JPH0498242A - Manufacture of silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To prevent deterioration of the face quality by forming particles for at least one of matting agents by a polymerization process and leaving these particles in water and/or a water-miscible organic solvent from finishing the particle formation to completing the coating process of the silver halide photographic sensitive material without drying these particles. CONSTITUTION:At least one kind of the matting agents is the particles formed by the polymerization process and these particles are not dried and allowed to remain in water or and/or the water-miscible organic solvent from finishing the particle formation to completing the coating process of the silver halide photographic sensitive material while keeping a weight ratio of the particles to the water or the solvent of 100:3-100:100.

Description

[Detailed Description of the Invention] [Industrial Application Field] The present invention relates to a method for producing a silver halide photographic light-sensitive material, and in particular, it relates to a method for producing a silver halide photographic light-sensitive material. The present invention relates to a method for producing a silver halide photographic material, which prevents clogging failures in the filtration process during production.

(Prior Art) Generally, silver halide photographic light-sensitive materials have a structure in which silver halide is coated with a hydrophilic colloid such as gelatin and fixed on a support. It has the function of holding the silver halide so that the photographic process can proceed smoothly, and it also has the function of protecting the silver halide from external physical influences.However, this hydrophilic colloid is easily affected by the humidity in the atmosphere. Therefore, when the photographic light-sensitive materials are stored under high humidity, they tend to adhere to each other, making them impossible to use.

On the other hand, the three-dimensional shape of the surface of a photographic light-sensitive material is easily influenced by the support (particularly when a hydrophilic colloid layer is coated on a smooth support, the surface becomes smooth and various For example, the adhesion phenomenon described above may occur more easily, and the surface of the photographic material may be easily scratched when it comes into contact with the outside, or if a large number of sheets of photographic material are When sheets are stacked and conveyed automatically, the peelability between the sheets is insufficient, resulting in poor conveyance.Furthermore, due to large friction, conveyance defects are likely to occur, especially in roll-shaped photographic materials. During printing during the photographic process, Newton's rings are more likely to occur, and furthermore, due to the smoothness of the material, surface gloss may increase, which may hinder the viewing of the photographic material after processing.

In order to avoid these disadvantages, a method has conventionally been adopted in which a matting agent consisting of inorganic or organic particles is contained in or near the outermost layer on the front/back side of a photographic light-sensitive material.

For example, US Pat. No. 3,523.022, US Pat. No. 3,492.9
No. 25, No. 3,647,454, Special Publication No. 39-551
No. 3, No. 43-22881, U.S. Patent No. 3,507,6
No. 78, German Patent No. 250L No. 450, etc., and U.S. Pat. No. 2,999.
2.101, 3.76'1.448, 3.02
2.169, 3,443,946, 4,172
, No. 731, Br1t No. 981, 198, 1.061
．． No. 018, L 532,708, Special Publication No. 1972-
No. 18004, JP-A-60-126644, JP-A-60-126644
No. 260038, No. 61-14632, No. 61-20
No. 027, No. 61-20028, No. 61-320.5
Matting agents made of organic particles described in Japanese Patent Publication No. 0, No. 62-14647, Japanese Patent Publication No. 46-1796, and Japanese Patent Application Laid-Open No. 53-7231 are listed.

Organic matting agents can be categorized based on their manufacturing method, such as U.S. Patent No. 2,992.101 and JP-A-61-3205.
0 or British Patent No. 1,532゜708, in which a polymer dissolved in an organic solvent is added to water or an aqueous solution, and then this mixture is stirred with a stirrer to form particles. Emulsion dispersion method, so-called coacervate method as typified by Japanese Patent Publication No. 461796, and in a solvent as typified by U.S. Pat. Examples include a so-called polymerization method in which monomers are polymerized while being suspended in the presence of a polymerization initiator to form particles.

In the production of silver halide photographic light-sensitive materials, the production process of the matting agent and the production process of the hydrophilic colloid coating solution prepared for coating the matting agent are usually discontinuous, so the matting agent is stored only after its production. be done. In order to minimize the volume of the matting agent during storage, Amoi stores the matting agent after drying it as much as possible in order to increase transportation efficiency.

In particular, the matting agent manufactured by the so-called polymerization method described above can be applied to a wide range of systems, so it is necessary to first dry it and then disperse it in an appropriate solvent as necessary for use. There is.

In this way, in silver halide photographic materials that use a matting agent that has undergone a drying process, the coated area of the surface of the photosensitive material after coating is likely to deteriorate due to the agglomerated matting agent, and the filtration process in the manufacturing process This has been a problem for some time because it is prone to clogging and malfunctions.

