JPH027447B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a method for producing photosensitive silver halide, and in particular, the present invention relates to a method for producing photosensitive silver halide, in particular, by allowing specific cations to be present during stoichiometric reaction of an organic halide compound to organic fatty acid silver suspended in an organic solvent. ,
The present invention relates to a method for producing photosensitive silver halide having a controlled grain size. Furthermore, the present invention relates to a method for producing photosensitive silver halide, which can be suitably used in heat-developable photosensitive materials using photosensitive silver halide as a photoreceptor. Japanese Patent Publication Nos. 43-4921 and 4924 disclose heat-developable photosensitive materials containing as essential components a reducible organic silver salt, a reducing agent, and a catalytic amount of photosensitive silver halide. There is. In the method for preparing a heat-developable photosensitive material described in Japanese Patent Publication No. 43-4921, a photosensitive silver halide prepared in advance is mixed with a reducible organic silver salt and a reducing agent. However, although the above method has advantages such as ease of chemical sensitization, the method described in Japanese Patent Publication No. 43-4924 (converting a part of the reducible organic silver salt to silver halide) It is said that this method is inferior due to insufficient contact between the reducible organic silver salt and the photosensitive silver halide. 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 aqueous solution of an organic solvent and an inorganic silver compound containing an oil-soluble binder is emulsified by ultrasonic liquid dispersion, an inorganic halogen compound dissolved in the organic solvent is added to this emulsion, and an inorganic silver compound is added to the oil-soluble binder. A method of forming photosensitive 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-A-52-17415 disclose photosensitive halogenation 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 of forming silver 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 in admixture with a synthetic silver halide is described. However, this method does not involve exposing the photosensitive silver halide to chemically active conditions after formation;
Since the photosensitive silver halide is placed in a high temperature atmosphere, it is impossible to maintain the characteristics of the various sensitization treatments applied to the photosensitive silver halide before it is mixed with the reducible organic silver salt. JP-A-47-9171 and JP-A-47-9308 disclose photosensitive halogen in the presence of a new amphiphilic copolymer, and JP-A-50-32928 discloses photosensitive halogen in the presence of a surfactant. The formation of silver oxides is described. However, this method is also difficult to operate, and it is difficult to prepare photosensitive silver halide with uniform grain shapes. In addition, in any of the above methods, the physical properties (e.g., grain shape, grain size, and grain size distribution) of the resulting photosensitive silver halide are controlled by conventional control techniques, such as addition rate of halogenating agent, aging time, It was difficult to control the temperature and stirring speed with good reproducibility. Accordingly, a first object of the present invention is to provide a method for stably and easily producing photosensitive silver halide in the form of fine particles of uniform grain shape in an organic solvent.
A second object of the present invention is to provide a method that allows free and easy control of the grain size and grain size distribution of the photosensitive silver halide produced. Another object of the present invention is to improve the photographic properties (sensitivity, gradation,
