JP2001109090A - Silver halide photographic sensitive material and method for producing same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a silver halide photographic sensitive material for medical X-ray photographing having no effect on sensitometry and excellent in scratch resistance, sticking preventiveness and conveyability. SOLUTION: The silver halide photographic sensitive material has at least one silver halide emulsion layer on each of both faces of the substrate and two or more non-photosensitive colloidal layers on the silver halide emulsion layer. The non-photosensitive colloidal layer as the middle layer contains spherical polymer particles having 1-10 μm average particle diameter and <=10% relative standard deviation and a polyalkylene oxide type nonionic surfactant. The non-photosensitive colloidal layer as the outermost layer contains a fluorine- containing surfactant.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a silver halide photographic light-sensitive material, and more particularly, to a silver halide for medical X-ray photography which has improved antistatic properties, abrasion resistance, anti-stickiness, transportability, and stains in processing solutions. It relates to a photosensitive material.

[0002]

2. Description of the Related Art Recently, various kinds of automation have been carried out in order to enhance work efficiency. For example, in the case of medical photosensitive materials, an auto feeder for automatically feeding a photographed sheet film to an automatic developing machine, an X-ray mono-cassette, etc. Receive supplier that automatically performs a series of operations to take out the film that has been taken from and load the unexposed film into the cassette,
Conveyor system that conveys the sheet film from each shooting room to the automatic processor by the conveyor, and changer that automatically changes the photographed and unexposed sheet film for the X-ray intensifying screen fixed at the photographing position. Film has been transported. In addition, as a result of the improvement of the processing speed of the automatic developing machine, ultra-rapid processing of 45 seconds or less in Dry to Dry has become widespread. With these automation and high-speed transport, photosensitive materials have good antistatic properties,
There is a strong demand for a property having high scratch resistance, no scratchiness, and good transportability.

[0003] Silver halide photographic light-sensitive materials are liable to be charged with static electricity by friction and peeling by a conveying roller or a conveying belt during high-speed conveyance under low humidity. And it causes pinholes and uneven development.
This will significantly degrade the quality of the photographic image. Therefore, many antistatic techniques have been proposed, and for example, various methods using various surfactants for the surface protective layer, or many inorganic salts, conductive metal oxides, and ionic polymers have been disclosed.

[0004] However, in these conventional techniques, originally,
In a low humidity atmosphere where conductivity needs to be imparted, there has been a problem that the conductivity decreases due to a decrease in water content. Therefore, if the amount of the conductive compound is increased in order to avoid such a drawback, this will result in excessive water retention in a high-temperature atmosphere, which will cause serious obstacles such as causing stickiness and stickiness between photosensitive materials. Will be invited. In addition, the use of a large amount of conductive compounds results in the accumulation of these compounds in the developing and fixing processing solutions, and the inhibition of development and fixing due to the compounds deposited from the processing solutions adhering to the photosensitive material surface. Causes inhibition. In recent years, from the viewpoint of environmental protection, the amount of replenishment tends to be reduced more and more in order to reduce the amount of processing solution waste, and the importance of an antistatic method free of processing solution contamination is increasing.

With respect to scratch resistance, it is effective to increase the elastic modulus of the protective layer or the silver halide emulsion layer, and to lower the pressure sensitivity by lowering the ratio of silver halide to the binder. The fixing speed and the washing speed are lowered, and the covering power is lowered. Therefore, it is difficult to apply the method to a photosensitive material corresponding to rapid processing in recent years. On the other hand, improving the slip on the film surface is also known as a means for improving the scratch resistance, but there is a problem that the slip agent accumulated in the processing tank of the automatic developing machine adheres to the film and causes processing defects.

[0006] Poor transport is caused when the film is repeatedly pressed, peeled, and slid between the transport roller and the material of each part and becomes charged and stuck due to static electricity, or the matting agent in the film is peeled off and transported. As a result of adhering and accumulating on the suction cup for use, the suction cup may not be adsorbed on the film, which may occur. In the former case, various antistatic techniques have been proposed and can be referred to.

[0007] Further, under conditions of high humidity, the films tend to stick together, and a plurality of films are likely to be simultaneously conveyed or clogged. With respect to such dustiness, a method of adding a matting agent to a film and a method of adding a fluorine-based surfactant are known. However, when the matting agent is used to improve the tightness, the above-mentioned scratches are deteriorated, and a defective conveyance due to the matting agent peeling off occurs. On the other hand, when a large amount of the fluorinated surfactant is used, a spot-like processing failure or processing unevenness may occur due to the adhesion of the active agent accumulated in the processing solution to the film.

[0008]

SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to provide an antistatic property, abrasion resistance of a film, a stickiness,
An object of the present invention is to provide a silver halide photographic light-sensitive material for medical X-ray photography which has improved transportability and contamination of a processing solution at the same time.

[0009]

The above objects of the present invention have been attained by the following constitutions. (1) A silver halide photographic material having at least one silver halide emulsion layer on each side of a support and two or more non-photosensitive colloid layers above the silver halide emulsion layer The non-photosensitive colloid layer of the intermediate layer contains spherical polymer particles having an average particle diameter of 1 to 10 μm and a relative standard deviation of 10% or less and a polyalkylene oxide-based nonionic surfactant; A silver halide photographic material comprising a non-photosensitive colloid layer containing a fluorine-containing surfactant. (2) A silver halide photographic material having at least one silver halide emulsion layer on each side of a support and two or more non-photosensitive colloid layers above the silver halide emulsion layer. The non-photosensitive colloid layer of the intermediate layer has an average particle diameter of 1 to 10 μm, contains polymer particles containing an acidic monomer in an amount of 5 to 15 mol%, and a polyalkylene oxide-based nonionic surfactant; A silver halide photographic material comprising a non-photosensitive colloid layer containing a fluorine-containing surfactant. (3) The silver halide according to (1) or (2) above, wherein the fluorine-based surfactant is a combination of at least one fluorine-based anion surfactant and at least one fluorine-based cationic surfactant. Photosensitive material. (4) at least one layer of a silver halide emulsion layer coating solution on a support, and spherical polymer particles having an average particle diameter of 1 to 10 μm and a relative standard deviation of 10% or less and a polyalkylene oxide based on an intermediate layer 2. The halogen according to the above 1, wherein a non-photosensitive colloid layer coating solution containing a nonionic surfactant and a non-photosensitive colloid layer coating solution containing a fluorine-based surfactant are simultaneously and multi-layer coated on the outermost layer. A method for producing a silver halide photographic light-sensitive material. (5) At least one layer of a silver halide emulsion layer coating solution on a support, polymer particles having an average particle diameter of 1 to 10 μm in an intermediate layer and containing 5 to 15 mol% of an acidic monomer, and a polyalkylene oxide-based 3. The halogen according to the above 2, wherein a non-photosensitive colloid layer coating solution containing a nonionic surfactant and a non-photosensitive colloid layer coating solution containing a fluorine-based surfactant are simultaneously and multi-layer coated on the outermost layer. A method for producing a silver halide photographic light-sensitive material. (6) The silver halide as described in (4) or (5) above, wherein the fluorine-based surfactant is a combination of at least one fluorine-based anion surfactant and at least one fluorine-based cationic surfactant. Manufacturing method of photographic photosensitive material.

Hereinafter, the present invention will be described in detail. The polymer particles according to claim 1 of the present invention will be described. The polymer particles of the present invention have an average particle diameter of 1 μm to 10 μm
And the relative standard deviation is 10% or less. Here, the average particle size is a number average particle size, and the relative standard deviation is a value obtained by dividing the standard deviation of the polymer particles by the average particle size. The average particle size of these polymer particles is preferably 2 μm to 9 μm, more preferably 3 μm to 8 μm.
μm. Further, the relative standard deviation is preferably 8% or less, more preferably 7% or less. If the relative standard deviation is too large, coarse particles are mixed and peeling tends to occur. The average particle diameter and the relative standard deviation in the present invention can be determined by taking an electron micrograph of polymer particles and randomly measuring 500 or more particle diameters from the photograph. The content of the polymer particles is 50 to 600 mg / m
^2. It is preferably one side, more preferably 80 to
400 mg / m ² · one side, more preferably 100 to 30
0 mg / m ² · one side. If it is smaller than 1 μm, the effect of preventing crackling is reduced.

The glass transition point (Tg) of the polymer compound used as the polymer particles is preferably 40 ° C. or higher. Among them, Tg is preferably 50 ° C. or higher, more preferably 60 ° C. or higher. If the Tg is less than 40 ° C., the blocking property in an environment at an air temperature of 40 ° C. or more deteriorates, which is not preferable. Further, the refractive index of the polymer particles of the present invention is preferably closer to the refractive index of the binder of the layer containing the polymer particles, and is preferably ± 0.2 with respect to the refractive index of the binder.
Within 5, more preferably ± 0.3, and even more preferably ± 0.1. The refractive index of the polymer particles of the present invention ± with respect to the refractive index of the binder of the layer containing the polymer particles
If it is out of the range of 0.5, it becomes a factor of deteriorating transparency. The polymer particles of the present invention can be used as a mixture of two or more kinds. Furthermore, the polymer particles of the present invention are truly spherical, and when the diameter of the polymer particles is measured using an electron micrograph, the ratio of the diameter to the minor axis of the same particle is usually 1.2 or less, preferably 1 .1 or less.

For the polymer particles of the present invention, a polymer compound synthesized by a seed polymerization method, a soap-free polymerization method, a suspension polymerization method, or a spherical polymer compound by a spray drying method or a dispersion method may be used. it can. Of these, the seed polymerization method is preferred, and the method described in JP-A-8-120005 can be particularly preferably used.
In order to polymerize a monomer onto a seed particle by a seed polymerization method, a monomer, a polymerization initiator and an emulsifier are charged into an aqueous medium to emulsify, and the seed particle is charged into the emulsion and polymerized.

[0013] The seed particles can be formed of various resins. In the present invention, examples of the resin forming the seed particles include a (meth) acrylic resin, a styrene resin, a mixed resin of a (meth) acrylic resin and a styrene resin, or a (meth) acrylic monomer. And styrene-based monomers. Furthermore, this (meth) acrylic resin or styrene resin
Another monomer copolymerizable with the (meth) acrylate-based monomer and / or the styrene-based monomer as described above may be copolymerized. Examples of such a monomer include a vinyl monomer and an unsaturated carboxylic acid monomer.