[Object of the present invention] The purpose of the present invention is to solve the above-mentioned problems, that is, to prevent the surface quality after coating from deteriorating due to agglomerated matting agents, and to prevent clogging failures caused by matting agents in the filtration process in manufacturing. The object of the present invention is to provide a method for producing a silver halide photographic light-sensitive material in which the above-mentioned problems are prevented.

Means for Achieving the Objects of the Invention The above objects of the invention are based on at least one hydrophilic colloid layer containing photosensitive silver halide and at least one layer of one or more mattes on a support. In a method for producing a silver halide photographic material having a non-photosensitive hydrophilic colloid layer containing a matting agent, at least one of the matting agents is formed into grains by a polymerization method, and after grain formation is completed, the silver halide photographic material is A silver halide photographic light-sensitive material characterized in that the polymerized matting agent remains in water and/or a water-miscible organic solvent without being dried until the coating process of the light-sensitive material is completed. Achieved by manufacturing method.

In the method of producing a matting agent using a polymerization method in the present invention, particles may be formed by any polymerization method as long as a polymer is not formed in advance before forming particles.In other words, even if the polymerization reaction is started after particle formation, particles may be formed by any polymerization method. Alternatively, particles may be formed during the polymerization reaction.Also, a polymerization method may be used in which seed particles are added to the system in advance and then particles are formed by the polymerization reaction.For example, a surfactant may be added in the aqueous phase. In the so-called emulsion polymerization method, radicals enter monomers incorporated into micelles to initiate polymerization and grow into particles.In the aqueous phase, monomers and radicals polymerize, become insolubilized, form nuclei, and force (further aggregate) The so-called soap-free polymerization method, in which the monomers grow into particles, the so-called dispersion polymerization method, in which the polymer is precipitated by polymerization in an organic solvent where the monomer is dissolved but the polymer is not, and an oil-soluble polymerization initiator. The so-called suspension polymerization method involves dissolving monomer in a monomer and dispersing it in water and polymerizing it in the form of droplets.The so-called seed polymerization method involves polymerizing the monomer in the presence of seed particles.
There are polymerization methods such as the so-called swelling polymerization method in which polymerization is performed by impregnating the matting agent, and these can be preferably used as a method for producing the particles of the matting agent of the present invention.

In other words, in the present invention, forming particles by a polymerization method refers to particles in which a compound that existed as a monomer before particle formation starts a polymerization reaction for the first time during particle formation to form particles made of a polymer. This refers to the formation method, that is, the method of forming the final particle size and morphology in the reaction solution during polymerization.For example, particles that are polymerized almost simultaneously with the formation of particles (including droplets), In some cases, monomers aggregate over time to form large polymer particles while polymerizing into an initial microscopic polymer, in others polymerization occurs after forming particles, or in some cases, fine particles are added to the reaction system in advance. Examples include those in which particles are formed by allowing a polymer to exist and forming a new polymer outside the core through a polymerization reaction. In this method, for example, a resin (often an uncrosslinked polymer) is formed in advance before particle formation, this is dissolved in a solvent, and then finely dispersed ( If necessary, this is followed by desolvation) to obtain particles of a desired particle size using a so-called emulsification method (in the present invention, the particle formation method using this method is referred to as an emulsification method, and is included in the present invention). (different from emulsion polymerization method).

More specifically, the monomer compounds of the polymer compound forming the particles of the matting agent of the present invention include acrylic acid esters such as methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, and n-butyl acrylate. Acrylate, isobutyl acrylate, sec-butyl acrylate, tert-butyl acrylate, amyl acrylate, hexyl acrylate, 2-ethylhexyl acrylate, octyl acrylate, tert-octyl acrylate, 2-chloroethyl acrylate, 2-bromoethyl acrylate,
4-chlorobutyl acrylate, cyanoethyl acrylate, 2-acetoxyethyl acrylate, dimethylaminoethyl acrylate, hensyl acrylate, methoxybenzyl acrylate, 2-chlorocyclohexyl acrylate, cyclohexyl acrylate, furupryl acrylate, tetrahydrofurfuryl acrylate, phenyl Acrylate, 2-hydroxyethyl acrylate, 5-hydroxypentyl acrylate, 2.2
-dimethyl-3-hydroxybrobyl acrylate, 2
-Methoxyethyl acrylate, 3-methoxybutyl acrylate, 2-ethoxyethyl acrylate, 2-i
s.