An object of the present invention is to provide a method for preparing photosensitive silver halide, which allows the image density, etc., to be freely adjusted. The object of the present invention is to react stoichiometrically (a) organic fatty acid silver suspended and dispersed in an organic solvent with (b) an organic halogen compound, in order to This is achieved by carrying out the process in the presence of at least one type of cation (hereinafter referred to as a particle control agent) belonging to the seventh period and excluding group A elements, silver, and group A elements. The grain control agent of the present invention can grow or refine the grain size of photosensitive silver halide depending on the type and amount of cations added. The photosensitive silver halide grains formed according to the present invention are fine grains of approximately 0.15 μm or less, and do not aggregate or settle when left for a long time. Further, more favorable results can be obtained by coexisting a binder soluble in the reaction solvent as a protective colloid during the formation of photosensitive silver halide. Furthermore, the photosensitive silver halide formed according to the present invention can be used as a photocatalyst in heat-developable photosensitive materials having photographic properties depending on the purpose of use. The (a) organic fatty acid silver used in the present invention 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 laurate, silver myristate, silver palmitate, silver stearate, silver alainate, silver behenate, silver lignocerate, silver oleate, silver linoleate, silver linoleate, silver hydroxystearate, 11-bromoundecanoic acid Examples include substituted or unsubstituted saturated or unsaturated fatty acid silver such as silver. Among the organic fatty acid silvers, those having 5 or more carbon atoms are particularly preferable because silver halide grains having a uniform shape and a narrow particle size distribution can be produced. Such organic fatty acid silver is prepared by adding a solution of a silver salt such as silver nitrate, ammoniacal silver nitrate, or a silver complex salt to a solution of organic fatty acid silver or an alkali metal salt of an organic fatty acid dissolved in an appropriate solvent. The method is common. (b) The organic halogen compound is capable of reacting with (a) the organic fatty acid silver to form a photosensitive silver halide. Preferred organic halogen compounds include compounds represented by the following general formula () or (). 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 () include N-bromsuccinimide, N-bromotetrafluorosuccinimide, N-bromphthalimide, N-bromglutarimide, 1,3
-Dibrome-5,5-dimethyl-2,4-imidazolidinedione, N,N'-dibrome-5,5-
Diethylbarbituric acid, N-bromoisocyanuric acid, N,N'-dibromoisocyanuric acid, N-
Bromooxazolinone, N-bromophthalazinone, N-chlorsuccinimide, N-iodosuccinimide, N-chlorphthalimide, N-bromosactucalin, N-bromocaprolactam, N-
Examples include bromobutyrolactam and N,N'-dibromothiohydantoin. Representative examples of compounds represented by the above general formula () include N-bromoacetamide, N-bromoacetanilide, N-bromobenzenesulfonylanilide, N-bromobenzamide, N-chloroacetamide, N-bromonaphthamide, N- Examples include bromo-P-hydroxybenzamide. Halogenated melamines can also be used; specific examples include tribromemelamine,
Trichlormelamine and the like can be mentioned. Furthermore, C-halogen compounds represented by the following general formula () are also effective as organic halogen compounds. 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 each represents a hydrogen atom, an unsubstituted or substituted alkyl group, or 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. . Examples of the compound represented by the above general formula () include α-haloketone compounds, α-haloamide compounds, halosulfonyl compounds, halonitro lower alkane compounds, and compounds having an unsaturated bond at the β-position carbon relative to the halogen atom. can. Specific examples of the compound represented by the general formula () 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-phenylbutylophenone, α
-Iodo-γ-nitro-β-phenylbutyrophenone, 2-bromo-2-nitro-1,3-propanediol, 2-bromo-2-nitrotrimethylene-1,3-bis(phenyl carbonate) ,α
-bromotoluene, α,p-dibromotoluene,
α, α′-dibrome-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. (b) The organic halogen compound may be used in a stoichiometric amount relative to (a) organic fatty acid silver, but preferably in an excess amount, that is, approximately 1 mole of component (a) to component (b). It is desirable to use a mole to about 3 moles. The particle control agent of component (c) is a cation that belongs to periods 3 to 7 of the periodic table and excludes group A elements, silver, and group A elements. Specifically, aluminum, silicon, phosphorus, sulfur, copper, zinc, scandium, gallium, titanium, germanium, vanadium, arsenic, chromium, selenium, manganese, iron, cobalt, nickel, cadmium, yttrium, indium, zirconium, tin,