The (meth) acrylic resin is a (co) polymer of (meth) acrylate or a copolymer of a (meth) acrylate monomer with another monomer. Is preferred. Examples of (meth) acrylate-based monomers include methyl (meth) acrylate, ethyl (meth) acrylate, and propyl (meth) acrylate.
Acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-propyl (Meth) acrylate, chloro-2-hydroxyethyl (meth) acrylate, diethylene glycol mono (meth) acrylate, methoxyethyl (meth) acrylate, glycidyl (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentenyl (meth) ) Acrylates and isoboronor (meth) acrylates.

Examples of the styrene monomer forming the seed particles include styrene, methyl styrene, dimethyl styrene, trimethyl styrene, ethyl styrene, diethyl styrene, triethyl styrene, propyl styrene, butyl styrene, hexyl styrene, Mention may be made of alkylstyrenes such as heptylstyrene and octylstyrene; halogenated styrenes such as fluorostyrene, chlorostyrene, bromostyrene, dibromostyrene and chloromethylstyrene; and nitrostyrene, acetylstyrene and methoxystyrene.

In the present invention, the seed particles are, for example, usually 0 to 100 parts by weight, preferably 50 to 100 parts by weight of a (meth) acrylic ester, and usually 0 to 80 parts by weight of a styrene-based monomer. Is from 0 to 50 parts by weight,
Other monomers such as vinyl monomers can be copolymerized usually in an amount of 0 to 80 parts by weight, preferably 0 to 50 parts by weight.

The seed particles preferably used in the present invention have a crosslinked structure. The gel fraction of the seed particles by the toluene extraction method is in the range of 10 to 85%, and more preferably 30 to 70%. %. To adjust the gel fraction of the seed particles,
A crosslinked structure is formed by using a functional or polyfunctional monomer. Examples of bifunctional or polyfunctional monomers include:
Ethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, 1,1,1-tris Hydroxymethylethane diacrylate, 1,1,1-trishydroxymethylethane triacrylate, 1,
1,1-trishydroxymethylpropane triacrylate and divinylbenzene can be mentioned.

In forming the seed particles, the bifunctional monomer or the polyfunctional monomer is usually used in an amount of 0.005 to 0.05 part by weight, preferably 100 to 100 parts by weight of the monomer. It is used in an amount of 0.01 to 0.04 parts by weight. In the present invention, the seed particles can be prepared by various methods such as soap-free emulsion polymerization, suspension polymerization, and emulsion polymerization. In the present invention, soap-free emulsion polymerization is particularly preferable.

Examples of the polymerization initiator used in the soap-free emulsion polymerization include persulfates such as potassium persulfate and ammonium persulfate. The initiator is not limited to this. The polymerization initiator is used usually in an amount of 0.1 to 10 parts by weight based on 100 parts by weight of the monomer used.

The seed particles thus formed are usually from 0.05 to 1 μm, preferably from 0.2 to 0.6 μm.
Average particle size. Further, the relative standard deviation of the particle diameter is usually 10% or less, preferably 5% or less.
The next polymerization step is usually carried out by blending seed particles, monomers and a polymerization initiator, and if necessary, an emulsifier and a dispersion stabilizer in an aqueous medium. The monomer used in this polymerization step is the monomer listed in the description of the production of the seed particles, and may be the same as or different from the monomer that formed the seed particles.

Examples of the polymerization initiator used in the seed polymerization include persulfates such as potassium persulfate and ammonium persulfate; peroxides such as benzoyl peroxide and lauryl peroxide;
An azo compound such as azobisisobutyronitrile can be used. The polymerization initiator is usually used in an amount of 0.1 to 10 parts by weight based on 100 parts by weight of the monomer. Examples of the emulsifier include alkylbenzene sulfonates such as sodium dodecylbenzenesulfonate, and polyethylene glycol alkyl ethers such as polyethylene glycol nonylphenyl ether. The emulsifier is usually used in an amount of 0.1 to 5 parts by weight based on 100 parts by weight of the monomer.

Examples of dispersion stabilizers include polyvinyl alcohol, polyvinyl alcohol, polyvinyl alcohol-polyacrylic acid copolymers and neutralized products thereof, and polymethacrylic acid, copolymers thereof, and polyvinyl alcohol obtained by partially saponifying vinyl acetate. Japanese products can be mentioned. This dispersion stabilizer is
It is usually used in an amount of 0.1 to 5 parts by weight based on 100 parts by weight of the monomer.

Through the polymerization step as described above, the monomers absorbed by the seed particles are polymerized and the seed particles grow. Usually, the polymerization of the second and subsequent stages is performed so as to be 2 to 100 times the weight of the seed particles. The second and subsequent polymerization steps are usually repeated 1 to 10 times, preferably 1 to 5 times. The particles used in the last polymerization step, which are used as seed particles in the final stage, have a crosslinked structure, and the seed particles have a gel fraction of 10 to 85% by a toluene extraction method. Use Further, the gel fraction is preferably in the range of 30 to 70%.

In order to adjust the gel fraction of the seed particles in the final stage, a bifunctional or polyfunctional monomer can be used as in the case of the seed particles in the first stage. Preparation Example of Polymer Particles of the Present Invention (P-1) [Preparation of Seed Particles] In a 1-liter four-necked flask equipped with a thermometer and a nitrogen inlet tube, 100 parts by weight of methyl methacrylate as a monomer was added. Then, 0.04 parts by weight of ethylene glycol dimethacrylate as a crosslinkable monomer and 900 parts by weight of ion-exchanged water were added and mixed, and the temperature was raised to 80 ° C. while stirring under a nitrogen stream.

Next, 0.2 parts by weight of potassium persulfate was added to 5 parts by weight.
It was dissolved in parts by weight of ion-exchanged water, added to the reaction solution in the four-necked flask, and reacted at 80 ° C. for 6 hours to obtain a dispersion of seed particles. Observation with an electron microscope photograph revealed that the particle size of the seed particles was 0.50
In μm, the standard deviation was 0.03 μm. The gel fraction obtained by the toluene extraction method was 80%. [Second stage polymerization] In the same apparatus as above, 100 parts by weight of methyl methacrylate as a monomer, 0.03 parts by weight of ethylene glycol dimethacrylate as a crosslinkable monomer and 0.2 parts by weight of benzoyl peroxide And dissolved in the solution, and 1 part by weight of sodium dodecylbenzenesulfonate and 88% of saponified polyvinyl alcohol
After mixing with 900 parts by weight of ion-exchanged water in which the parts by weight were dissolved, the mixture was mixed for 30 minutes under strong stirring.

Next, 33 parts by weight of the above-mentioned seed emulsion was added to the above-mentioned mixture, and the mixture was gently stirred at 40 ° C. for 30 minutes and then reacted at 80 ° C. for 6 hours to obtain a dispersion of polymer particles. . The average particle diameter of the obtained polymer particles is 1.20 μm
And the standard deviation was 0.05 μm. The gel fraction obtained by the toluene extraction method was 60%. [Third-stage polymerization] Next, 5 parts by weight of ethylene glycol dimethacrylate and 0.2 parts by weight of benzoyl peroxide were mixed as crosslinkable monomers with 95 parts by weight of methyl methacrylate as a monomer in the same apparatus. Then, 900 parts by weight of ion-exchanged water in which 1 part by weight of sodium dodecylbenzenesulfonate and 1 part by weight of 88% saponified polyvinyl alcohol were added and mixed with the solution, and then mixed under strong stirring. Mix for minutes.

Next, 20 parts by weight of the seed emulsion obtained in the second stage was added to the mixture, and the mixture was gently stirred at 40 ° C. for 30 minutes, followed by a reaction at 80 ° C. for 6 hours to obtain polymer particles. A dispersion was obtained. Observation with an electron microscope photograph revealed that the average particle size was 4.4 μm and the standard deviation was 0.4 μm.
The particles were perfectly spherical monodisperse particles having a size of 20 μm, and their relative standard deviation was 4.5%.

Next, the polymer particles according to the second aspect of the present invention will be described. The polymer particles according to claim 2 have an average particle size of 1 to 10 µm,
It is a copolymer comprising 5% of an acidic monomer and at least one or more nonionic monomers. Here, the average particle size is a number average particle size, and the relative standard deviation is a value obtained by dividing the standard deviation of the polymer particles by the average particle size. The average particle size of these polymer particles is preferably 2 μm to 9 μm, more preferably 3 μm to 8 μm. Examples of the acidic monomer include acrylic acid, methacrylic acid, itaconic acid, maleic acid, styrenesulfonic acid, vinylbenzylsulfonic acid, vinylsulfonic acid, and acryloyloxyalkylsulfonic acid (for example, acryloyloxymethylsulfonic acid); methacryloyloxyalkylsulfone Acid (for example, methacryloyloxyethylsulfonic acid, etc.); acrylamidoalkylsulfonic acid (for example, 2-acrylamido-2-methylethanesulfonic acid, etc.); methacrylamidoalkylsulfonic acid (for example, 2-methacrylamido-2-methylethanesulfonic acid) Acryloyloxyalkyl phosphate (eg, acryloyloxyethyl phosphate). These acids may be salts of alkali metals (eg, Na, K, etc.) or ammonium ions. Acrylic acid and methacrylic acid are preferred, and methacrylic acid is particularly preferred. The content of the acidic monomer is 5 to 15 mol%, preferably 7 to 12 mol% of all the monomers. If the acid component is contained in an amount of 15 mol% or more, it will be dissolved at the time of development processing.

Examples of the nonionic monomer copolymerized with the acidic monomer include acrylates, methacrylates, itaconic diesters, crotonic esters, maleic diesters, and phthalic diesters. , Methyl, ethyl, propyl, isopropyl, butyl, hexyl, 2-ethylhexyl, 2-chloroethyl, cyanoethyl, 2-acetoxyethyl, dimethylaminoethyl, benzyl, cyclohexyl, furfuryl, phenyl, 2-hydroxyethyl, 2-ethoxyethyl, Glycidyl, ω-methoxypolyethylene glycol, and the like. In addition, vinyl esters, olefins, styrenes, acrylamides, methacrylamides, allyl compounds, vinyl ethers, vinyl ketones, vinyl heterocyclic compounds, unsaturated nitriles and the like are also used. Furthermore, monoalkyl itaconate (for example, monoethyl itaconate, etc.); monoalkyl maleate (for example, monomethyl maleate, etc.), and N- (2-acetoacetoxyethyl) acrylamide, N- (2 -(2-acetoacetoxyethoxy) ethyl) acrylamide, divinylbenzene, ethylene glycol dimethacrylate and the like. Among these monomers, acrylates, methacrylates, vinyl esters, styrenes, and olefins are preferably used, and particularly preferred are methyl methacrylate and ethyl methacrylate. Further, the present invention relates to
-14647, 62-17744, 62-17
Particles having a fluorine atom or a silicon atom as described in U.S. Pat. No. 743 may be used. Particularly preferred among the polymer particles of the present invention are those containing 80% by mass or more of acrylic acid and its esters, methacrylic acid and its esters in the composition of the polymer particles. In that case, vinyl esters, olefins, styrenes, acrylamides,
Methacrylamides, allyl compounds, vinyl ethers, vinyl ketones, vinyl heterocyclic compounds, unsaturated nitriles and the like are used. Preferred are styrene and styrene derivatives. Preferred embodiments of the polymer particles of the present invention include methyl methacrylate / acrylic acid copolymer (95/5 to 85/15 (molar ratio)) and methyl methacrylate / methacrylic acid copolymer (95/5 to 85/85 Fifteen
(Molar ratio)), ethyl methacrylate / methacrylic acid copolymer (95/5 to 85/15 (molar ratio)), and more preferably methyl methacrylate / acrylic acid copolymer (93/7 to 88). / 12 (molar ratio)), methyl methacrylate / methacrylic acid copolymer (93/7 to 88/12
(Molar ratio)) and an ethyl methacrylate / methacrylic acid copolymer (93/7 to 88/12 (molar ratio)).