Propoxy acrylate, 2-butoxyethyl acrylate, 2-(2-methoxyethoxy)ethyl acrylate, 2-(2-butoxyethoxy)ethyl acrylate, ω-methoxypolyethylene glycol acrylate (
addition mole number n-9), 1-bromo-2-methoxyethyl acrylate, 1,1-dichloro-2-ethoxyethyl acrylate, and the like.

Examples of methacrylic acid esters include methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, 5ec-butyl methacrylate, tert-butyl methacrylate, amyl methacrylate, hexyl methacrylate, cyclo Hexyl methacrylate, benzyl methacrylate, chlorobenzyl methacrylate, octyl methacrylate, sulfopropyl methacrylate, N-ethyl-N-phenylaminoethyl methacrylate, 2-(3-phenylpropyloxy)ethyl methacrylate, dimethylaminophenoxyethyl methacrylate, flu Furyl methacrylate, tetrahydrofurfuryl methacrylate,
Phenyl methacrylate, talesyl methacrylate, naphthyl methacrylate, 2-hydroxyethyl methacrylate, 4-hydroxybutyl methacrylate, trithielene gelicol monomethacrylate, dipropylene glycol monomethacrylate, 2-methoxyethyl methacrylate, 3-methoxybutyl methacrylate, 2-
Atothekidiethyl methacrylate, 2-acetoacetoxyethyl methacrylate, 2-ethoxyethyl methacrylate, 2-3so-propoxyethyl methacrylate, 2-butoxyethyl methacrylate, 2(2-methoxyethoxy)ethyl methacrylate, 2-(2-ethoxyethoxy) Ethyl methacrylate, 2-(2-butoxyethoxy)ethyl methacrylate, ω-methoxypolyethylene glycol methacrylate (additional mole number n = 6
), allyl methacrylate, methacrylic acid dimethylaminoethyl methyl chloride salt, and the like.

Examples of vinyl esters include vinyl acetate, vinyl propinate, vinyl butyrate, vinyl isobutyrate, vinyl caproate, vinyl chloroacetate,
Examples include vinyl methoxy acetate, vinyl phenylacetate, vinyl benzoate, vinyl salicylate, and the like.

Examples of olefins include dichloropentadiene, ethylene, propylene, ■-butene, 1-pentene,
Examples include vinyl chloride, vinylidene chloride, isoprene, chlorobrene, butadiene, 2,3 dimethylbutadiene, and the like.

Examples of styrenes include styrene, methylstyrene, dimethylstyrene, trimethylstyrene, ethylstyrene, isopropylstyrene, chloromethylstyrene, methoxystyrene, acetoxystyrene, chlorstyrene, dichlorostyrene, bromstyrene, trifluoromethylstyrene, vinyl Examples include benzoic acid methyl ester.

Examples of crotonate esters include butyl crotonate, hexyl crotonate, and the like.

Examples of itaconic diesters include dimethyl itaconate, diethyl itaconate, and dibutyl itaconate.

Examples of diethyl maleates include diethyl maleate, dimethyl maleate, and dibutyl maleate.

Examples of the fumaric acid diesters include diethyl fumarate, dimethyl fumarate, and dibutyl fumarate.

Acrylamides include acrylamide, methylacrylamide, ethylacrylamide, propylacrylamide, butylacrylamide, tert-butylacrylamide, cyclohexylacrylamide, benzylacrylamide, hydroxymethylacrylamide,
Methoxyethylacrylamide, dimethylaminoethylacrylamide, phenylacrylamide, dimethylacrylamide, diethylacrylamide, β-cyanoethylacrylamide, N-(2-acetoacetoxyethyl)acrylamide, etc.; Methacrylamides, such as methacrylamide, methylmethacrylamide, ethylmethacrylamide amide, propyl methacrylamide, butyl methacrylamide, ter
t-butylmethacrylamide, cyclohexylmethacrylamide, benzylmethacrylamide, hydroxymethylmethacrylamide, methoxyethylmethacrylamide, dimethylaminoethylmethacrylamide, phenylmethacrylamide, dimethylmethacrylamide, diethylmethacrylamide, β-cyanoethylmethacrylamide, N-(2-acetoacetoxyethyl) methacrylamide, etc.; Allyl compounds, such as allyl acetate, allyl caproate, allyl laurate, allyl benzoate, etc.; Vinyl ethers, such as methyl vinyl ether, butyl vinyl ether, hexyl vinyl ether, methoxyethyl Vinyl ether, dimethylaminoethyl vinyl ether, etc.; Vinyl ketones, such as methyl vinyl ketone, phenyl vinyl ketone, methoxyethyl vinyl ketone, etc.; Vinyl heterocyclic compounds, such as vinyl pyridine, N-vinylimidazole, N-vinyloxazolidone, N- Vinyltriazole, N-vinylpyrrolidone, etc.; Glycidyl esters, such as glycidyl acrylate, glycidyl methacrylate, etc.; Unsaturated nitriles, such as acrylonitrile, meccrylonitrile, etc.; Polyfunctional monomers, such as divinylbenzene, methylenebisacrylamide, such as ethylene glycol dimethacrylate.