Niobium, antimony, molybdenum, tellurium, technetium, ruthenium, rhodium, palladium,
Gold, mercury, lanthanides, thallium, hafnium, lead, tantalum, bismuth, tungsten, polonium, rhenium, osmium, iridium,
Refers to platinum and actinide cations. The cations that are particle control agents of the present invention include hydroxides, halides, nitrites, nitrates, sulfites, sulfates, thiosulfates, oxyacids, rhodanates, sulfides, and phosphates. Inorganic salt compounds, organic acid salts such as saturated or unsaturated aliphatic carboxylates, aromatic carboxylates, sulfonates and nitric acid salts, as well as unsubstituted or substituted alkyl or unsubstituted or substituted aryl groups. It is used as an organic metal compound and an organic chalcogenide compound. The above compound is preferably liquid or solid at room temperature and dissolved in a solvent such as water, alcohols or ketones. Specific examples of compounds include thallium hydroxide (), copper hydroxide (), silicon fluoride, tantalum fluoride, titanium fluoride, niobium fluoride, vanadium fluoride (,), bismuth fluoride (), and fluoride. Arsenic (,), phosphorus fluoride (), subsalt chloride, aluminum chloride, antimony chloride (), sulfur chloride, yttrium chloride,
Iridium chloride (), indium chloride (), uranium chloride (,) erbium chloride, cadmium chloride, gallium chloride (), gold chloride (), chromium chloride (), germanium chloride (), cobalt chloride (), samarium chloride () , zirconium chloride, mercury chloride (), tin chloride (,), cerium chloride (), selenium chloride (), thallium chloride (), tungsten chloride (,), tantalum chloride (), titanium chloride (,), iron chloride ( ，
), terbium chloride (), tellurium chloride (),
Copper chloride (), thorium chloride, niobium chloride (),
Nickel chloride, neodymium chloride, platinum chloride (),
Vanadium chloride (,), palladium chloride (), bismuth chloride, arsenic chloride (), praseodymium chloride (), manganese chloride (), molybdenum chloride (), radium chloride, lanthanum chloride, phosphorus chloride, ruthenium chloride (,), chloride Rhenium (), rhodium chloride, zinc bromide, aluminum bromide, antimony bromide, cadmium bromide, gold bromide (), chromium bromide (), germanium bromide (,
), cobalt bromide, mercury bromide (), tin bromide (,), thallium bromide (,), tungsten bromide, tantalum bromide (), titanium bromide (),
Iron bromide (,), copper bromide (), nickel bromide,
Platinum bromide (), vanadium bromide (), bismuth bromide (), manganese bromide (), radium bromide,
Phosphorus bromide (), zinc iodide, aluminum iodide, antimony iodide (), cadmium iodide,
Germanium iodide (), cobalt iodide (), mercury iodide (), tin iodide (), thallium iodide (), tungsten iodide (), nickel iodide, bismuth iodide, arsenic iodide (), Cadmium nitrate, chromium nitrate (), cobalt nitrate, mercury nitrate (), scandium nitrate,
Cerium nitrate, thallium nitrate, iron nitrate (), copper nitrate (), thorium nitrate, nickel nitrate, neodymium nitrate, bismuth nitrate (), manganese nitrate,
Lanthanum nitrate, lead sulfite (), gallium sulfate (), chromium sulfate (), cobalt sulfate (), copper sulfate (), nickel sulfate, lanthanum sulfate, zinc thiocyanate, mercury thiocyanate (), iron thiocyanate (), Copper thiocyanate (), uranium oxysulfate (), uranium oxynitrate (), chromium oxychloride (), zircolium oxychloride, niobium oxychloride, vanadium oxychloride (),
Bismuth oxychloride (), arsenic sulfide, zinc acetate,
Cobalt acetate (), mercury acetate (), chromium acetate (), nickel acetate, palladium acetate (), thallium acetate (), lead acetate (), cadmium acetate, manganese acetate (), lanthanum acetate, cadmium propionate, malonic acid Thallium, zinc terephthalate, lead metasulfonate, mercury succinimide (), triphenylsilane, trimethylphosphine, dimethylethylphosphine, triphenylphosphine, diphenylphosphine, tri-P-triphosphine, tri- -P-Chlorphenylphosphine, triphenylphosphine selenide, trimethyl arsenic, triphenyl arsenic, antimony triacetate, triphenyl antimony, trimethyl bismuth, triphenyl bismuth, diethyl sulfide, diethyl selenide, dimethyl selenide, bis( P-methoxyphenyl) selenide, diphenyl telluride, phenyl germanium bromide, triphenyl tin bromide, tris(P-methoxy phenyl) bismuth dibromide, phenyl arsenic dichloride, diphenyl tellurium diiodide, etc. . (c) The amount of particle control agent used is (b) per mole of organic halogen compound.