5-15% of the acidic monomer and at least 1
The polymer particles of the present invention, which are copolymers of at least one kind of nonionic monomer, are preferably monodisperse, and preferably 30% or less, and more preferably 20% or less, expressed as a relative standard deviation. Is more preferable. The polymer particles of the present invention may be classified and monodispersed after polymerization. As a classification means, a centrifugal separation method can be used. That is, the dispersion of the polymer particles is diluted, centrifuged, and the particles that settle out are selected according to the rotation speed of the centrifuge. By repeating this operation several times, the monodispersity can be improved. Examples of monodispersion by polymerization include soap-free polymerization, suspension polymerization, seed polymerization, molecular diffusion, two-stage swelling, dynamic swelling, accelerated diffusion polymerization, and dispersion polymerization. For example, a known method is used.

Hereinafter, specific examples of the polymer particles of the present invention will be described. (These were obtained by classification by centrifugation.) Composition ratio Average particle size Relative standard deviation P-2 MMA: AA = 90: 10 4.5 μm 30% P-3 MMA: MAA = 90: 10 4.5 μm 20% P-4 EMA: AA = 85: 15 4.6 μm 30% P-5 MMA: AA = 95: 5 4.5 μm 20% P-6 EMA: MAA = 90: 10 4.4 μm 20% (However, MMA = (Methyl methacrylate, EMA = ethyl methacrylate, AA = acrylic acid, MAA = methacrylic acid) The silver halide photographic light-sensitive material obtained from the polymer particles of the present invention has a matte degree of 6.65 to 39.9.
kPa, preferably 19.95 to 33.25 k
Pa. In the present specification, the term "mat degree" refers to a value obtained by expressing, as a change in pressure, the amount of air inflow that varies depending on the smoothness (mat degree) of the film surface using a vacuum air micrometer. The suction pressure of an unexposed photosensitive material (so-called raw film) that was conditioned for 3 hours under the condition of% RH was measured under the same conditions, and kP
The larger the value, the higher the matte degree. In the examples described later, a smoother (manufactured by Toei Electronics Co., Ltd.) can be used for measuring the suction pressure. The polymer particles in the present invention are contained below the outermost layer of the light-sensitive material and above the light-sensitive silver halide emulsion layer. The content of the polymer particles is 50 to 6
Is preferably 00mg / m ² · sided, more preferably 80~400mg / m ² · sided, more preferably from 100 to 300 mg / m ² · sided. The desired mat degree obtained by using the polymer particles of the present invention can be obtained in a large amount when the average particle size of the polymer particles is small, and can be obtained in a small amount when the average particle size is large. . In addition, the polymer particles may be deformed, such as sinking or crushing, due to pressure from a conveying roller or the like during coating and drying.

The preferred fluorine-based surfactant used in the present invention has, as a hydrophobic group, an alkyl group, an alkenyl group or an aryl group containing at least three fluorine atoms, and the hydrophilic group includes an anion Groups (eg, sulfonic acid, sulfuric acid, carboxylic acid, phosphoric acid and their salts), cationic groups (eg, amine salts, ammonium salts,
Aromatic amine salts, sulfonium salts, phosphonium salts),
Surfactants having a betaine group (carboxyamine salt, carboxyammonium salt, sulfoamine salt, sulfoammonium salt, phosphoammonium salt) or a nonionic group (for example, substituted or unsubstituted polyoxyalkylene group, polyglyceryl group, sorbitan residue) Is mentioned. These fluorine-based surfactants are described in JP-A-49-10722,
Nos. 55-149938 and 58-196544, British Patent Nos. 1,330,356 and 1,417,915
No. 1,439,402, US Pat. No. 4,335,2
No. 01 and the like.

Further, in the present invention, it is preferable to use a fluorine-based anionic surfactant and a fluorine-based cationic surfactant in combination. The fluorinated anionic surfactant and fluorinated cationic surfactant preferably used in the present invention will be described. As the fluorine-based anionic surfactant, a compound represented by the following general formula [F1] or [F2] can be used. General Formula [F1] (Cf)-(Y) n wherein Cf is an n-valent group containing at least three fluorine atoms and at least two carbon atoms, and Y is -COO
_{H, -SO 3 M, -OSO 3} M or -P (= O) (OM)
Represents ₂ . M is a hydrogen atom or an alkali metal or quaternary
Represents a cation such as a quaternary ammonium salt, wherein n is 1 or 2
It is. Formula [F2] Rf'-LX ⁺ Z ^{-In the} formula, Rf 'represents a hydrocarbon group having 1 to 20 carbon atoms, and at least one hydrogen atom is substituted with a fluorine atom. L represents a chemical bond or a divalent group. X represents a cation and Z represents a counter anion.

In the present invention, the fluorine anion activator represented by the general formula [F1] is particularly preferably the one represented by the following general formula [F1a]. Formula [F1a] Rf- (D) _t -Y In the formula, Rf represents an alkyl group or an aryl group substituted with at least 3 fluorine atoms having 3 to 30 carbon atoms, and D represents -O-,-. _{COO -, - CON (R 1} ) - or -SO ₂ N (R ₁₎ - represents a composed combine at least one divalent group having 1 to 12 carbon atoms. R ₁ has ₁ carbon atom
Represents an alkyl group of 5 to 5, t is 1 or 2, and Y is-
_{COOM, -SO 3 M, -OSO 3} M or -P (= O)
(OM) ₂ , wherein M represents a hydrogen atom or a cation such as an alkali metal or a quaternary ammonium salt.

Next, the general formula [F1] and the general formula [F1a]
Specific examples of the compound represented by are shown below, but the present invention is not limited thereto.

[0036]

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[0037]

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[0038]

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[0039]

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[0040]

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Next, the fluorinated cationic activator used in the present invention will be described. In the general formula [F2], Rf ′ in the formula represents a hydrocarbon group having 1 to 20 carbon atoms, and at least one hydrogen atom is substituted with a fluorine atom. Rf '
The example _{-C k F k + 1 (k} = 1~20, especially 3-1
2 is _{preferred), - C m F 2m,} -C m F 2m -1 (m = 2~2
0, particularly preferably 3 to 12).

As an example of L, -SO_TwoN (R¹) (CH
_Two)_p-, -CON (R¹) (CH_Two) _p-, -OSO_TwoN
(R¹) (CH_Two)_p-, -OCON (R¹) (CH_Two)
_p-, -O (CH_Two)_p-, -O (CH_Two)_p-, -O (C
H_TwoCH_TwoO)_q(CH_Two)_p-, -O (CH_Two)_p-, -N
(R¹) (CH_Two)_p-, -SO_TwoN (R¹) (CH_Two)_pO
(CH_Two)_r-, -CON (R¹) (CH_Two)_pO (CH_Two)
_r-, -OSO_TwoN (R¹) (CHR¹)_pO-,-(C
H_Two)_p(CHOH)_s(CH_Two)_r-
Wear.

As an example of X, -N⁺(R¹)_Three, -N
⁺(CH_TwoCH_TwoOCH_Three)_Three, -N⁺C_FourH ₈O (R¹),-
N⁺(R¹) (R^Two) (CH_TwoCH_TwoOCH_Three), -N⁺C_FiveH
_Five, -N⁺(R¹) (R^Two) (CH_Two)_pC₆H_Five, -N
⁺(R¹) (R^Two)_TwoAnd the like. Where R¹
And R^TwoIs a hydrogen atom or an alkyl having 1 to 6 carbon atoms, respectively.
Represents a kill group (which may have a substituent), p, r and s
Are each 0 to 6 and q is 1 to 20.

[0044] Examples of Y are ^{I -, Cl -, Br -} , CH 3
SO ₃ ⁻ and CH ₃ —C ₆ H ₄ —SO ₃ ^{— and the} like can be mentioned. Hereinafter, specific examples of the fluorine-based cation activator preferably used in the present invention will be described, but the present invention is not limited thereto.

[0045]

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[0046]

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In the present invention, particularly, the hardly soluble -SO ₂ N (R ¹ )
It is more preferable to use a fluorine-based cation activator containing at least one bond of Here, the poor solubility is 2
2.0 g of the activator was added to 100 ml of pure water at 3 ° C.
After stirring for 24 hours at 23 ° C. for 24 hours, a precipitate is formed, or when a floating substance is observed, the substance is made hardly soluble. For example, F2-1, F2-8, F2-15, F2-16, and the like correspond to, but are not limited to, and can be classified by the above test.

The fluorinated anionic activator or fluorinated cationic activator according to the present invention is described, for example, in US Pat.
Nos. 59,751, 2,567,011, 2,73
No. 2,398, No. 2,764, 602, No. 2,80
6,866, 2,809,998, 2,91
5,376, 2,915,528 and 2,91
8,501, 2,934,450 and 2,93
7,098, 2,957,031, 3,47
2,894, 3,555,08, British Patent 1,1
43,927, 1,130,822
No. 37304, JP-A-47-9613 and 49-1.
No. 34614, No. 50-117705, No. 50-11
Nos. 7727, 50-123243, 52-411
Nos. 82 and 51-12392, British Chemical Society (J.C.
hem. Soc. 1950, 2789, 1957
Years 2574 and 2640, American Chemical Society (J. Am
er. Chem. Soc. 79, 2549 (195)
7 years), oil chemistry (J. Japan Oil Chemi)
sts Soc. 12, p. 653, Journal of the Society of Organic Chemistry (J. 0rg. Chem.), Vol. 30, p. 3524 (196).
5 years).

