JP2001117203A - Silver halide photographic sensitive material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a silver halide photographic sensitive material for medical X-ray photographing having no effect on sensitometry and excellent in scuffing 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 a non-pbotosensitive colloidal layer above the emulsion layer. The non- photosensitive colloidal layer contains spherical polymer particles having 1-10 μm average particle diameter and <=10% relative standard deviation and a polymer latex having at least one monomer whose solubility in water at 25 deg.C is <=0.025 wt.% as a monomeric unit.

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 photographic light-sensitive material for medical X-ray photography having improved scratch resistance, anti-stickiness and transportability.

[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. Along with these automation and high-speed conveyance, it is strongly desired that photosensitive materials have high abrasion resistance, are free from cracks, and have good conveyance properties.

With respect to scratch resistance, it is effective to increase the elastic modulus of the protective layer and 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.

[0004] 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.

[0005] Further, under conditions of high humidity, the films tend to stick together, and a plurality of sheets are simultaneously conveyed and the film is liable to be 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 fluorine-based surfactant is used, a spot-like processing failure or processing unevenness may occur due to the adhesion of the surfactant accumulated in the processing liquid to the film.

[0006]

SUMMARY OF THE INVENTION An object of the present invention is to provide a silver halide photographic light-sensitive material for medical X-ray photography in which the film has improved scratch resistance, dustiness and transportability at the same time.

[0007]

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 both surfaces of a support and a non-photosensitive colloid layer above the silver halide emulsion layer, In the non-photosensitive colloid layer, at least one kind of spherical polymer particles having an average particle size of 1 to 10 μm and a relative standard deviation of 10% or less and a solubility in water at 25 ° C. of 0.025% by weight or less is used. A silver halide photographic material comprising a polymer latex having a monomer as a monomer unit.

(2) A silver halide photographic material having at least one silver halide emulsion layer on both sides of a support and a non-light-sensitive colloid layer above the silver halide emulsion layer, In the non-photosensitive colloid layer, spherical polymer particles having an average particle diameter of 1 to 10 μm and a relative standard deviation of 10% or less, and the following general formula (1)
A silver halide photographic material comprising at least one compound represented by the formula:

[0010]

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Wherein R ₁ and R ₂ each represent a substituent.
Here, at least one of R ₁ and R ₂ represents an alkoxy group or an aryloxy group. X ₁ and X ₂ each represent a halogen atom. m, n, p and q each represent an integer of 0-4. However, the sum of m and n and the sum of p and q are each an integer of 0 to 4, and both m and n are not 0. or,
When m, n, p or q is 2 or more, a plurality of R ₁ , R ₂ , X
₁ or X ₂ may be the same or different. (3) In a silver halide photographic material having at least one silver halide emulsion layer on both surfaces of a support and a non-photosensitive colloid layer above the silver halide emulsion layer, The hydrophilic colloid layer contains at least one of spherical polymer particles having an average particle diameter of 1 to 10 μm and a relative standard deviation of 10% or less and a compound represented by the following general formula (2). Silver halide photographic material.

[0012]

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Wherein R ₁₁ and R ₁₂ are each an alkyl group,
R ₁₃ represents an aryl group, an alkoxy group or an aryloxy group, and R ₁₃ represents an alkoxy group or an aryloxy group. (4) In a silver halide photographic material having at least one silver halide emulsion layer on both surfaces of a support and a non-photosensitive colloid layer above the silver halide emulsion layer, Silver halide, characterized in that the colloidal 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 colloidal silica having an average particle diameter of 100 nm or less. Photosensitive material.

(5) A silver halide photographic material having at least one silver halide emulsion layer on both sides of a support and a non-photosensitive colloid layer above the silver halide emulsion layer, The non-photosensitive colloid layer contains spherical polymer particles having an average particle diameter of 1 to 10 μm and a relative standard deviation of 10% or less, a fluorine-based cationic surfactant, and a fluorine-based anionic surfactant. Silver halide photographic material.