The range is 0.00001 mol or more and 0.3 mol or less. 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 restrictions. Specifically, alcohols, ketones, esters, aliphatic hydrocarbons, aromatic hydrocarbons,
Alcohols, ethers, phenyl acids, etc. 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 diethyl 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 salt (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., if necessary. This suspension is referred to as a liquid (A), and a liquid in which the organic halogen compound of component (b) is dispersed, preferably dissolved, in the above-mentioned organic solvent is referred to as a liquid (B). Liquid (A) and liquid
The concentration of (B) can be set arbitrarily, but preferably 0.5
% to 50% by weight. As a method for mixing liquid (A) and liquid (B), techniques known in the field of photography, such as a forward flow method, a reverse flow method, a simultaneous mixing method, etc., can be used. However, the simple and preferred method is
This method involves adding liquid (B) to liquid (A) which is being stirred. The photosensitive silver halide can be formed by adding the solution (B) all at once, intermittently, or continuously and gradually. However, in order to grow silver halide grains with a uniform grain size and shape, it is preferable to add them intermittently or gradually and continuously.
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 is
Although it is possible to continue the reaction until the end of addition of liquid (B), it is generally preferable to continue the reaction for an additional 30 minutes to 24 hours after the end of addition of liquid (B). Component (c) of the present invention is a component that can freely control the grain size of the photosensitive silver halide formed by the reaction of the above-mentioned components (a) and (b). Photosensitive silver halide is made fine except when a mercury compound is applied. Component (c) is added as is or dissolved in an appropriate solvent, and added to solution (A) or solution (B), or solution (A) and solution before the start of the reaction.
(B) can be mixed in portions or added separately as a liquid (C). 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, it is preferable to use alcohols as the main reaction solvent because the temperature can be set lower than that of other solvents. In the present invention, a polymer soluble in the reaction solution, preferably in the dispersion solvent of liquid (A), can be added to this solvent. 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 are polyvinyl acetals. The amount of polymer soluble in this organic solvent is
Approximately 0.05g to approximately 20% per gram of organic fatty acid silver salt
g, preferably in the range of 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, stirred and dissolved, and the organic fatty acid silver containing the polymer is suspended and dispersed. Prepare the liquid. This dispersion is kept at a constant temperature while stirring under safe light, and an organic halogen compound dissolved in a suitable organic solvent (e.g. acetone) and at least one particle control agent are added thereto for about 30 minutes to about 5 hours. Preferably from about 30 minutes to about 3
Add intermittently or gradually continuously over time. 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.Also, as a halogen compound, N
-When using a halogeno compound, the Special Publication Act of 1973-
It can also be determined by decolorizing a merocyanine dye as described in Publication No. 40484. ). After the reaction is completed, the reaction solution is returned to room temperature to obtain a mixed dispersion of photosensitive silver halide and by-product organic fatty acid. 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 also be used as an image forming component of a conventional wet silver halide emulsion, and can be subjected to known chemical sensitization methods such as sulfur sensitization, gold sensitization, reduction sensitization, etc. In addition, spectral sensitization can be performed using known sensitizing dyes. A preferred embodiment of using the photosensitive silver halide prepared according to the present invention is a heat-developable photosensitive material using the photosensitive silver halide as a photocatalyst. The structure and manufacturing method of this heat-developable photosensitive material are disclosed in Japanese Patent Publication No. 43-4921, for example.
No. 52-17415, JP-A-47-9171, No. 50-
32928, the specification of British Patent No. 1362970, and Japanese Patent Application No. 1987-71787. Hereinafter, the present invention will be further explained based on Examples. Example 1 6.8g of silver stearate and 150ml of ethyl alcohol
and stirred to disperse. 6 g of polyvinyl butyral was added and dissolved in this dispersion under red safety light to prepare a polymer suspension dispersion of silver salt, and the temperature was controlled to 50° C. while stirring. Separately, 20 ml of an acetone solution was prepared containing 2.5 g of N-bromoacetamide (1.04 times the mole of silver stearate) and 14 mg of cadmium bromide tetrahydrate (particle control agent), and the temperature was adjusted as above. The mixture was added dropwise into the silver salt polymer dispersion over 1 hour. After the addition, the reaction temperature was maintained for 1 hour and stirring was continued, and the dispersion was cooled to room temperature again to obtain a silver bromide dispersion ().