Certain of these fluorine-based activators are obtained from Dainippon Ink and Chemicals, Inc.
gafac) F under the trade name Minnesota Mining
And Manufacturing Company, Inc. under the trade name Fluorad FC, Imperial Chemical Industries, Inc. under the trade name Monflor, and E.I. ), And Falbeberke
Each is commercially available from Hoechst under the trade name Licovet VPF.

The total amount of the fluorinated cationic activator and the fluorinated anionic activator used in the present invention is preferably from 0.1 to 1000 mg, preferably from 0.5 to 30 mg / m ^2.
0 mg, more preferably 1.0 to 150 mg. When used together, two or more of them may be used in combination. The molar ratio of the fluorine-based anion activator and the fluorine-based cation activator of the present invention is preferably 1:10 to 10: 1, and more preferably 3: 7 to 7: 3.

Next, fluorine betaine activators and fluorine nonion activators which can be used in the present invention will be exemplified, but the compounds are not limited to the exemplified compounds. Further, these compounds can be used in combination with the above-mentioned fluorine-based anionic surfactant, fluorine-based cationic surfactant, and a combination thereof.

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[0053]

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Next, the polyalkylene oxide nonionic activator according to the present invention will be described. Examples of the polyalkylene oxide-based nonionic activator preferably used in the present invention include a compound represented by the following general formula (3). Formula (3) _{R 1 -A- (B) n-} R expression, R represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms (e.g., methyl group, ethyl group, hydroxyethyl group, an isopropyl group, etc.), carbon Represents an alkylcarbonyl group of the formulas 1 to 5 (for example, an acetyl group, a chloroacetyl group, a carboxymethylcarbonyl group, etc.).

R ₁ represents a substituted or unsubstituted alkyl, alkenyl or aryl group having 1 to 30 carbon atoms. A is -O -, - S -, - COO -, - N (R 2) -, - CO
—N (R ₂ ) —, —SO ₂ —N (R ₂ ) —, wherein R ₂ represents a hydrogen atom or a substituted or unsubstituted alkyl group.

B represents an oxyalkylene group (for example, an oxyethylene group, an oxypropylene group, an oxyhydroxypropylene group, an oxybutylene group, etc.). Preferred are an oxyethylene group and an oxyhydroxypropylene group. n represents an average degree of polymerization of the oxyalkylene group;
This is a natural number of 50. Next, compounds having a polyoxyalkylene group preferably used in the present invention will be exemplified.

3-1 C₈H₁₇O (CH_TwoCH_TwoO)₇H 3-2 C₁₁H_{twenty three}O (CH_TwoCH_TwoO)₈H 3-3 C₁₂H_{twenty five}O (CH_TwoCH_TwoO)_TenH 3-4 C₁₆H₃₃O (CH_TwoCH_TwoO)₁₂H 3-5 C₂₀H₄₁O (CH_TwoCH_TwoO)₂₀H 3-6 C₁₈H₃₇O (CH_TwoCH (OH) CH_TwoO)
_Two(CH_TwoCH_TwoO)_TenH 3-7 C₁₆H₃₃O (CH_TwoCH_TwoO)_Four(CH_TwoCH (O
H) CH_TwoO)_Two(CH _TwoCH_TwoO)_FourH 3-8 C₁₁H_{twenty three}COO (CH_TwoCH_TwoO)₈H 3-9 C_FifteenH₃₁COO (CH_TwoCH_TwoO)₁₃H 3-10 C₁₆H₃₃COO (CH_TwoCH_TwoO)_FifteenH 3-11 C₁₈H₃₅COO (CH_TwoCH_TwoO)_FifteenH 3-12 C₁₂H_{twenty five}S (CH_TwoCH_TwoO)_FifteenH

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[0059]

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The addition amount of the nonionic activator having a polyoxyalkylene group according to the present invention is from 1 to 500 mg /
m ² is preferred, and more preferably ⁵ to 250 mg / m ² . In the present invention, two or more non-photosensitive colloid layers are provided above the silver halide emulsion layer, and the average particle diameter is 1 to 10 μm in the non-photosensitive colloid layer of the intermediate layer.
And containing spherical polymer particles having a relative standard deviation of 10% or less and a polyalkylene oxide-based nonionic surfactant, and the above-mentioned fluorine-based surfactant in the outermost non-photosensitive colloid layer.

Further, there are provided two or more non-photosensitive colloid layers above the silver halide emulsion layer, and the non-photosensitive colloid layer in the intermediate layer has the above-mentioned average particle diameter of 1 to 10 μm; It contains polymer particles containing 5 to 15 mol% of an acidic monomer and a polyalkylene oxide-based nonionic surfactant, and the above-mentioned fluorine-based surfactant is contained in the outermost non-photosensitive colloid layer.

The non-photosensitive colloid layer above the silver halide emulsion layer preferably contains 0.2 to 1.5 g / m ² of gelatin as a hydrophilic binder, and more preferably 0.3 to 0.9 g / m ^2. It is preferable to contain m ² . In addition to gelatin, a water-soluble polymer, a latex polymer or the like may be contained. The ratio of the hydrophilic binder in the intermediate layer containing the polymer particles and the polyalkylene oxide-based nonionic surfactant and the outermost layer containing the fluorine-based surfactant is preferably from 1:10 to 10: 1, and more preferably from 1: 3 to 10: 1. 3:
1 is preferred.

The amount of gelatin in the silver halide emulsion layer, the intermediate layer, the outermost layer, and the other layers was 0.5% in total on one side of the support.
To 3.5 g / m ² , particularly preferably 1.0 to 3.0 g / m ² . In order to obtain the effects of the present invention, the silver halide emulsion coating solution, the intermediate layer coating solution containing polymer particles and a polyalkylene oxide surfactant, and the outermost layer coating solution containing a fluorine-based surfactant have been subbed. Is preferred. As a method of simultaneous multilayer coating, a method using a slide hopper, a curtain coating method, or the like can be used.

An antihalation layer, a crossover cut layer and the like may be provided between the undercoat layer and the emulsion layer. At the same time as multi-layer coating. The silver halide photographic light-sensitive material of the present invention has photosensitive silver halide emulsion layers on both sides of a support, and the photographic characteristics of the silver halide emulsion layers on each side may be the same or different. The layer structure on each side may be a method of applying and drying one side and then applying the other side, or a method of simultaneously applying to both sides.

The silver halide grains used in the present invention may have any shape, for example, cubic, octahedral, tetradecahedral, spherical, flat, potato-like, and the like. Particularly preferred are tabular silver halide grains. Tabular silver halide grains are crystallographically classified as twins. A twin is a crystal having one or more twin planes in one grain. Classification of a twin form in a silver halide grain is based on a report by Klein and Moiser, Ph.
autographfish Korresponden
z, Vol. 99, p. 99, and Vol. 100, p. 57. Tabular silver halide grains related to the present invention,
The grains have one or two or more twin planes parallel to each other in the grains, and these twin planes have the largest area among the planes forming the surface of the tabular grains (also referred to as the main plane). ) Exist almost in parallel to each other. The most preferable form in the present invention is a case having two parallel twin planes.

In the present invention, the aspect ratio refers to the ratio between the area-converted particle size and the particle thickness (aspect ratio = equivalent circle diameter / thickness). Here, the area-converted particle size means the diameter of a circle having an area equal to the area when the particle is projected perpendicular to the main plane. On the other hand, the volume-converted particle size is
It refers to the diameter of a sphere having the same volume as the individual silver halide grains. Grain thickness is the thickness of a grain in a direction perpendicular to the major plane and generally corresponds to the distance between the two major planes.

The average equivalent circle diameter of the tabular silver halide grains of the present invention is preferably 0.1 to 10.0 μm, more preferably 0.2 to 5.0 μm, and particularly preferably 0.3 to 2.0 μm.
m is preferred. The average grain thickness of the tabular silver halide grains of the present invention is preferably from 0.01 to 0.3 μm, more preferably from 0.05 to 0.25 μm, particularly preferably from 0.07 to 0.25 μm.
0.2 μm is preferred.

The projected area and thickness of the particles for calculating the area-converted particle diameter and the volume-converted particle diameter can be obtained by the following methods.
A sample was prepared by coating a latex ball having a known particle size as an internal standard on a support and silver halide particles such that the main plane was oriented parallel to the substrate, and shadowing was performed by carbon deposition from a certain angle. Thereafter, a replica sample is prepared by a normal replica method. An electron micrograph of the sample is taken, and the projected area and thickness of each particle are determined using an image processing device or the like. In this case, the projected area of the particle can be calculated from the projected area of the internal standard, and the thickness of the particle can be calculated from the length of the internal standard and the shadow of the particle. In the present invention, the average value of the aspect ratio, the area-converted particle size, the grain thickness, and the volume-converted particle size is arbitrarily set to 500 by using the above-mentioned replica method for the silver halide grains contained in the silver halide emulsion.
A value obtained by measuring more than one piece and calculating as an arithmetic average thereof.

In the present invention, the coefficient of variation of the silver halide grain in terms of volume is a value defined by the following equation using the value obtained from the above measurement. The coefficient of variation of the silver halide grains related to the present invention in terms of volume is preferably 0.2 or less, more preferably 0.15 or less, and particularly preferably 0.1 or less. Coefficient of variation of volume-converted particle size = (standard deviation of volume-converted particle size /
Similarly, from the above measurement, the coefficient of variation of the area-converted particle size of silver halide grains can be determined. Here, the variation coefficient of the area-converted particle diameter is a value defined by the following equation. The variation coefficient of the area-converted grain size of the silver halide grains related to the present invention is preferably 0.2 or less, more preferably 0.15 or less, and particularly preferably 0.1 or less. Coefficient of variation of area-converted particle size = (standard deviation of area-converted particle size /
(Average value of area-converted grain size) The silver halide emulsion relating to the present invention contains 50% of the total projected area of the silver halide grains contained in the silver halide emulsion.
The above is preferably tabular silver halide grains having an average aspect ratio of 1.5 to 300 (hereinafter also simply referred to as aspect ratio), and 50% or more of the total projected area is a tabular silver halide having an aspect ratio of 3 to 50. Silver halide grains are more preferred, and tabular silver halide grains having an aspect ratio of 5 to 25 are particularly preferred. Further, the total projected area of the silver halide grains contained in the silver halide emulsion is 8%.
It is preferred that 0% or more be tabular silver halide grains.