Furthermore, acrylic acid, methacrylic acid, itaconic acid, maleic acid, monoalkyl itaconates such as monomethyl itaconate, monoethyl itaconate, monobutyl itaconate, etc.; monoalkyl maleates such as monomethyl maleate, monoethyl maleate, maleic acid, etc. monobutyl acids, etc.; citraconic acid, styrene sulfonic acid, vinylbenzyl sulfonic acid, vinyl sulfonic acid, acryloyloxyalkylsulfonic acid, such as acryloyloxymethylsulfonic acid, acryloyloxyethylsulfonic acid, acryloyloxypropylsulfonic acid, etc.; methacryloyloxyalkyl Sulfonic acids, such as methacryloyloxymethylsulfonic acid, methacryloyloxyethylsulfonic acid, methacryloyloxypropylsulfonic acid; acrylamide alkylsulfonic acid,
For example, 2-acrylamido-2-methylethanesulfonic acid, 2-acrylamido-2-methylpropanesulfonic acid, 2-acrylamido-2-methylbutanesulfonic acid, etc.; methacrylamide alkylsulfonic acid, such as 2-methacrylamido-2- methylethanesulfonic acid,
2-methacrylamido-2-methylpropanesulfonic acid, 2-methacrylamido-2-methylbutanesulfonic acid, etc.; acryloyloxyalkyl phosphates, such as acryloyloxyethyl phosphate, 3-acryloyloxypropyl-2-phosphate, etc.; methacryloyloxyalkyl Phosphates, such as methacryloyloxyethyl phosphate and 3-methacryloyloxypropyl 2-phosphate; sodium 3aryloxy-2-hydroxypropanesulfonate having two hydrophilic groups, and the like. These acids may be salts of alkali metals (eg, Na, etc.) or ammonium ions. Furthermore, as other monomer compounds, U.S. Pat.
No. 438,708, No. 3.554,987, No. 4
, 215.195, 4,247,673, JP-A-57-205735, and the like can be used. Examples of such crosslinking monomers include N-(2-acetoacetoxyethyl)acrylamide, N(1-(2-acetoacetoxyethoxy)ethyl)acrylamide, and melamine or benzoguanamine. can be mentioned.

These monomer compounds may be used as a matting agent made of a polymer obtained by polymerizing them alone, or as a matting agent made of a copolymer obtained by combining a plurality of monomers.

Among these monomeric compounds, acrylic esters,
Methacrylic acid esters, vinyl esters, and styrenes are preferably used. Further, as the matting agent of the present invention, particles containing fluorine atoms or silicon atoms as described in JP-A-62-14647, JP-A-62-17744, and JP-A-62-17743 may be used. No. 64-77052, European Patent 307855
It is also possible to use particles having reactive groups (particularly on gelatin) as described in the above-mentioned patent application.

After the completion of particle formation, the matting agent may be present alone in water and/or a water-miscible organic solvent, or two or more thereof may be present in a mixture.

The water-miscible organic solvent used in the present invention refers to the solubility in water (organic solvent/H20) when mixed with water at 20°C.
+ organic solvent) is 5% by weight or more, and refers to an organic solvent that forms a homogeneous layer within this range. Examples of such organic solvents include methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, sec-butatol, tert-butanol, acetone, methyl ethyl ketone, diacetone alcohol, acetaldehyde, methyl acetoacetate. , acetonitrile, acetonitrile acetone, amyl methyl ketone, allyl alcohol, ethylamine, 2-ethylbutyl cellosolub, cellosolve, butyl cellosolve, methyl cellosolve, ethyl methyl ether, ethylene oxide, ethylene glycol, diethylene glycol, glycerin, ethylene chlorohydrin, methyl formate , methyl acetate, methyl cellosolve acetate, ethyl lactate, dioxane-1,4, dimethyl sulfoxide, acetic acid, propionic acid, butyric acid, pyridine, phenol, acrylic acid, methacrylic acid, among others, methanol, ethanol, isopropanol, n-
Propertool, n7'tanol, acetone, ethylene glycol, etc. are preferably used.