This silver bromide dispersion () did not precipitate even when left for a long time. Silver bromide particles were isolated from this dispersion () by centrifugation (6000 RPM), and the silver bromide particles obtained by electron microscopy (1000x, 10000x, and 30000x) using the replica method. The type and particle size distribution were measured. For comparison, a dispersion () was prepared using the same procedure except that cadmium bromide tetrahydrate was not used during the process of obtaining the dispersion (), and the type and particle size distribution of the resulting silver bromide particles were measured. did. The results obtained are shown in Table-1.

[Table] The results in Table 1 show that extremely fine silver halide grains can be prepared by using the grain control agent of the present invention. Example 2 35.8g of silver behenate was dissolved in isopropyl alcohol.
The mixture was added to 700 ml and stirred to disperse. 24 g of polyvinyl butyral was added and dissolved in this dispersion to prepare a silver salt polymer suspension dispersion, which was divided into four equal parts. The mixture was heated to 60° C. under the same conditions under red safety light, and lead acetate trihydrate (particle control agent) was added at varying concentrations to each mixture, followed by further stirring for 20 minutes. Separately, prepare 30 ml of an acetone solution in which 3.6 g of N-bromosuccinimide (1.01 times the mole of silver behenate is used), adjust the temperature, and drop it into the silver salt polymer dispersion containing the particle control agent over 1 hour. did. After the dropwise addition, the reaction was continued for 1 hour, and the temperature was returned to room temperature to prepare silver bromide dispersions (), (), (), and (). Example 1 from this dispersion () to ()
The type and particle size distribution of silver bromide grains were measured in the same manner as above. The results obtained are shown in Table 2.

[Table] From the results in Table 2, it can be seen that by increasing the amount of grain control agent added, the produced silver halide becomes even finer. Example 3 10 g of silver cerotate and 150 g of n-butyl alcohol
ml and stirred to disperse. Under red safety light, 6 g of polyvinyl butyral was added and dissolved in this dispersion to prepare a silver salt polymer suspension dispersion, and the temperature was controlled to 80° C. while stirring. Separately, prepare 20 ml of a methanol solution consisting of 3.5 g of α-bromotoluene (1.03 times the molar amount relative to silver cerotate) and 9 mg of zinc bromide (particle control agent), and add this to the polymer dispersion of silver salt at the above temperature. It was added dropwise into the liquid over 1 hour. After the dropwise addition, the reaction was continued for 30 minutes and the temperature was returned to room temperature to prepare a silver bromide dispersion (). For comparison, dispersion () was prepared in the same manner as dispersion () except that zinc bromide was not used. This dispersion (),
() The type and particle size distribution of silver bromide grains were measured in the same manner as in Example 1. The results obtained are shown in Table 3.

[Table] The results in Table 3 show that fine silver halide grains can be prepared by the grain control agent of the present invention even when a C-halogeno compound is used as a halogenating agent. Example 4 Silver bromide dispersions () to () were prepared in the same manner as in Example 2, except that 0.2 mol% of each of the compounds shown in Table 4 was added to silver behenate as a grain control agent. . This dispersion (XI)
From ~(), the type and particle size distribution of silver bromide grains were measured in the same manner as in Example 1. The results obtained are shown in Table 4.

【table】

[Table] The results in Table 4 show that fine silver halide grains can be controlled by the grain control agent of the present invention. It is also found that mercury compounds exceptionally coarsen the grain size of silver halide grains. Application example 1 100 g of each of the four types of silver bromide dispersions () to () prepared in Example 2 were stirred in water.