The tabular silver halide grains related to the present invention have one or two or more twin planes parallel to each other in the grains. The above are preferably tabular grains having two twin planes parallel to each other in the grains, and more preferably 80% or more. These twin planes can be observed with a transmission electron microscope. The specific method is as follows. First, a silver halide emulsion is applied on a substrate so that the main plane of the contained tabular grains is oriented substantially parallel to the substrate to prepare a sample. This is continuously cut perpendicular to the substrate using a diamond cutter to obtain a continuous thin section having a thickness of about 0.1 μm. By observing this section with a transmission electron microscope, the existence and position of the twin plane can be confirmed.

The composition of the silver halide grains in the present invention is preferably silver iodobromide, silver bromide, silver chlorobromide, or silver chloroiodobromide. It is particularly preferred that the silver halide emulsion is silver iodobromide having an average silver iodide content of 2 mol% or less, more preferably an average silver iodide content of 1 mol% or less. Molar% or less is particularly preferred. The composition of the silver halide grains can be determined by a composition analysis method such as an EPMA method and an X-ray diffraction method.

The average silver iodide content of the surface phase of the silver halide grains related to the present invention is preferably 3 mol% or less, more preferably 0.1 mol% or more and 2 mol% or less. , 0.2 mol% or more and 1 mol% or less are more preferable. Here, the average silver iodide content of the surface phase of the silver halide grains is a value obtained by using the XPS method or the ISS method. For example, the surface silver iodide content by the XPS method can be obtained as follows. The sample was cooled to −155 ° C. or less in an ultrahigh vacuum of 13.3322 Pa or less, and irradiated with MgKa as an X-ray for a probe at an X-ray source current of 40 mA.
Ag3d5 / 2, Br3d, and I3d3 / 2 electrons are measured. The integrated intensity of the measured peak is corrected by a sensitivity factor, and the composition such as the silver iodide content of the silver halide surface phase is determined from these intensity ratios.

In the silver halide emulsion relating to the present invention, the silver iodide content between silver halide grains is preferably more uniform. That is, the coefficient of variation of the silver iodide content in the silver halide emulsion is preferably 30% or less, and more preferably 20% or less. Here, the coefficient of variation is a value obtained by dividing the standard deviation of the silver iodide content by the average value of the silver iodide content and multiplying by 100, and the silver halide grains contained in the silver halide emulsion. Refers to a value obtained by arbitrarily measuring 500 or more.

The photographic silver halide grains are microcrystals composed of silver chloride, silver bromide, silver iodide, or a solid solution thereof. It is possible to form. As a grain having such a structure, a grain composed of an inner core phase and an outer surface phase having mutually different silver halide compositions is known, and is generally called a core / shell type grain. The silver halide grains related to the present invention preferably have a core / shell type grain structure in which the outer surface phase has a higher silver iodide content than the inner core phase.

The silver halide emulsion relating to the present invention preferably has dislocation lines. The dislocation line is preferably located near the outer periphery, near the ridgeline, or near the vertex of the tabular silver halide grains. In terms of the positional relationship of dislocation introduction in each grain, it is preferable that the silver is introduced after 50% of the silver amount of the whole grain, more preferably between 60% and 95%.
Most preferably, it is introduced between 0% and 90%.

As a method for introducing dislocation lines into silver halide grains, for example, a method of adding an aqueous solution containing iodide ions such as potassium iodide and a water-soluble silver salt solution by double jetting, or a method of introducing silver iodide fine grains. Addition method, method of adding only a solution containing iodide ions, Japanese Patent Application Laid-Open No. HEI 6-11781
A known method such as a method using an iodide ion releasing agent as described in No. 1 can be used to form a dislocation originating a dislocation line at a desired position.

Further, by using a production method in which an aqueous solution containing a salt is appropriately extracted from the reaction solution by an ultrafiltration apparatus, the efficiency of introducing dislocation lines into a silver halide emulsion can be drastically increased. For example, the average intergranular distance at the time of dislocation line introduction in the growth process of silver halide grains,
0.60 times or more 1.00 of the average interparticle distance at the start of growth
It is preferably controlled to be at most 0.60 times and at most 0.60 times.
More preferably, it is controlled to 80 or less. In particular,
The value of the average interparticle distance when dislocation lines are introduced is preferably controlled to 3.2 μm or less, more preferably to 2.8 μm or less, and particularly preferably to 0.90 μm or more and 2.0 μm or less. .

The dislocation lines of the silver halide grains are described, for example, in J. Am. F. Hamilton, Photo. Sci. E
ng. 11 (1967) 57 and T.I. Shiozaw
a, J. et al. Soc. Photo. Sci. Japan35
(1972) 213 can be observed by a direct method using a transmission electron microscope at a low temperature. That is, the silver halide grains taken out from the emulsion so as not to apply enough pressure to generate dislocations on the grains are placed on a mesh for an electron microscope so as to prevent damage by electron beams (such as printout). Observation is performed by a transmission method while the sample is cooled. At this time, the thicker the particles, the more difficult it is for an electron beam to pass through, so that a clearer observation can be obtained by using a high-pressure electron microscope. From the grain photograph obtained by such a method, the position and number of dislocation lines in each grain can be determined.

As a preparation form of the silver halide emulsion related to the present invention, a method known in the art can be appropriately applied. For example, a so-called controlled double jet method or controlled triple jet method for controlling pAg of a reaction solution at the time of forming silver halide grains can be used. In addition, a silver halide solvent can be used if necessary. Examples of useful silver halide solvents include ammonia, thioethers, and thioureas. Regarding thioethers, U.S. Pat.
No. 71,151, No. 3,790,387, No. 3,
No. 574,626 can be referred to. The method for preparing the grains is not particularly limited, and an ammonia method, a neutral method using no ammonia, an acidic method, and the like can be used.From the viewpoint of suppressing fog during silver halide grain formation, it is preferable. It is preferable to form particles in an environment where the pH (logarithm of the reciprocal of the hydrogen ion concentration) is 5.5 or less, more preferably 4.5 or less.

The silver halide emulsion relating to the present invention contains a dispersion medium together with silver halide grains. The dispersion medium is a compound having a protective colloid property for silver halide grains, and is preferably present from the nucleation step to the end of grain growth. Dispersion media that can be preferably used in the present invention include gelatin and protective colloid polymers. As gelatin, usually, alkali-treated gelatin or acid-treated gelatin having a molecular weight of about 100,000, or a molecular weight of 5,000 to
About 30,000 low molecular gelatin or oxidized gelatin can be preferably used. In particular, at the time of nucleation, oxidized gelatin, low molecular weight gelatin, and oxidized low molecular weight gelatin can be suitably used.

In order to more precisely control the silver halide composition between silver halide grains and inside the grains, at least a part of the formation of the silver iodide-containing phase of the silver halide grains is controlled by 1
It can be formed by supplying only silver halide fine particles of more than one kind. For the same reason, at least a part of the formation of the silver iodide-containing phase of the silver halide grains can be performed in the presence of silver halide grains having a lower solubility than the silver halide grains. It is desirable to use silver iodide fine grain emulsions as silver halide grains having low solubility.

In the silver halide emulsion of the present invention, Research Disclosure No. 308119
(Hereinafter abbreviated as RD308119) can be used. When the dye containing the photosensitive silver halide emulsion of the present invention or at least one of the constituent layers other than the emulsion layer contains a dye capable of decoloring and / or flowing out during the development processing, high sensitivity, A photosensitive material having high sharpness and little dye stain can be obtained. The dye used in the photosensitive material may be appropriately selected from dyes that can improve sharpness by absorbing a desired wavelength and removing the influence of the wavelength, depending on the photosensitive material. I can do it. It is preferable that the dye is decolorized or flows out during the development processing of the light-sensitive material, and that the coloring is not visible when the image is completed. The dye used in the light-sensitive material of the present invention is substantially insoluble in water at pH 7 or lower, is pH 8 or higher, and is substantially water-soluble. The amount added can be varied depending on the sharpness goal. Preferably, it is 0.2 mg / m ^{2 to} 20 mg / m ² , more preferably 0.1 mg / m ² .
It is ^{8mg / m 2 ~15mg / m 2} . Known dyes can be used as these dyes.

The silver halide light-sensitive material according to the present invention includes:
Various photographic additives can be used. Known additives include, for example, Research Disclosure No.
No. 17643 (December 1978); 18716
(November 1979) and the same No. 308119 (19
(December 1989). The types of compounds and the locations described in these three research disclosures are listed below.

RD-17643 RD-18716 RD-308119 page classification page classification page classification chemical sensitizer 23 III 648 upper right 996 III sensitizing dye 23 IV 648-649 996-8 IVA desensitizing dye 23 IV 998 IVB dye 25 6VIII 649-650 1003 VIII Development accelerator 29 XXI 648 Upper right Fogging inhibitor / stabilizer 24 IV 649 Upper right 1006-7 VI Brightener 24 V 998 V Hardener 26 X 651 Left 1004-5 X Surfactant 26- 7 XI 650 right 1005-6 XI Antistatic agent 27 XII 650 right 1006-7 XIII plasticizer 27 XII 650 right 1006 XII sliding agent 27 XII matting agent 28 XVI 650 right 1008-9 XVI binder 26 XXII 1003-4 IX 28 XVII 1O09 XVII Supports that can be used in the photosensitive material of the present invention. The body, for example, page 28 of the aforementioned RD-17643 and RD
-308119 on page 1009. A suitable support is a plastic film or the like, and the surface of these supports may be provided with an undercoat layer, or subjected to corona discharge, ultraviolet irradiation, etc. in order to improve the adhesion of the coating layer. The undercoat layer preferably contains an antistatic improver such as tin oxide sol.

Preferred developing solutions for developing the light-sensitive material of the present invention include, as developing agents, JP-A-4-15641;
Dihydroxybenzenes described in JP-A-4-16841 and the like; hydroquinone, paraaminophenols such as p-aminophenol, N-methyl-p-aminophenol, and 2,4-diaminophenol;
-As the pyrazolidones, for example, 1-phenyl-3-
Pyrazolidone, 1-phenyl-4-methyl-4-hydroxymethyl-3-pyrazolidone, 5,5-dimethyl-1
-Phenyl-3-pyrazolidone and the like and ascorbic acids are preferably used in combination. Further, the total mole number of dihydroxybenzenes, paraaminophenols, 3-pyrazolidones, and ascorbic acids contained in the components of all the developing solutions was 0.1 mol / mol.
Liter or more is preferred.

The preservative may include sulfites, for example, potassium sulfite, sodium sulfite, reductones, for example, piperidinohexose reductatone, etc.
These are preferably used in an amount of 0.2 to 1 mol / l, more preferably 0.3 to 0.6 mol / l. Also, addition of a large amount of ascorbic acids leads to processing stability.