In the present invention, the ratio of water and/or water-miscible organic solvent containing the matting agent to the matting agent from the completion of particle formation of the matting agent to the completion of the coating process of the photographic light-sensitive material is expressed as a weight ratio of matting agent/solvent = If the ratio of the solvent is higher than 100/3, the purpose can be sufficiently achieved, especially when taking into account the reduction of the volume (bulk) of the matting agent during storage, the ratio is 100/3 to 1001500. More preferably 1
It is preferable that it is 00/3 to 100/100.

Water and water-miscible organic solvents may be used alone or in combination of two or more.

There is no particular limit to the amount of matting agent used in the present invention, but 5
It is preferably from 10 to 200 .mu./po, particularly from 10 to 100 .mu./po.

The matting agent is preferably added to one or both of the outermost layers of the support, but it may be added to a layer adjacent to the outermost layer.

There is no particular restriction on the particle size of the matting agent, but the particle size is 1 to 1.
It is preferably 30 μm5, particularly 3 to 20 μm.

In the present invention, a matting agent formed into particles by a polymerization method and other matting agents (for example, an emulsion matting agent or an inorganic matting agent as referred to in the present invention) can be used in combination. Both may be present in the same layer or may be present in different layers.

In the present invention, the non-photosensitive hydrophilic colloid layer includes, for example, an emulsion layer, a protective layer, a yellow filter layer, an intermediate layer, an antihalation layer, a subbing layer, etc. In the case of one side, ie, the backing layer, it refers to all its layers.

The photographic material to which the matting agent of the present invention relates is not particularly limited, and includes, for example, color negative, color reversal, color paper, color reversal paper, color instant, black and white negative, black and white paper, graphic arts, micro,
It can be applied to various silver halide photographic materials such as facsimile, X-ray, black and white instant.

As a component of the photographic light-sensitive material in which the matting agent of the present invention is involved, the silver halide emulsion can be
They can be produced by any of the double jet method, controlled double jet method, acid method, ammonia method, and neutral method, and there are no particular restrictions on the shape, size, and size distribution of the silver halide grains. As the silver halide, any of silver chloride, silver chlorobromide, silver bromide, silver iodobromide, silver chloroiodobromide, etc. can be used.

The binder constituting the hydrophilic colloid layer is not particularly limited, but gelatin, so-called alkali-treated gelatin, acid-treated gelatin, gelatin derivatives, modified gelatin, etc., carboxymethyl cellulose, hydroxyethyl cellulose, starch derivatives, polyvinyl alcohol, poly-N-pyrrolidone, Polyacrylic acid copolymers, polyacrylamide, etc. can be used alone or in combination. Further, a latex-like water-dispersed vinyl compound polymer can also be contained in the hydrophilic colloid layer. As such a latex, homo- and copolymers such as alkyl acrylate, alkyl methacrylate, acrylic acid, methacrylic acid, glycidyl acrylate, styrene, vinyl chloride, vinylidene chloride, and polymers providing cation sites can be used.

Silver halide emulsions can be chemically sensitized by conventional methods. For example, US Pat. No. 2,3.99,083, US Pat.
Gold compounds, salts of noble metals such as platinum, palladium, rhodium, and iridium, as described in U.S. Pat. No. 97,856, U.S. Pat.
Chemical sensitization can be carried out using the sulfur compound described in No. 13, other stannous salts, amines, and the like.

Various compounds can be added as stabilizers to the silver halide emulsions involved in the present invention. For example, 4-hydroxy-6-methyl-1,3,3α.

Many heterocyclic compounds including 7-titrazaindene, 3-methyl-benzothiazole, 1-phenyl-5-mercaptotetrazole, polyhydroxybenzene compounds,
Many compounds such as mercury-containing compounds, mercapto compounds, and metal salts can be used.

In addition, various spectral sensitizing dyes such as merocyanine dyes, carbocyanine dyes, cyanine dyes, etc. can be used in the silver halide emulsion to which the present invention relates, depending on the purpose.

In addition, the photographic materials to which the present invention relates include hardeners, couplers, slip agents, surfactants, antistatic agents, thickeners, dyes, ultraviolet absorbers, matting agents, pH adjusters, conductive polymers, It can include conductive inorganic particles, tetrazolium compounds and hydrazine derivatives, developing agents, colloidal silica, and the like.

Examples of hardening agents include aldehyde compounds, active halogen-containing compounds such as 2-hydroxy-4,6-dichloro-1,3,5 triazine, vinylsulfone compounds, N-methylol compounds, and mucochloric acid. Halogen carboxaldehyde compounds and the like can be used.