(6) A silver halide photographic material having at least one silver halide emulsion layer on each side of a support and a non-photosensitive colloid layer above the silver halide emulsion layer, In the non-photosensitive colloid layer, the average particle diameter is 1 to 10 μm, and 5 to 15 mol%
Silver halide photographic light-sensitive material comprising a polymer particle containing an acidic monomer of formula (I) and a polymer latex having as a monomer unit at least one monomer having a solubility in water at 25 ° C. of not more than 0.025% by weight. material.

(7) A silver halide photographic material having at least one silver halide emulsion layer on each side of a support and a non-photosensitive colloid layer above the silver halide emulsion layer, In the non-photosensitive colloid layer, the average particle diameter is 1 to 10 μm, and 5 to 15 mol%
A silver halide photographic light-sensitive material comprising at least one of polymer particles containing an acidic monomer of formula (1) and a compound represented by formula (1).

(8) A silver halide photographic material having at least one silver halide emulsion layer on both surfaces of a support and a non-photosensitive colloid layer above the silver halide emulsion layer, In the non-photosensitive colloid layer, the average particle diameter is 1 to 10 μm, and 5 to 15 mol%
A silver halide photographic material comprising at least one of polymer particles containing an acidic monomer of formula (1) and a compound represented by formula (2).

(9) A silver halide photographic light-sensitive material having at least one silver halide emulsion layer on each side of a support and a non-light-sensitive colloid layer above the silver halide emulsion layer. In the non-photosensitive colloid layer, the average particle diameter is 1 to 10 μm, and 5 to 15 mol%
A silver halide photographic light-sensitive material characterized by containing a polymer particle containing an acidic monomer, a fluorinated cationic surfactant and a fluorinated anionic surfactant.

(10) The silver halide as described in (1), (4), (5), (6) or (9) above, which contains at least one of the compounds represented by formulas (1) and / or (2). Photosensitive material.

(11) Matt degree is 150 to 250 mm
Hg (2.0 to 3.3 × 10 ³ Pa), wherein the silver halide photographic light-sensitive material as described in any one of 1 to 10 above.

(12) The above-mentioned item (1), which comprises a polyalkylene oxide-based nonionic surfactant,
2. The silver halide photographic light-sensitive material according to any one of 1.

(13) A silver halide photographic material, wherein the spherical polymer particles according to any one of the above items (1) to (5) contain a crosslinkable monomer as a monomer unit.

(14) A silver halide photographic light-sensitive material, wherein the true spherical polymer particles described in any one of (1) to (5) are synthesized by a seed polymerization method.

Hereinafter, the present invention will be described in more detail.

The polymer particles according to claims 1 to 5 of the present invention will be described. Polymer particles of the present invention,
The average particle diameter is 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
And more preferably 3 μm to 8 μm. The relative standard deviation is preferably 8% or less, more preferably 7%.
It is as follows. 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 preferably from 50 to 600 mg / m ² · sided, more preferably 80~400mg / m ² · sided,
More preferably, it is 100 to 300 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 the seed polymerization method, a monomer, a polymerization initiator and an emulsifier are charged into an aqueous medium to be emulsified, and the seed particle is charged into the emulsion to carry out polymerization. Let it.

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) acrylic ester or a copolymer of (meth) acrylic ester monomer and 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, and usually 0 to 80 parts by weight, preferably 0 to 80 parts by weight of a (meth) acrylate. 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, and the gel fraction of the seed particles by a 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.

When forming the seed particles, the above bifunctional monomer or polyfunctional monomer is usually used in an amount of 0.005 to 0.05 parts by weight, preferably 100 parts by weight, based on 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 preferred.

Examples of the polymerization initiator used in the soap-free emulsion polymerization include persulfates such as potassium persulfate and ammonium persulfate. The polymerization initiator is soluble in the aqueous medium used in the polymerization. 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, a monomer 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-polyacrylic acid copolymers and neutralized products thereof, and polyvinyl methacrylic acid, copolymers thereof, 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] A monomer, methyl methacrylate 100, was placed in a 1-liter four-necked flask equipped with a thermometer and a nitrogen inlet tube. To the parts by weight, 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 diameter of the seed particles was 0.50 μm and 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 0.1 parts by weight of benzoyl peroxide. 2 parts by weight were added and dissolved, and ion-exchanged water 90 in which 1 part by weight of sodium dodecylbenzenesulfonate and 1 part by weight of 88% saponified polyvinyl alcohol were dissolved was further added.
After mixing with 0 parts by weight, 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 size of the obtained polymer particles was 1.2.
0 μm with a standard deviation of 0.05 μm. The gel fraction obtained by the toluene extraction method was 60%.