As the alkaline agent, sodium hydroxide,
PH adjusters such as potassium hydroxide, sodium carbonate, potassium carbonate, sodium tertiary phosphate and potassium tertiary phosphate are included. Further, buffers such as borate described in JP-A-61-28708 and saccharose, acetoxime, 5-sulfosalicylic acid, phosphate and carbonate described in JP-A-60-93439 may be used. The content of these agents raises the pH of the developer to 8.5 to 11.5, preferably to pH 9.
Choose to be 5-10.5.

The dissolution aids may contain diethylene glycol, triethylene glycols and esters thereof, and the sensitizers may contain, for example, development accelerators such as quaternary ammonium salts, surfactants and the like. As a silver sludge inhibitor, JP-A-56-106
No. 244, a silver stain inhibitor, a sulfide and disulfide compound described in JP-A-3-51844, and a JP-A 5-2
A cysteine derivative or a triazine compound described in No. 89255 is preferably used.

As organic inhibitors, azole organic antifoggants such as indazole, imidazole, benzimidazole, triazole, benztriazole, tetrazole, thiadiazole, mercaptoazole (eg, 1-phenyl-5-mercapto) A tetrazole) compound. As the inorganic inhibitor, sodium bromide, potassium bromide, potassium iodide and the like can be contained. In addition, L. F. A. Mason, "Photographic Processing Chemistry", Focal Press (1966), pp. 226-229,
U.S. Pat. Nos. 2,193,015 and 2,592,364
And those described in JP-A-48-64933. As a chelating agent for concealing calcium ions mixed in tap water used in the treatment liquid, a chelating agent having a chelate stabilization constant with iron of 8 or more described in JP-A-1-193853 as an organic chelating agent is preferably used. Can be Examples of the inorganic chelating agent include sodium hexametaphosphate, calcium hexametaphosphate, and polyphosphate.

As the developing hardener, a dialdehyde compound may be used. In this case, glutaraldehyde is preferably used. The replenishment of the developer during the development processing of the light-sensitive material of the present invention is 50 to 150 m / m ² of the light-sensitive material.
1 is preferable, and 65 to 130 ml is more preferable. Preferred fixing solutions can include fixing materials commonly used in the art.

As the fixing agent, ammonium thiosulfate,
It is a thiosulfate such as sodium thiosulfate, and ammonium thiosulfate is particularly preferred from the viewpoint of fixing speed. The concentration of the ammonium thiosulfate is preferably in the range of 0.1 to 5 mol / l, more preferably in the range of 0.8 to 3 mol / l. The pH of the fixing solution is 3.8 or more, preferably 4.2 or more.

In the present invention, the fixing solution may be one which forms an acidic hardening. In this case, an aluminum compound is preferably used as a hardener. For example, it is preferable to add in the form of aluminum sulfate, aluminum chloride, potash and the like. In addition, the fixing solution may optionally contain a preservative such as a sulfite or a bisulfite, a pH buffer such as acetic acid or boric acid, a mineral acid (sulfuric acid, nitric acid) or an organic acid (citric acid, oxalic acid,
Various acids such as malic acid), hydrochloric acid and the like, pH adjusters such as metal hydroxides (potassium hydroxide and sodium hydroxide) and chelating agents having a water softening ability can be contained.

Examples of the fixing accelerator include, for example,
No. 35754, No. 58-122535, No. 58-12
No. 2536, thiourea derivatives, U.S. Pat.
Thioether described in US Pat. No. 6,459. The replenishment of the fixing solution during the fixing processing of the light-sensitive material of the present invention is preferably 50 to 150 ml per 1 m ² of the light-sensitive material,
~ 130 ml is more preferred.

The treatment method of the present invention is preferably a method using a solid treating agent. To solidify the photographic processing agent, a concentrated liquid or fine powder or granular photographic processing agent and a water-soluble binder are kneaded and molded, or the water-soluble binder is sprayed on the surface of the temporarily molded photographic processing agent. Any means such as forming a coating layer can be adopted (see JP-A-4-29136 and JP-A-4-29136).
-85535, 4-85536, 4-8553
No. 3, 4-85534 and 4-172341).

A preferred tablet production method is a method in which a powdery solid processing agent is granulated and then subjected to a tableting step to form the tablet. There is an advantage that the solubility and storage stability are improved and the photographic performance becomes stable as compared with a solid processing agent formed by simply mixing a solid processing agent component and forming a tablet. Granulation methods for tablet formation include rolling granulation, extrusion granulation, compression granulation,
Known methods such as crushing granulation, stirring granulation, fluidized bed granulation, and spray drying granulation can be used. For tablet formation, the average particle size of the obtained granules is 100 to 800 μm in that, when the granules are mixed and pressed and compressed, non-uniformity of components, so-called segregation hardly occurs. It is preferable to use one having a thickness of 200 to 750 μm. Further, the particle size distribution is such that 60% or more of
Those with a deviation of 50 μm are preferred. Next, when the obtained granules are compressed under pressure, a known compressor, for example, a hydraulic press, a single-shot tableting machine, a rotary tableting machine, or a briquetting machine can be used. The solid processing agent obtained by pressurizing and compression can take any shape, but from the viewpoint of productivity, handleability, or the problem of dust when used on the user side, a cylindrical, so-called tablet is used. preferable. More preferably, at the time of granulation, the above-mentioned effect becomes more remarkable by separately granulating each component, for example, an alkali agent, a reducing agent, a preservative, and the like.

The method for producing a tablet processing agent is described, for example, in JP-A-51-61837, JP-A-54-155038, and JP-A-52-55038.
-88025, British Patent 1,213,808, etc., and can be produced by a general method. Further, granulating agents are described in, for example, JP-A Nos. 2-109042 and 2-1.
No. 09043, No. 3-39735 and No. 3-3993
It can be produced by a general method described in the specification such as No. 9. Furthermore, powder processing agents are described, for example, in JP-A-54-13.
No. 3332, British Patent Nos. 725,892 and 729,8
No. 62 and German Patent 3,733,861, etc., it can be produced by a general method.

[0097] The bulk density of the solid processing agent, and in view of its solubility, if a tablet from the viewpoint of the effect of the object of the present invention 1.0g / cm ³ ~2.5g / cm ³ is preferably 1. 0g
/ Cm ³ in terms of the strength of the solid obtained,
If it is less than 2.5 g / cm ³ , it is more preferable in terms of solubility of the obtained solid. When the solid processing agent is granules or powder, the bulk density is preferably 0.40 to 0.95 g / cm ³ .

As the automatic developing machine used in the present invention, a known roller-type automatic developing machine is preferably used. When processing the silver halide photographic light-sensitive material of the present invention, the total processing time (dry to dry) is 1 using an automatic processor.
The treatment is preferably performed in 0 to 45 seconds, and more preferably in 15 to 30 seconds. Here, the time from the time when the tip of the photosensitive material to be processed is immersed in the developing tank liquid of the automatic developing machine to the time when it comes into contact with the fixing tank liquid in the next process is referred to as “development time”. "Fixing time" refers to the time until it comes into contact with the washing tank
When the time of dipping in the washing tank liquid is referred to as “washing time” and the time of entering the drying zone of the automatic developing machine is referred to as “drying time”, the developing time is 3 to 15 seconds (further 3 to 10 seconds).
Developing temperature 25-50 ° C (further 30-40 ° C), fixing time 2-12 seconds (further 2-10 seconds), fixing temperature 20-5
0 ° C (further 30-40 ° C), water washing (stabilization) time 2 ~
15 seconds (further 2 to 8 seconds), water washing (stabilization) temperature 0 to 5
0 ° C (further 15 to 40 ° C), drying time 3 to 12 seconds (further 3 to 8 seconds), drying temperature 35 to 100 ° C (further 40 ° C).
-80 ° C) is preferred. The silver halide photographic light-sensitive material of the present invention is subjected to development, fixing and washing with water (or stabilization), dried with a squeeze roller and then dried.

[0099]

EXAMPLES Hereinafter, the present invention will be described specifically with reference to examples, but the present invention is not limited to these embodiments. Example 1 All the emulsions shown below were prepared using a reaction vessel having a volume of 32 liters. Asahi Kasei SIP-1013 ultrafiltration unit and DAID circulating pump
O Rotary Pump was used. The volume of the emulsion circulation portion of the ultrafiltration step was 1.2 liters, and the emulsion was circulated at a constant flow rate of 15 liters / minute. Therefore, the residence time of the reactant solution is 4.8 seconds, and the volume of the emulsion circulation part in the ultrafiltration step is 3.8 times the volume of the reaction vessel.
%Met. The control of the distance between particles in the particle growth process was performed by appropriately controlling the permeation flux in the ultrafiltration step. Specifically, the flow control valve 1 shown in FIG.
9 and ultrafiltration of the reactant solution in the reaction vessel over the entire area of the particle growth step-1 and the particle growth step-2 so that the average interparticle distance at the start of the particle growth step-1 is maintained. Concentration was performed by circulation to the apparatus. (Em-1: Preparation of Ultrafiltered Emulsion) [Nucleation Step] The following gelatin solution B-10 in a reaction vessel
1 was maintained at 30 ° C., and the pH was adjusted to 1.96 with 1N sulfuric acid while stirring at 450 rpm using the mixing and stirring apparatus of FIG. Thereafter, the S-101 solution and the X-101 solution were added at a flow rate of 5.0 ml / sec by using the double jet method to form nuclei. (B-101) Low molecular weight gelatin (average molecular weight 20,000) 32.4 g Potassium bromide _{9.92g H 2 O 12938.0ml (S-} 101) silver nitrate _{50.43g H 2 O 225.9ml (X-} 101) odor Potassium iodide 35.33 g H ₂ O 224.7 ml [Aging step] After the completion of the above addition, the following G-101 solution was added, and the temperature was raised to 60 ° C. over 30 minutes. After heating, 60
The stirring was maintained for 20 minutes while maintaining the temperature. Subsequently, the pH was adjusted to 9.5 by adding a 28% aqueous ammonia solution, and the mixture was maintained for 7 minutes. A 1N aqueous nitric acid solution was added thereto to adjust the pH to 5.
Adjusted to 8. During this time, the silver potential of the solution (measured with a silver ion selective electrode using a saturated silver-silver chloride electrode as a reference electrode) was controlled at 14 mV using a 1N potassium bromide solution. (G-101) Alkali-treated inert gelatin (average molecular weight 100,000) 139.1 g HO (CH ₂ CH ₂ O) _m [CH (CH ₃ ) CH ₂ O] _19.8 (CH ₂ CH ₂ O) _n H (m + n = 9.77) 10% by mass methanol solution 4.64 ml H ₂ O 3266.0 ml [Grain growth step-1] After ripening, the S-102 solution and the X-102 solution are flowed using the double jet method. While accelerating (the ratio of the addition flow rate at the end to the start is about 12 times)
Added in 38 minutes. After completion of the addition, the G-102 solution was added, and the stirring rotation speed was adjusted to 550 rpm. Then, the S-103 solution and the X-103 solution were successively accelerated while increasing the flow rates (the addition flow rates at the end and at the start). (Roughly twice the ratio) was added in 40 minutes. During this time, the silver potential of the solution was controlled at 14 mV using a 1N potassium bromide solution. (S-102) Silver nitrate _{639.8g H 2 O 2866.2ml (X-} 102) Potassium bromide _{448.3g H 2 O 2850.7ml (G-} 102) alkali-treated inert gelatin (average molecular weight 100,000) 203. 4 g 10% by mass methanol solution of the above [Compound A] 6.20 ml H ₂ O 1867.0 ml (S-103) Silver nitrate 989.8 g H ₂ O 1437.2 ml (X-103) Potassium bromide 679.6 g Potassium iodide 19.35g H ₂ O 1412.0ml [grain growth process -2] the additive after terminated, and the solution temperature in the reaction vessel was cooled to take to 40 ° C. for 20 minutes. afterwards,
After adjusting the silver potential in the reaction vessel to -32 mV using a 3.5 N aqueous potassium bromide solution, the following silver iodide fine grain emulsion a was added in an amount corresponding to 71.2 g of silver nitrate, and the S-104 solution and X- Solution 104 was added for 7 minutes while accelerating the flow rate (the ratio of the addition flow rate at the end to the start was 1.2 times). Over (S-104) Silver nitrate _{672.0g H 2 O 975.8ml (X-} 104) Potassium bromide 470.8g H ₂ O 959.4ml entire area of the particle growth step 1 and the particle growth step 2,
The reaction solution in the reaction vessel was circulated to the ultrafiltration device so as to maintain the average interparticle distance at the start of the particle growth step 1, and concentration was performed. (Preparation of silver iodide fine grain emulsion a) A 2000 ml aqueous solution containing 35 g of gelatin was stirred at 40 ° C. Using a KI aqueous solution, the silver potential was set to -150 m with respect to the saturated calomel electrode.
After adjusting to V, AgNO ₃ (178 g) aqueous solution and KI
(174 g) The aqueous solution was added over 13 minutes while accelerating the flow rate by the double jet method. After desalting, gelatin was added and the pH was adjusted to 6.8 and pAg9 at 50 ° C. This silver iodide fine grain emulsion had an average equivalent circle diameter of 0.05 μm.