As the slipping agent, for example, liquid paraffin, waxes, polyfluorinated hydrocarbons, silicones, etc. can be used.

Color couplers include 4-equivalent diketomethylene yellow couplers, 2-equivalent diketomethylene yellow couplers, 4-equivalent or 2-equivalent pyrazolone magenta couplers and indashilon magenta couplers 1,
α-naphthol cyan couplers, phenolic cyan couplers, and so-called D4R couplers can also be used.

Examples of surfactants include natural surfactants such as saponin, nonionic surfactants such as alkylene oxides, higher alkylamines, cationic surfactants such as quaternary ammonium salts, and acidic groups such as carboxylic acids and sulfonic acids. Any of the anionic surfactants and the like can be used.

As the antistatic agent, the above-mentioned surfactants, alkali metal salts of styrene-maleic acid copolymers, and antistatic agents described in U.S. Pat. No. 3,206,312, U.S. Pat. be able to.

Further, in the photographic material to which the present invention relates, matting agents other than those of the present invention can be used in combination with the matting agent of the present invention. For example, silica, titanium oxide,
Inorganic matting agents such as magnesium oxide, organic matting agents that are not based on polymerization methods, and polymerizable organic matting agents that have undergone a drying process after polymerization, such as polymethyl methacrylate,
Polystyrene etc. can be used.

As the support for the photographic material to which the present invention relates, any support commonly used in the art, such as cellulose acetate film, polyethylene terephthalate film, baryta, or paper coated with α-olefin polymer, can be used.

There are no particular restrictions on the coating method for the photographic material to which the present invention relates, and methods include dip coating, air knife coating, curtain coating, extrusion coating, and U.S. Pat. A multilayer simultaneous coating method described in No. 2,761,791 and the like can be used.

The feature of the present invention is that after the matting agent is formed into particles using a polymerization method, it is added to the coating solution for photographic light-sensitive materials until it is actually coated.
The matting agent is present in water and/or a water-miscible paid solvent without drying the matting agent particles, but there are no particular restrictions on the drying process of the photosensitive material after coating, and ordinary drying methods can be used. Can be used.

For example, JP-A No. 1-229244, JP-A No. 1-22924
No. 0, No. 1-270046, No. 1-296242,
Reference may be made to the description in No. 1-306838 and the like.

Examples will be described below, but the present invention is not limited thereto.

Preparation Example-1 2 g of polyvinyl alcohol was dissolved in 300 d of water, and 2 g of methyl methacrylate solution LO in which 2 g of hairzobisisobutyronitrile was dissolved was added.

This mixed solution was stirred for 10 minutes at 3000 rpm using a mixer, and immediately reacted under a nitrogen atmosphere at 75° C. for 4 hours with gentle stirring.

After the reaction, the mixture was slightly dehydrated by centrifugation, and the product was washed with water. After washing, it was dispersed in water. The average particle size of the polymethyl methacrylate particles obtained was 13.degree. 2 .mu.m.

Preparation Example-2 The same procedure as Preparation Example-1 was carried out except that the rotation speed of the mixer in Preparation Example-1 was changed to 600 rpm.

The average particle size of the obtained polymethyl methacrylate particles was 3
．． It was 4 μm.

Preparation Example-3 2 g of polyvinyl alcohol and 28 g of methacrylic acid were dissolved in 300 ra of water, and 74 g of a methyl methacrylate solution containing 2 g of hairzobisisobutyronitrile was added thereto. This mixed solution was subjected to the same steps as in Preparation Example 2, including dispersion using a mixer, to obtain particles of poly(methyl methacrylate/methacrylic acid) having an average particle size of 2.8 μm.

Preparation Example-4 Dissolve 5 g of gelatin in 300 d of water, and dissolve Hestylene 2
A mixture of 5g1 divinylhenzene 5g2 benzoyl peroxide 1.5g was added. This mixture was stirred for 10 minutes at 3000 rpm using a mixer, and immediately reacted under a nitrogen atmosphere at 80'C for 3 hours with gentle stirring. After the reaction, the mixture was slightly dehydrated by centrifugation, and the product was washed with water. After washing, it was dispersed in water. The average particle size of the obtained polystyrene particles was 12.4 μm.

Preparation Example-5 The same procedure as Preparation Example-4 was carried out except that the mixer rotation speed in Preparation Example-4 was changed to 600 rpm.

The average particle size of the obtained polystyrene particles was 2.8 μm.

Preparation example-6 Mixing conditions for matting agents and solvents prepared by various synthesis methods.