[Third Stage Polymerization] Next, in a similar apparatus, 95 parts by weight of methyl methacrylate as a monomer, 5 parts by weight of ethylene glycol dimethacrylate as a crosslinkable monomer and 0.2 parts by weight of benzoyl peroxide were used. And 1 part by weight of sodium dodecylbenzenesulfonate and 900 parts by weight of ion-exchanged water in which 1 part by weight of 88% saponified polyvinyl alcohol was added and mixed. Mix for 30 minutes below.

Next, 20 parts by weight of the seed emulsion obtained in the second stage was added to this 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 0.20 μm.
And the relative standard deviation was 4.5%.

The polymer particles according to claims 6 to 9 of the present invention have an average particle diameter of 1 to 10 μm,
It is a copolymer comprising 5 to 15% 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.
m. 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 is dissolved at the time of development processing, and 5 mol%
In the following cases, it is easy to peel off.

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 into monodisperse 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 diameter 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) At least one of the monomers forming the polymer latex used in the present invention has a solubility in water at 25 ° C. of 0.025% by weight or less.
It is 0.015% by weight or less. Such ethylenic monomers include, for example, hexyl acrylate, 2-ethylhexyl acrylate, octyl acrylate, tert
-Octyl acrylate, nonyl acrylate, iso
-Nonyl acrylate, cyclohexyl acrylate,
n-stearyl acrylate, lauryl acrylate,
Acrylic esters such as tridecyl acrylate, butyl methacrylate, iso-butyl methacrylate,
tert-butyl methacrylate, hexyl methacrylate, 2-ethylhexyl medallylate, octyl methacrylate, iso-octyl methacrylate, tert-
Octyl methacrylate, nonyl methacrylate, iso-
Nonyl methacrylate, cyclohexyl methacrylate, n
-Stearyl methacrylate, lauryl methacrylate,
Examples include methacrylates such as tridecyl methacrylate and the like, and divinylbenzene.

The solubility of the monomer forming the polymer latex used in the present invention in water at 25 ° C. can be measured by the method described in Basic Experiment 1 of New Experimental Chemistry Course (Maruzen Chemical, 1975). . When measured by this method, the solubility of the monomer of the present invention in water at 25 ° C. is, for example, 0.01% with 2-ethylhexyl acrylate.
Wt%, 0.01 in 2-ethylhexyl methacrylate
% By weight, and 0.01% by weight in cyclohexyl methacrylate. The comparative monomers were styrene, 0.03% by weight, butyl acrylate, 0.32% by weight, and butyl methacrylate, 0.03% by weight.

The polymer latex used in the present invention may be copolymerized with other monomer compounds other than the above monomer compounds.
For example, acrylates, methacrylates, vinyl esters, olefins / styrenes / crotonates, itaconic diesters, maleic diesters, fumaric diesters, acrylamides, allyl compounds, vinyl ethers Examples thereof include monomer compounds selected from one or two or more selected from vinyl ketones, vinyl heterocyclic compounds, glycidyl esters, unsaturated nitriles, polyfunctional monomers, and various unsaturated acids.