After completion of the growth, desalting and washing are carried out according to a conventional method, and gelatin is added and dispersed well.
H was adjusted to 5.8 and pAg to 8.1. The resulting emulsion had an average grain thickness of 0.18 microns and an average grain diameter of 1.
16, hexagonal tabular grains having an average aspect ratio of 6.4. When dislocation lines were observed, an average of 16 dislocation lines were observed in the particle fringe portion. This emulsion was designated as Em-1.

After the above emulsion was heated to 60 ° C., adenine, ammonium thiocyanate, chloroauric acid was added 10 minutes after the spectral sensitizing dye (the following compound and amount) was added as a dispersion in the form of solid fine particles. And a mixed solution of sodium thiosulfate and a dispersion of triphenylphosphine selenide were added, and 30 minutes later, silver iodide fine grain emulsion a was added, followed by ripening for a total of 2 hours. At the end of ripening, 4-hydroxy-6-methyl-1,3,3a, 7-
A predetermined amount of tetrazaindene was added.

The amount added per mole of AgX is shown below. 5,5-dichloro-9-ethyl-3,3'-di- (sulfopropyl) -oxacarbocyanine sodium salt anhydrous 270 mg 5,5-di- (trifluoromethyl) -1-methyl-1'-ethyl -3,3'-Di- (sulfopropyl) -benzimidazolocarbocyanine sodium salt anhydrous 100 mg adenine 10 mg potassium thiocyanate 90 mg chloroauric acid 20 mg sodium thiosulfate 2.0 mg triphenylphosphine selenide 0.2 mg iodide Silver fine particles a Equivalent to 0.3 mol 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene 500 mg A solid fine particle dispersion of a spectral sensitizing dye was prepared by a known method.

That is, the predetermined amount of the spectral sensitizing dye is
It was obtained by adding to water adjusted to ° C. and stirring with a high-speed stirring (dissolver) at 3,500 rpm for 30 to 120 minutes. The dispersion of the above selenium sensitizer was prepared as follows. That is, 120 g of triphenylphosphine selenide was added to 30 kg of ethyl acetate at 50 ° C., and the mixture was stirred and completely dissolved. On the other hand, 3.8 kg of photographic gelatin was dissolved in 38 kg of pure water, and 93 g of a 25 mass% aqueous solution of sodium dodecylbenzenesulfonate was added thereto.
Was added. Next, these two liquids are mixed to obtain a diameter of 10c.
m with a high-speed stirring type disperser having a dissolver of 50 m.
Dispersion was performed at a dispersion blade peripheral speed of 40 m / sec at 30 ° C. for 30 minutes. Thereafter, ethyl acetate was removed while stirring under reduced pressure until the residual concentration of ethyl acetate became 0.3% by mass or less. Thereafter, this dispersion was diluted with pure water to finish up to 80 kg. A part of the dispersion thus obtained was fractionated and used in the above Examples. <Preparation of Emulsion Layer Coating Solution> The following various additives were added to each emulsion obtained above.

1,1-Dimethylol-1-bromo-1-nitromethane 0.1 mg / m ² t-butyl-catechol 2 mg / m ² polyvinylpyrrolidone (molecular weight 10,000) 15 mg / m ² styrene-maleic anhydride copolymer Combined 30 mg / m ² Sodium polystyrene sulfonate 30 mg / m ² Trimethylolpropane 100 mg / m ² Nitrophenyl-triphenyl-phosphonium chloride 0.2 mg / m ² Sodium 1,3-dihydroxybenzene-4-sulfonate 10 mg / m ² Sodium 2-mercaptobenzimidazole-5-sulfonate 0.2 mg / m ² nC ₄ H ₉ OCH ₂ CH (OH) CH ₂ N (CH ₂ COOH) ₂ 10 mg / m ² Gelatin 1.2 g / m ² ( monolayer preparation of protective layer coating solution) gelatin 0.9 g / m ² polymer particles Tables 1-6 set forth the particles) Table 1-6 becomes mattness amount adjusting hardener _{(CH 2 = CHSO 2 CH 2} CONHCH 2 -) adjusting compound amount to ₂ swelling ratio is 150% (S-1) 7 mg / m ² polyalkylene oxide-based nonionic surfactant (exemplary compound) Amount shown in Tables 1 to 6 Fluorine-based surfactant (exemplary compound) Amount shown in Tables 1 to 6 (Coating solution for multilayer protective layer) Preparation) Coating solution for upper protective layer Gelatin Amount shown in Tables 1 to 6 Polymer particles (particles described in Tables 1 to 6) Adjusted to an amount that gives a matte degree shown in Tables 1 to 6 Hardener (CH ₂ = CHSO ₂ CH ₂ CONHCH ₂ −) ₂ ) Adjust the addition amount so that the swelling ratio becomes 150% Compound (S-1) 7 mg / m ² Polyalkylene oxide nonionic surfactant (exemplary compound) Amount shown in Tables 1 to 6 Fluorine surfactant ( Exemplified compound) Amount shown in Tables 1 to 6 Lower protective layer coating solution Gelatin Amount shown in Tables 1 to 6 Polymer particles (particles described in Tables 1 to 6) Adjusted to an amount that gives a matte degree of Tables 1 to 6 Polyalkylene oxide nonionic surfactant (exemplary compound) Table 1 the amount shown on the amount fluorinated surfactant (compound) table 1-6 indicated in 6 Note that the amount with the material is one-sided 1 m ² per silver coverage becomes 1.5 g / m ² as a one-sided partial Was adjusted as follows. (Preparation of filter layer) Glycidyl methacrylate 50
A copolymer dispersion obtained by diluting a copolymer composed of three types of monomers of 10% by mass, 10% by mass of methyl acrylate, and 40% by mass of butyl methacrylate so as to have a concentration of 10% by mass was used as a subbing liquid. on both surfaces of the coated thickness of 175μm blue colored polyethylene terephthalate support to prepare a support sample coating amount per surface 1 m ² was coated with a filter layer so that the following composition.

Solid fine particle disperse dye (AH) 50 mg Gelatin 0.2 g Sodium dodecylbenzenesulfonate 2 mg Compound (I) 5 mg Colloidal silica (average particle size 0.014 μm) 10 mg Potassium polystyrene sulfonate 50 mg

[0106]

Embedded image

(Coating) Using these coating solutions, two slide hopper type coaters were used at a speed of 120 m / min using two slide hopper type coaters so that the coating amount was 1.5 g / m ² per one side. The body sample was simultaneously coated on both sides with the following layer constitution and dried for 2 minutes and 20 seconds to prepare a coated sample. <Preparation of solid developer> [Granulated product (A)] 1050 g of sodium metabisulfite,
450 g of 1-phenyl-3-pyrazolidone, 7200 g of sodium erysorbate monohydrate, 810 g of binder D-sorbit, N-acetyl-DL-penicillamine 7
g, 300 g of glutaraldehyde bisulfite in a commercially available stirring granulator at room temperature for about 3 minutes.
Of water is added over 1 minute, and the granulated material is dried at 50 ° C. for 2 hours with a fluidized-bed drier to almost completely remove water from the granulated material. [Granulated material (B)] An average of 10500 g of potassium carbonate and 6.0 g of potassium iodide were averaged in a commercially available bantam mill.
Grind to μm. These fine powders and DTPA-N
a 170 g, sodium sulfite 425 g, 5-mercapto- (1H) -tetrazolylacetic acid Na salt 8.3 g, 1-
(3-sulfophenyl) -5-tetrazole-Na salt 4
0 g, binder mannitol 1500 g, and D-sorbit 600 g were added, mixed at room temperature for about 3 minutes in a commercially available stirring granulator, and granulated by adding 125 ml of water over 1 minute. Is dried at 40 ° C. for 2 hours in a fluidized drier to remove almost completely the water content of the granulated product.