The so-called wet matting agents of the present invention were prepared as shown in Table 1 by mixing the matting agents (particles) prepared in Preparation Examples 1 to 5 with a solvent under the following conditions without drying them at all.

For comparison, a so-called dry matte agent was prepared as shown in Table 2.

Table 2 [Examples] Examples will be described below, but the present invention is not defined by these examples.

Example 1 A photographic material sample containing the matting agent of the present invention was prepared as follows.

On the undercoated cellulose triacetate paste, an antihalation layer, an intermediate layer, a red-sensitive emulsion layer, an intermediate layer, a green-sensitive emulsion layer, a yellow filter layer, a blue-sensitive emulsion layer, and a protective layer as shown in Table 3 are formed. , in this order starting from the support and sample 1.
01 to 118 were produced. The matting agent listed in Table 4 was added to the gelatin aqueous solution, an anionic surfactant was added, and the mixture was mixed at 8000 rpm using a mixer.
The dispersion was stirred for 0 minutes and added to the protective layer coating solution.

(However, the emulsion-method matting agent was added as is to the protective layer coating solution.) After coating, the degree of generation of aggregates on the sample surface was visually observed and evaluated using a magnifying glass. The results are listed in Table 4. As for the evaluation criteria, the frequency of E-aggregates is extremely high.

A few C-aggregates are seen. A- No aggregates at all.

For binding, D was set between E and C, and B was set between C and A.

(Preparation method of emulsification matting agent) Poly (methyl methacrylate/methacrylic acid-6/4
) was dissolved in ethyl acetate, and this solution was added to a weakly acidic gelatin solution containing dodecylbenzenesulfonic acid and stirred for 30 minutes. After stirring, ethyl acetate was removed by distillation under reduced pressure to obtain a matting agent dispersion of poly(methyl methacrylate/methacrylic acid-6/4) having an average particle size of 3.times.2 .mu.m.

From the results in Table 4, sample 10 using the matting agent of the present invention
7 to 117 are samples 102 to 106 using comparative matting agents.
．． Compared to No. 118, the number of aggregates on the surface of the sample after coating was clearly reduced, which is clearly due to the effect of the present invention.

Example-2 To a gelatin aqueous solution kept at 48°C, add 1lrCfi6 to a silver nitrate aqueous solution and 3X10-7 mol per mol of silver.
and 3X10-7 moles of (Nl(a) 3Rhc
30 per mole of sodium chloride and silver containing l b
A monodisperse silver chlorobromide emulsion with an average grain size of 0.28 μm was prepared by simultaneously adding an aqueous sodium bromide solution corresponding to the mol % for 30 minutes and maintaining the potential at 70 mV during that time. To this emulsion, 0.2 mol % of a 1% aqueous potassium iodide solution was added per mole of silver to carry out conversion, and then desalting was carried out by a flocculation method. Hypo and chloroauric acid were added to this emulsion, and after chemical ripening at 60°C, 4-hydroxy-6-methyl-1,
30 m of 1% aqueous solution of 33a, 7-chitrazaindene per mole of silver! added.

0 of the infrared sensitizing dye shown below is added to 1 kg of this emulsion.
．． Sensitization in the infrared region was carried out by adding a 05% solution of 60%.

This emulsion was treated with 0.5 g of 4,4'-bis-(4,6-dinaphthoxypyrimidin-2-ylamino)-stilbenedisulfonic acid disodium salt for supersensitization and stabilization.
% methanol solution 10 rrdl and 2,5-dimethyl-3
90 ml of a 0.5% methanol solution of -allyl-benzothiazole iodo salt was added. Furthermore, as a hydrazine derivative, the compound (2) below was added at 1.3×10. -3 mol 1 mol Ag, 5.3XlO-3 mol 1 mol Ag2 hydroquinone 100 μ/bo, polyethyl acrylate latex as a plasticizer at 25% gelatin binder ratio, 2-bis(vinyl 160 ml of (sulfonylacetamido)ethane was added and coated on a polyester support at 3.1 g of silver/rd. Gelatin was 2.5 g/bo.

On top of this, 0.6 g/rrf of gelatin and colloidal silica with a particle size of 10 to 20 mμ (as shown in Table 5) as a matting agent (
Snowtex C) 70■/Bo, Compound Postscript ■100■
/bo, dodecylbenzenesulfonate sodium salt as a coating aid, and a fluorine-based surfactant of the following structural formula (2) were added to the upper protective layer and gelatin 0.7 g/nf.
, polyethyl acrylate latex 225mg/r4
, Dye 20■/I of the following structural formula 〇, Dye 10■/I
A lower protective layer containing Tr and sodium dodecylhenzenesulfonate as a coating aid was simultaneously coated on a polyethylene terephthalate film having a thickness of 100 μm.