More specifically, these acrylates include methyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, sec-butyl acrylate, tert-butyl acrylate, and the like. Amyl acrylate, hexyl acrylate, 2-chloroethyl acrylate, 2-bromoethyl acrylate, 4-
Chlorobutyl acrylate, cyanoethyl acrylate, 2-acetoxyethyl acrylate, dimethylaminoethyl acrylate, methoxybenzyl acrylate, 2-chlorocyclohexyl acrylate, furfuryl acrylate, tetrahydrofurfuryl acrylate, phenyl acrylate, 2-hydroxyethyl acrylate, 5-hydroxypentyl Acrylate, 2 ・
2-dimethyl-3-hydroxypropyl acrylate,
2-methoxyethyl acrylate, 3-methoxybutyl acrylate, 2-ethoxyethyl acrylate, 2-
iso-propoxy acrylate, 2-butoxyethyl acrylate, 2- (2-methoxyethoxy) ethyl acrylate, 2- (2-butoxyethoxy) ethyl acrylate, ω-methoxy polyethylene glycol acrylate (additional mole number n = 9), 2- Bromo-2-methoxyethyl acrylate, 1,1-dichloro-2-ethoxyethyl acrylate and the like can be mentioned. Examples of methacrylates include methyl methacrylate, gamma propyl methacrylate, isopropyl methacrylate,
Amyl methacrylate, chlorobenzyl methacrylate, sulfopropyl methacrylate, N-ethyl-N-
Phenylaminoethyl methacrylate, 2- (3-phenylpropyloxy) ethyl methacrylate, dimethylaminophenoxyethyl methacrylate, furfuryl methacrylate, tetrahydrofurfuryl methacrylate, phenyl methacrylate, cresyl methacrylate, naphthyl methacrylate, 2-hydroxyethyl methacrylate, 4- Hydroxybutyl methacrylate,
Triethylene glycol monomethacrylate, dipropylene glycol monomethacrylate, 2-methoxyethyl methacrylate, 3-methoxybutyl methacrylate, 2-acetoxyethyl methacrylate, 2-acetoacetoxyethyl methacrylate, 2-ethoxyethyl methacrylate, 2-iso-propoxyethyl methacrylate , 2-butoxyethyl methacrylate, 2-
(2-methoxyethoxy) ethyl methacrylate, 2-
(2-ethoxyethoxy) ethyl methacrylate, 2-
(2-butoxynitoxy) ethyl methacrylate, ω-
Examples include methoxypolyethylene glycol methacrylate (additional mole number n = 6), allyl methacrylate, dimethylaminoethyl methyl methacrylate methacrylate, and the like.

Examples of vinyl esters include vinyl acetate, vinyl propionate, vinyl butyrate,
Examples thereof include vinyl isobutyrate, vinyl caproate, vinyl chloroacetate, vinyl methoxy acetate, vinyl phenyl acetate, vinyl benzoate, and vinyl salicylate.

Examples of olefins include dicyclopentadiene, ethylene, propylene, 1-butyne,
-Penten, vinyl chloride, vinylidene chloride, isoprene, chloroprene, butadiene, 2,3-dimethylbutadiene and the like.

Examples of styrenes include styrene,
Methyl styrene, dimethyl styrene, trimethyl styrene, ethyl styrene, isopropyl styrene, chloromethyl styrene, methoxy styrene, acetoxy styrene, chloro styrene, dichloro styrene, bromo styrene, triple olo methyl styrene, methyl vinyl benzoate and the like can be mentioned.

Examples of crotonates include butyl crotonate and hexyl crotonate.

Examples of the diethyl itaconates include dimethyl itaconate, diethyl itaconate, and dibutyl itaconate.

The maleic acid diesters include, for example, diethyl maleate, dimethyl maleate, dibutyl maleate and the like.

As the fumaric acid diesters, for example,
Examples thereof include diethyl fumarate, dimethyl fumarate, and dibutyl fumarate.

Examples of acrylamides include acrylamide, methylacrylamide, tert-butylacrylamide, cyclohexylacrylamide, benzylacrylamide, hydroxymethylacrylamide, methoxyethylacrylamide, dimethylaminoethylacrylamide, phenylacrylamide, dimethylacrylamide, diethylacrylamide, β-cyanoethylacrylamide , N- (2-acetoacetoxyethyl) acrylamide and the like.

Methacrylamides such as methacrylamide, methyl methacrylamide, propyl methacrylamide, tert-butyl methacrylamide, cyclohexyl methacrylamide, benzyl methacrylamide,
Hydroxymethyl methacrylamide, methoxyethyl methacrylamide, dimethylaminoethyl methacrylamide, phenyl methacrylamide, dimethyl methacrylamide, diethyl methacrylamide, θ-cyanoethyl methacrylamide, N- (2-acetoacetoxyethyl)
Methacrylamide and the like.