It was gradually dropped into 500ml. Filter the precipitate and dry it to obtain silver bromide-polyvinyl butyral solid (),
(), () and () were obtained. Silver behenate separately
20 g of behenic acid and 16 g of behenic acid were placed in a dispersion solvent consisting of 200 ml of xylene and 200 ml of n-butyl alcohol, and dispersed using a homomixer. Add 32g of polyvinyl butyral as a binder to this dispersion,
A polymer dispersion of silver salt was prepared by stirring. This polymer dispersion was divided into four equal parts, 2 g of the previously prepared silver bromide-polyvinyl butyral solids () to () were added to each, thoroughly stirred, and four types of behemoths containing photosensitive silver halide were prepared. An acid silver-polyvinyl butyral dispersion was prepared. Four types of photosensitive slurries were prepared by sequentially adding the following components to this dispersion. Solution consisting of 4 g of 1,1'-bis-(2-hydroxy-3,5-dimethylphenyl)-3,5,5-trimethylhexane and 10 ml of ethanol 0.005 g of mercuric acetate 1-carboxymethyl-5-[ (3-Ethylnaphtho[1,2-d]oxazolin-2-ylidene)-ethylidene]-3-allylthiohydanthone 0.001g This spectrally sensitized photosensitive slurry was mixed with vinyl chloride-vinyl acetate copolymer (87: 13 weight ratio) to 1
It was coated on art paper provided as an undercoat of 1 g per m ² at a silver content of 0.55 g per m ² and dried. Further, on this coated surface, apply the following topcoat composition so that the amount is 1.5g per 1 m ² when dry,
Heat-developable photosensitive materials (), (), () and ()
It was created. All of the above operations were performed under red safety light. Topcoat composition Cellulose acetate 15.0g Phthalazinone 7.5g Acetone 300ml The above heat-developable photosensitive materials () to () were exposed to 700 lux seconds of tungsten light through an optical wedge (Kodatsu Step Tablet No. 2) under red safety light. exposure. Next, heat development was performed at a temperature of 125° C. for 10 seconds to obtain step-like images corresponding to each light amount. The characteristic curves of the obtained heat-developable photosensitive materials () to () are shown in FIG. Figure 1 shows that by using the photosensitive silver halide obtained by the method of the present invention as a photocatalyst, heat-developable photosensitive materials with desired photographic properties (sensitivity, maximum density, gradation, etc.) can be easily produced. I know what I can do. Application example 2 Silver bromide dispersion (XI) prepared in Example 4
700ml of cyclohexane with vigorous stirring
It was gradually dripped inside. The precipitate was filtered and dried to obtain a silver bromide-polyvinyl butyral solid (XI). Add 15g of this solid (XI) to ethyl alcohol.
After dispersion in 50 ml and 50 ml of toluene, the following components were sequentially added to prepare a photosensitive slurry. Ethylene thiourea 0.05 g Dithiourazole 0.10 g Lithium iodide 0.05 g Polyvinyl butyral 3 g This photosensitive slurry was applied to a photographic base paper coated with polymethyl methacrylate as an undercoat layer of 2 g per 1 m ² at an amount of 0.8 silver per 1 m ² A print-out type photosensitive material (2) was prepared by coating and drying the film in an amount of 100 g. This print-out type photosensitive material () was exposed to light of 200,000 lux seconds using a white fluorescent lamp. A blue printed image with a maximum density of 0.9 was formed in the exposed area. All of the above operations were performed under red safety light.

[Brief explanation of drawings]

Figure 1 shows the heat-developable photosensitive material of Application Example 1 ()~
() represents the characteristic curve.

Claims (1)

[Claims] 1. A method of forming photosensitive silver halide by stoichiometrically reacting (a) organic fatty acid silver suspended and dispersed in an organic solvent and (b) an organic halogen compound, comprising:
The reaction of (a) organic fatty acid silver and (b) organic halogen compound with (c) at least one group A element belonging to periods 3 to 7 of the periodic table, excluding silver and group A elements, A method for producing photosensitive silver halide, characterized by carrying out in the presence of cations. 2 (a) Claim 1 characterized in that the organic fatty acid silver is an organic fatty acid silver having 5 or more carbon atoms.
A method for producing photosensitive silver halide as described in Section 1.