■ c8 F, 7SO2N-CH2C00K3
H7 (CH2) 4S03- (CH2)
Next to 4SO3, there is a fifth on the opposite side of the support.
As shown in the table, the following head layer with different matting agents was applied, and a bank protective layer was applied on top of it.

(Hack layer) Gelatin 0.75g/Pomat agent (Table 5) Sodium dodecylbenzenesulfonate 20mg/Bofluorinated surfactant (said compound ■) Sliding agent (compound ■) (Gelatin dispersion) (Pack protective layer) Gelatin dodecylbenzenesulfonate sodium dye Previous ■ Postscript ■ Postscript ■ 1.3-Divinylsulfonyl 2-propatol Polyvinyl-Potassium benzenesulfonate ■ 2■/Po100■/Po3.0g/Po80■ 80■ 30 ■ 100 ■ 60 ■ / po 30 g / rd Compound ■ Compound ■ (Sliding agent) Samples 201 to 211 prepared in this way were used in Examples -
In the same manner as in Example 1, the degree of aggregates was evaluated on the emulsion side and the back side of the sample after coating.

The results are shown in Table 5.

Sensitizing dye ■ Compound ■ From the results in Table 5, sample 205 using the matting agent of the present invention
-211 are samples 202-204 using comparative matting agents
In comparison, the number of aggregates on the emulsion side and back side of the sample after coating was clearly reduced, which is clearly due to the effect of the present invention.

Example 3 A filterability test was conducted on the matting agents M-1 to 13 of the present invention prepared in Preparation Example 6 and the comparative matting agents M-a-e by the following method.

Add a matting agent (or matting agent dispersion), water, and sodium dodecylbenzenesulfonate to a 20% aqueous solution of gelatin, and then mix this mixture with a mixer to 80%
Mixed for 10 minutes at 00 rpm. The concentrations of each material were 6% gelatin, 6% matting agent, and 0.18% sodium dodecylbenzenesulfonate. The obtained gelatin dispersion of the matting agent was subjected to a filtration test using a suction filtration method using a filter with a diameter as shown in Table 6, and the amount of filtrate (i.e., the amount of liquid that passed through the filter) was determined. I asked for The filter used is a disc-shaped one with a diameter of 47III11, and the vacuum capacity is 730 mm for suction.
A mmHg electric pump was used. A 2000 d gelatin dispersion liquid for the matting agent was prepared, and the liquid temperature at the time of the test was 40°C.
Met. The evaluation results are shown in Table 6.

Table 6 From Table 6, it can be seen that for the matting agents M-1 to 13 of the present invention, almost the entire amount of the prepared matting agent gelatin dispersion passed through the filtration filter, and for the comparative matting agent Ma-e, it was about 400 to 5.
It can be seen that clogging occurs when the temperature is 00. It is clear that the above-mentioned matting agent having excellent filterability is due to the effect of the present invention.

[Effects of the Invention] Particles are formed by a polymerization method, and are kept in water and/or water-miscible organic solvents without being dried during the period from the completion of particle formation to the completion of the coating process of the silver halide photographic material. By the method of producing the matting agent of the present invention in which the matting agent remains present, it is possible to prevent deterioration of the coated surface quality of the surface of the photosensitive material after coating due to aggregates, and also to prevent clogging during filtration of the coating solution. It could be prevented. These effects were first revealed by the present invention.

Patent applicant: Fuji Photo Film Co., Ltd. 4. Subject of amendment: ``Detailed description of the invention'' in the specification.

Claims (2)

[Claims] (1) Silver halide having at least one photosensitive hydrophilic colloid layer containing silver halide and at least one non-photosensitive hydrophilic colloid layer containing one or more matting agents on a support. In the method for producing a photographic material,
At least one of the matting agents is formed into particles by a polymerization method, and the polymerization matting agent is not dried during the period from the completion of particle formation to the completion of the coating process of the silver halide photographic material. A method for producing a silver halide photographic material, characterized in that the material remains in a water-miscible organic solvent. (2) The weight ratio of the matting agent and water and/or water-miscible organic solvent between the completion of grain formation and the completion of the coating process of the silver halide photographic light-sensitive material is as follows. 2. The method for producing a silver halide photographic material according to claim 1, wherein the silver halide photographic material is present in a solvent having a ratio of 100/3 to 100/100.