromide dispersion (14) was prepared in the same manner as in Production Example 5, except that a mixture of 1.8 g of N-bromosuccinimide and 0.12 g of N-iodosuccinimide was used as the halogen compound. This dispersion (14)
Sample (14) was prepared from Table 8 shows the measurement results using an electron microscope.

[Table] From the results in Table 8, it can be seen that even if the silver halide is silver iodobromide, fine silver halide grains with uniform shapes and a narrow particle size distribution can be obtained. Production Example 7 In the same manner as Production Example 5, a polymer dispersion of silver behenate containing a polymer was prepared, and 3.6 g of N-bromosuccinimide (2.0 g per silver behenate) was added to this dispersion.
(using twice the molar amount) was added over one hour at a reaction temperature of 60°C, and the reaction was continued for an additional 2 hours. The temperature was then returned to room temperature to obtain a dispersion (15). A sample (15) was prepared from this dispersion (15). Table 9 shows the measurement results using an electron microscope.

[Table] From the results in Table 9, it can be seen that even if an excessive amount of the halogen compound is used, the crystal type of the silver halide grains produced is well-ordered, and silver halide with a fine and narrow particle size distribution can be obtained. Production Example 8 4.5g of silver behenate was mixed with the following nine solvents: ethanol, n-propanol, isopropyl alcohol, n-butanol, isobutyl alcohol,
The mixture was dispersed in 100 ml of sec-butanol, benzyl alcohol, methyl ethyl ketone, and n-propanol/toluene (50/50 by volume), and 2 g of polyvinyl butyral was added and dissolved with stirring to prepare a polymer dispersion of silver salt. Each of these dispersions
The mixture was heated to 60 DEG C., and 1.5 g of N-bromoacetamide dissolved in 30 ml of acetone was added over 1 hour under a red safety light, and the reaction was continued for an additional 2 hours. Samples (16) to (24) were then prepared from the resulting dispersion which was returned to room temperature. Table 10 shows the measurement results using an electron microscope.

[Table] From the results in Table 10, when alcohols, ketones, and mixed solvents of alcohols and other organic solvents are used as the reaction solvent, the silver halide grains are fine and have a narrow particle distribution. It can be seen that silver oxide can be obtained. Production Example 9 2.3 g of silver behenate was dispersed in 50 ml of cyclohexanol, and 1.5 g of polyvinyl butyral was added and dissolved with stirring to prepare a polymer dispersion of silver salt.
This dispersion was heated to 70℃ and α-
Dilute 0.9g of bromotoluene with acetone and make 30ml
The solution was added dropwise over a period of 2 hours. The reaction was continued for an additional hour, and then the temperature was returned to room temperature, and a dispersion (25) was prepared. A sample (25) was prepared from this dispersion (25). Table 11 shows the measurement results using an electron microscope.

[Table] From the results in Table 11, it can be seen that even when a C-halogen compound is used as the organic halogen compound, fine-grained silver halide particles with well-shaped silver halide grains can be obtained. Production Example 10 Same procedure as Production Example 9, except that 2.4 g of 3-bromopropene and 3-bromopropene were used instead of α-bromotoluene.
Using 2.5g of bromopropyl, the reaction temperature was 80℃.
And so. The reaction in this case was carried out in a reaction vessel equipped with a condenser, and dispersions (26) and (27) were prepared. Samples (26) and (27) were prepared from this dispersion. Table 12 shows the measurement results using an electron microscope.

[Table] From the results in Table 12, it can be seen that compounds having an unsaturated bond at the β-carbon of the halogen are effective as the halogenating agent of the present invention. Production Example 11 A dispersion (28) was prepared under the same conditions as for preparing sample (16) in Production Example 8, except that polyvinyl butyral was replaced with the same amount of nitrocellulose as the protective colloid. A sample (28) was prepared from this dispersion. Table 13 shows the measurement results using an electron microscope.