Allyl compounds such as allyl acetate, allyl caproate, allyl laurate and allyl benzoate; vinyl ethers such as methyl vinyl ether, butyl vinyl ether and hexyl vinyl ether;
Methoxyethyl vinyl ether, dimethylaminoethyl vinyl ether and the like.

Vinyl ketones, for example, methyl vinyl ketone, phenyl vinyl ketone, methoxyethyl vinyl ketone and the like.

Glycidyl esters such as vinyl heterocyclic compounds such as vinylpyridine, N-vinylimidazole, N-vinyloxazolidone, N-vinyltriazole and N-vinylpyrrolidone, and unsaturated compounds such as glycidyl acrylate and glycidyl methacrylate. Nitriles, for example, acrylonitrile, methacrylonitrile, and other polyfunctional monomers, for example, divinylbenzene,
Methylene bisacrylamide, ethylene glycol dimethacrylate, etc.

Further, acrylic acid, methacrylic acid, itaconic acid, maleic acid, monoalkyl itaconate, for example,
Monomethyl itaconate, monobutyl itaconate, and the like, monoalkyl maleate, for example, monoethyl maleate, monobutyl maleate, and the like, citraconic acid, styrene sulfonic acid, vinyl benzyl sulfonic acid, vinyl sulfonic acid, aggryloyloxyalkyl sulfonic acid, for example, Methacryloyloxyalkyl sulfonic acids, such as acryloyloxymethyl sulfonic acid, aglyloyloxypropyl sulfonic acid, and the like, acrylamide alkyl sulfonic acid, such as methacryloyloxydimethyl sulfonic acid, methacryloyloxyethyl sulfonic acid, and methacryloyloxypropyl sulfonic acid; −
Methacrylamidoalkylsulfonic acids such as acrylamide, 2-methylethanesulfonic acid, 2-acrylamido-2-methylpropanesulfonic acid, and 2-acrylamido-2-methylbutanesulfonic acid, for example, 2-methacrylamido-2-methylethanesulfonic acid Acids, 2-methacrylamido-2-methylpropanesulfonic acid, 2-methacrylamido-2-methylbutanesulfonic acid, etc., aglyloyloxyalkyl phosphates, such as aglyloyloxyethyl phosphate, 3-agryloyloxypropyl-2- 3-allyloxy- having two hydrophilic groups such as methacryloyloxyalkyl phosphates such as phosphates, for example, methacryloyloxyethyl phosphate, 3-methacryloyloxypropyl-2-phosphate, etc. - such as hydroxy propanesulfonic acid naphthyl. These acids may be salts of alkali metal or ammonium ions.

Still other monomer compounds are described in US Pat. Nos. 3,459,790 and 3,438,708.
Nos. 3,554,987 and 4,215,195
No. 4,247,673, JP-A-57-20573.
A crosslinkable monomer described in the specification of JP-A-5 No. 5 can be used.

Specific examples of such a crosslinkable monomer include N- (2-acetoacetoxyethyl) acrylamide and N- ｛2- (2-acetoacetoxyethoxy).
Ethyl acrylamide and the like can be mentioned.

Of these monomer compounds, acrylic esters, methacrylic esters, vinyl esters, styrenes, and olefins are preferably used.

The surfactant used in the polymerization of the polymer latex of the present invention includes an anionic surfactant,
Any of a nonionic surfactant, a cationic surfactant, and an amphoteric surfactant can be used, but an anionic surfactant and / or a nonionic surfactant are preferable. As the anionic surfactant and the nonionic surfactant, various compounds known in the art can be used, and an anionic surfactant is particularly preferably used.

The water-soluble polymer used in the polymerization of the polymer latex of the present invention includes, for example, a synthetic polymer and a natural water-soluble polymer, and any of them can be preferably used in the present invention. Among them, synthetic water-soluble polymers include those having a nonionic group in the molecular structure, those having an anionic group, those having a cationic group, those having a nonionic group and an anionic group, those having a nonionic Examples include those having a group and a cationic group, those having an anionic group and a cationic group, and the like. Examples of the nonionic group include an ether group, an alkylene oxide group, a hydroxy group, an amide group, and an amino group. Examples of the anionic group include a carboxylic acid group or a salt thereof, a phosphoric acid group or a salt thereof, a sulfonic acid group or a salt thereof, and the like. Examples of the cationic group include a quaternary ammonium base and a tertiary amino group.