The granulated product (A) thus obtained was added with 1
1.0% of total weight of sodium octanesulfonate,
Methyl-β-cyclodextrin at 3% of total weight, 25%
At room temperature adjusted to 40 ° C. or less, and further, the granulated product (B) contained sodium 1-octanesulfonate at 1.2% of the total weight and methyl-β-cyclodextrin at the total weight. In a room conditioned at 25 ° C. and 40% RH or less, and mixed with Kikusui Seisakusho tough press collect 15
Compressed tableting was performed using a modified tableting machine of 27HU to produce each of the developed tablets (A) and (B). The filling amount per tablet was (A) 8.45 g and (B) 12.4 g. (A) 60 pieces, (B) 50 pieces (volume after dissolution is 5.0
The tablets were sealed and packaged using a packaging material having the following layer structure for moisture prevention.

The packaging material is biaxially stretched nylon (ONY)
15 μm thickness / aluminum oxide deposited PET 12 μm thickness /
This bag is made of a laminate material consisting of biaxially oriented polypropylene (OPP) 25 μm thick / low density polyethylene (LLDP) 40 μm thick. The effective surface area on the side (inside) of the packaging material that contacts the tablet is 1300 cm ^2. Was. <Preparation of solid fixing agent> [Granulated product (C)] In a commercially available bantam mill, 14580 g of ammonium thiosulfate / sodium thiosulfate (weight ratio: 90/10) is pulverized to an average of 10 µm. The compound HO—CH ₂ CH ₂ —S—CH ₂ CH ₂ —SC is added to this fine powder.
H ₂ CH ₂ -OH1000g, sodium metabisulfite 9
After adding 20 g, 50 g of 5-mercapto-tetrazole and 900 g of binder pine flow, mixing in a commercially available stirring granulator at room temperature for about 3 minutes, and granulating by adding 150 ml of water over 1 minute. The granulated product is dried at 40 ° C. in a fluidized bed drier to remove water almost completely. [Granulated product (D)] 250 g of boric acid, 1500 g of aluminum sulfate octahydrate, 1150 g of succinic acid, 250 g of tartaric acid, 208 g of mannite, and 100 g of D-sorbite are added, and the mixture is added at room temperature in a commercially available stirring granulator. Mix for 3 minutes, 150ml
Of water is added over 1 minute to granulate, and the granulated material is dried at 40 ° C. in a fluidized bed drier to remove water almost completely.

The granulated product (C) thus obtained, 1400 g of sodium acetate and sodium 1-hexanesulfonate in a room conditioned at 2.5% of the total weight, 25 ° C. and 40% RH or less. 1400 g of sodium acetate was added to the granulated product (D), and 3.0% of the total weight of sodium 1-hexanesulfonate was added at 25 ° C and 40 ° C.
% RH was added and mixed in a room conditioned to be not more than% RH, and compression tableting was performed using a tableting machine modified from Tough Press Collect 1527HU manufactured by Kikusui Seisakusho to produce fixing tablets (C) and (D). The filling amount per tablet is (C) 10.5 g,
(D) The weight was 8.95 g. This is (C) 92 pieces, (D)
Twenty-eight tablets (volume having a volume of 5.0 liters after dissolution) were sealed and packaged using the packaging material used in the developing tablets (A) and (B) for moisture prevention. Development starter formulation (addition amount per liter of developer) N-acetyl-DL-penicillamine 0.11 g diethylene glycol 48.5 g 5-mercapto- (1H) -tetrazolylacetic acid Na 0.12 g acetic acid 90% 11.5 g KBr 8.0 g Finishing with pure water 67 ml TCX-701 (manufactured by Konica Corporation) was used as an automatic developing machine. At the start, 7.8 liters of the developing solution in which the developing tablet was dissolved was added to the developing solution in the developing tank, and a starter was added to fill the developing tank as a starting solution to start processing.
The starter was added in an amount of 67 ml / liter of the developing solution, which was equivalent to the capacity of the developing tank of 7.8 liter. As a fixing solution, 5.6 liters of the fixing solution prepared in the same manner was placed in a fixing tank of TCX-701 to be used as a starting solution.

In each of the developing and fixing steps, the one in which each packaging bag was opened by hand was set at the inlet of each solid agent, the tablets were dropped into the built-in chemical mixer, and at the same time hot water (25 to 3) was added.
(0 ° C) and dissolving with stirring for 25 minutes while stirring and dissolving.
Adjust to 0 liters. This was used as a developing and fixing replenisher. The pH when the developer was dissolved was 10.15, and the pH when the starter was added was 9.90. The dissolution pH of the fixing solution was 4.25.

The built-in chemical mixer is divided into a liquid preparation tank and a spare tank tank. The capacity of the liquid preparation tank is 5.0 liters and the capacity of the spare tank is 5.0 liters. The film is produced in the liquid preparation tank during the running process. A spare tank is provided to supply the replenisher so that the replenisher does not enter the non-replenished state during the stirring and dissolving time (about 25 minutes) even if the replenisher runs out.

Development temperature 35 ° C. (replenishment rate is 100 ml / m
² ) The evaluation was performed at a fixing temperature of 35 ° C. (replenishment rate was 100 ml / m ² ), water at 18 ° C. (5 liter / min), a drying temperature of 55 ° C., and a processing time of 30 seconds. <Evaluation of Sensitometry> The prepared sample was sandwiched between two fluorescent intensifying screens XG-S (manufactured by Konica Corporation) and the tube voltage was 90 k.
X-ray irradiation was performed under the conditions of Vp, current of 100 mA, and time of 0.05 seconds, development was performed, and then a sensitometric curve was prepared by a distance method to determine sensitivity and fog. The value of the sensitivity was determined as the reciprocal of the X-ray dose required to obtain a density of fog + 1.0, and the sample No. The relative sensitivity was evaluated with the value of the film No. 1 as 100. <Scratch resistance evaluation> Unexposed sample film was heated at 23 ° C.
After leaving for 2 hours under the condition of a relative humidity of 40%, rubbing with a commercially available nylon scourer under the same conditions under a load of 100 g / cm ² , processing with an automatic developing machine under the above conditions, and visual observation An evaluation was performed.

A: Almost no scratch B: Practically no problem, but a few scratches C: Scratch occurs to the extent of being noticeable, practically problematic D: Very many scratches <Evaluation of cut-out resistance> The same sample conditioned for 12 hours under the air-conditioning conditions of 23 ° C. and 80% RH is superimposed on each other at 20 g / cm.
^A load was applied so that a pressure of ² was applied, and the film was allowed to stand for 3 days, and the degree of tightness between the films was evaluated in four stages of A to D as follows.

A: No dustiness B: Less than 5% area C: Less than 15% area D: More than 15% area <Evaluation of transportability> Using an auto feeder KDA-500 (manufactured by Konica Corporation), four pieces were used. Ten sets were transported in 100 pieces of one cut size, and the number of occurrences of defective transport was measured.
Each time the sample was changed, the suction cup was cleaned with gauze moistened with alcohol. The sample is 23 ° C, 20% RH, 80% R
H was conditioned for 2 hours, and the transportability was evaluated under the same conditions.

[0116]

[Table 1]

[0117]

[Table 2]

[0118]

[Table 3]

[0119]

[Table 4]

[0120]

[Table 5]

[0121]

[Table 6]

[0122]

According to the present invention, a silver halide photographic light-sensitive material for medical X-ray photography which has no influence on sensitometry and has excellent scratch resistance, anti-stickiness and transportability can be provided.

[Brief description of the drawings]

FIG. 1 is a schematic view showing an example of a silver halide emulsion manufacturing apparatus applicable to the present invention.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 Reaction container 2 Stirring mechanism 3 Dispersion medium 4 Silver addition line 5 Halide addition line 6 Dispersion medium addition line 7 Addition line 8 Liquid take-out line 9 Liquid return line 10 Permeate discharge line 11 Permeate return line 12 Ultrafiltration unit 13 Circulation Pump 14 Flow meter 15, 16, 17 Pressure gauge 18 Pressure adjusting valve 19 Flow adjusting valve 20 Silver addition valve 21 Halide addition valve 22 Liquid extraction valve 23, 24, 25 Valve 26 Ultrafiltration permeate 27 Permeate receiver 28 Scale 29,30 Silver halide fine grain emulsion addition line 31,32 Fine grain addition valve

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) G03C 1/85 G03C 1/85

Claims (6)

[Claims] 1. A silver halide photographic light-sensitive material having at least one silver halide emulsion layer on each side of a support and two or more non-light-sensitive colloid layers above the silver halide emulsion layer. In the material, the non-photosensitive colloid layer of the intermediate layer contains true spherical polymer particles having an average particle diameter of 1 to 10 μm and a relative standard deviation of 10% or less and a polyalkylene oxide-based nonionic surfactant. A silver halide photographic material comprising a fluorine-containing surfactant in the non-photosensitive colloid layer as an outer layer. 2. A silver halide photographic light-sensitive material having at least one silver halide emulsion layer on each side of a support and two or more non-light-sensitive colloid layers above the silver halide emulsion layer. In the material, the non-photosensitive colloid layer of the intermediate layer has an average particle size of 1 to 10 μm,
A silver halide photograph containing polymer particles containing 5 mol% of an acidic monomer and a polyalkylene oxide-based nonionic surfactant, and containing a fluorine-based surfactant in the outermost non-photosensitive colloid layer. Photosensitive material. 3. The method according to claim 1, wherein the fluorine-based surfactant is a combination of at least one fluorine-based anion surfactant and at least one fluorine-based cationic surfactant. Silver halide photographic material. 4. A coating solution of at least one layer of a silver halide emulsion layer on a support, and an intermediate layer having an average particle diameter of 1 to 10 μm.
m, a non-photosensitive colloid layer coating solution containing spherical polymer particles having a relative standard deviation of 10% or less and a polyalkylene oxide-based nonionic surfactant, and a non-photosensitive solution containing a fluorine-based surfactant in the outermost layer The method for producing a silver halide photographic light-sensitive material according to claim 1, wherein the coating liquid for the aqueous colloid layer is applied simultaneously and in layers. 5. A coating solution of at least one layer of a silver halide emulsion layer on a support, and an intermediate layer having an average particle diameter of 1 to 10 μm.
m, a non-photosensitive colloid layer coating solution containing polymer particles containing 5 to 15 mol% of an acidic monomer and a polyalkylene oxide-based nonionic surfactant, and a non-photosensitive solution containing a fluorine-based surfactant in the outermost layer 3. The method for producing a silver halide photographic light-sensitive material according to claim 2, wherein a coating liquid for the aqueous colloid layer is applied simultaneously and in layers. 6. The fluorinated surfactant according to claim 4, wherein the fluorinated surfactant is a combination of at least one fluorinated anionic surfactant and at least one fluorinated cationic surfactant. A method for producing a silver halide photographic material.