[Table] From the results in Table 13, it can be seen that even when nitrocellulose is used as a protective colloid, fine grained silver halide particles with well-shaped grains can be obtained. Example 1 51 g of silver behenate and 39 g of behenic acid were mixed with 440 g of xylene.
ml and n-butanol, and dispersed using a homomixer. 80 g of polyvinyl butyral was added as a binder to this dispersion and stirred to prepare a polymer dispersion of silver salt. This dispersion was divided into 82 g portions, and each portion was mixed with the silver bromide dispersion shown below. A 10.0 g of dispersion (1) prepared in Production Example 1 B 10.0 g of dispersion (B) prepared in Comparative Production Example 2 C 0.42 g of solid material (B)' prepared in Comparative Production Example 2
xylene/n-butanol (50/50 by volume)
Redissolved in 100 ml The following components were sequentially added to each of the above polymer dispersions of silver behenate containing the three types of silver bromide to prepare photosensitive slurries. Solution consisting of 4 g of 2,2'-bis-(2-hydroxy-3,5-dimethylphenyl)-3,5,5-trimethylhexane and 10 ml of ethanol Mercury acetate 0.005 g 1-Carboxymethyl-5-[ (3-ethylnaphtho[1,2-d]oxazolin-2-ylidene)
-ethylidene]-3-allyl-thiohydantoin
0.0013 g of these three types of photosensitive slurries were applied to art paper with an undercoat layer of 1 g of vinyl chloride-vinyl acetate (87.13 weight ratio) per m ² at the amount of silver per 1 m ² .
It was applied to a weight of 0.55g and dried. Furthermore, on this coated surface, apply the following topcoat composition per 1 m ² when dry.
Coat it to a weight of 1.5g and prepare a sample for image testing (A).
(B) and (C) were created. All of the following operations were performed under red safety light. Topcoat composition Cellulose acetate 15.0 g Phthalazinone 7.5 g Acetone 300 ml Samples (A), (B) and (C) above were exposed to 700 lux of tungsten light through an optical wedge (Kodak Step Tablet No. 2) under red safety light. A second exposure was given. Next, heat development was performed at a temperature of 125° C. for 10 seconds to obtain step-like images corresponding to each amount of light. The sensitivity (S), gradation (), maximum reflection density (Dmax), and thermal fog density (Dmin) of the obtained image were measured (measurements were made in the same manner in the examples described later). The results are shown in Table 14. show. In addition, the sensitivity in the table is thermal fog +
It was expressed as the reciprocal of the exposure amount required to give a density of 0.15, and expressed as a relative sensitivity with the sensitivity of sample (B) set as 100 (the same expression was used in Examples described later).

[Table] From the results in Table 14, it can be seen that sample (A), which is the heat-developable photosensitive material of the present invention, has a higher contrast and higher density than the conventional samples (B) and (C). Example 2 Samples (D) and (E) were prepared in the same manner as in Example 1, and their photographic properties were measured. As the silver halide dispersion, the silver bromide dispersion shown below was used. D 11.0 g of the dispersion (9) prepared in Production Example 4 E 11.0 g of the dispersion (11) prepared in Production Example 4 The measurement results are shown in Table-15.

[Table] From the results in Table 15, it can be seen that the heat-developable photosensitive material using a silver halide photoreceptor prepared from organic fatty acid silver and an N-halogen compound has high sensitivity. Example 3 Sample (F) was prepared in the same manner as in Example 2, except that 12.0 g of the dispersion (25) of Production Example 9 was used as the silver bromide dispersion, and the measurement results shown in Table 16 below were obtained. Ta.

[Table] From the results in Table 16, the heat-developable photosensitive material prepared using a C-halogeno compound as an organic halogen compound and using a photosensitive silver halide as a photoreceptor is as follows:
It can be seen that this is an excellent heat-developable photosensitive material with high sensitivity, gradation, and maximum density, and low fog density. Example 4 Sample (6) was prepared in the same manner as in Example 2. However, the silver halide dispersion is the dispersion of Production Example 7 (15) 10.5
g was centrifuged (8000 RPM, 30 minutes) to remove the supernatant liquid, and a xylene/n-butanol solution in which 0.3 g of polyvinyl butyral was dissolved was added to the remaining precipitate, which was then dispersed by ultrasonic waves.
The obtained sample (G) was an excellent heat-developable photosensitive material having high sensitivity, gradation, and maximum density, and low minimum density. Example 5 Sample (H) was prepared in the same manner as in Example 2. However, as the silver halide dispersion, the dispersion of Production Example 6 (14)
10.2g was used. Table 17 shows the measurement results.

[Table] The results in Table 17 show that even when the photosensitive silver halide of the present invention is silver iodobromide, a heat-developable photosensitive material having excellent properties can be obtained. Example 6 A sample () was prepared in the same manner as in Example 2. However, silver partinmate 0.4 is used instead of silver behenate.
g, and 10.0 g of the dispersion (16) of Production Example 8 was used as the silver halide dispersion. Table 18 shows the measurement results.

[Table] From the results in Table 18, it can be seen that the sample () of the present invention has high sensitivity, gradation, and maximum density.

Claims (1)

[Scope of Claims] 1. A photosensitive composition comprising at least (c) an oxidation-reduction image forming component comprising a reducible organic silver salt and a reducing agent, (d) a photosensitive silver halide, and (e) a binder on a support. (d) photosensitive silver halide in an organic solvent, (a) organic fatty acid silver suspended and dispersed in the organic solvent; (b) A heat-developable photosensitive material characterized in that it is formed by a stoichiometric reaction with an inorganic or organic halogen compound. 2 (a) Claim 1 characterized in that the organic fatty acid silver is an organic fatty acid silver having 5 or more carbon atoms.
The heat-developable photosensitive material described in .