The natural water-soluble polymers also include those having a nonionic group in the molecular structure, those having an anionic group, those having a cationic group, those having a nonionic group and an anionic group, Examples include those having a nonionic group and a cationic group, those having an anionic group and a cationic group, and the like.

The water-soluble polymer used in the polymerization of the polymer latex of the present invention may be any of a synthetic water-soluble polymer and a natural water-soluble polymer having an anionic group, a nonionic group and an anionic group. Those having the following can be preferably used.

In the present invention, the water-soluble polymer is 2
It is sufficient to dissolve 0.05 g or more in 100 g of water at 0 ° C., and preferably 0.1 g or more.

As a natural water-soluble polymer, a comprehensive technical data collection of water-soluble polymer water-dispersed resin (Management Development Center)
Preferred are lignin, starch, pullulan, cellulose, dextran, dextrin, glycogen, alginic acid, gelatin, collagen, guar gum, gum arabic, laminaran, lichenin, nigran and the like and derivatives thereof. is there. As the derivative of the natural water-soluble polymer, sulfonated, carboxylated, phosphorylated, sulfoalkylated, carboxyalkylated, alkylphosphorylated, and salts thereof are preferably used. Particularly preferred are glucose, gelatin, dextran, cellulose and derivatives thereof.

The polymer latex used in the present invention can be easily produced by various methods. For example, there is a method of redispersing a polymer obtained by an emulsion polymerization method, a solution polymerization, a bulk polymerization, or the like.

In the emulsion polymerization method, water is used as a dispersing medium, and 10 to 50% by weight of the monomer and 0.0
Using 5 to 5% by weight of a polymerization initiator and 0.1 to 20% by weight of a dispersant, about 30 to 100 ° C, preferably 60 to 90 ° C.
For 3 to 8 hours with stirring.
The monomer concentration, initiator amount, reaction temperature, time, etc. are wide,
And can be easily changed.

Examples of the initiator include water-soluble peroxides (eg, potassium persulfate, ammonium persulfate, etc.) and water-soluble azo compounds (eg, 2,2′-azobis- (2-amidinopropane) -hydrochloride, etc.). Can be mentioned.

Examples of the dispersant include anionic surfactants, nonionic surfactants, cationic surfactants and amphoteric surfactants in addition to the water-soluble polymer. These may be used alone or in combination. Preferably, a combination of a water-soluble polymer and a nonionic or anionic activator is used.

In the solution polymerization, a mixture of monomers (usually 40% by weight or less, preferably 10 to 25% by weight, based on the solvent) of an appropriate concentration in a suitable solvent (eg, ethanol, methanol, water, etc.) is generally used. Mixture) with a polymerization initiator (eg, benzoyl peroxide, azobisisobutyronitrile,
The copolymerization reaction is carried out by heating to an appropriate temperature (for example, 40 to 120 ° C, preferably 50 to 100 ° C) in the presence of ammonium persulfate or the like. Thereafter, the reaction mixture is poured into a medium that does not dissolve the formed copolymer, the product is allowed to settle, and then the unreacted mixture is separated and removed by drying.

Next, the copolymer is dissolved in a solvent that dissolves but is insoluble in water (eg, ethyl acetate, butanol, etc.), and is vigorously dispersed in the presence of a dispersant (eg, a surfactant, a water-soluble polymer, etc.). Is distilled off to obtain a polymer latex.

The Tg (glass transition temperature) of the polymer constituting the polymer latex used in the present invention is preferably 60 ° C. or lower, particularly preferably 40 ° C. or lower.

The Tg of many polymers of the ethylenic monomers used in the present invention can be found in Brand Polymer, et al., "Polymer Handbook", pages III-139 to III-179 (1966) (Wiley & Sons). The Tg (° K) of the copolymer is represented by the following formula:

Tg (copolymer) = v ₁ Tg ₁ + v ₂ Tg ₂
+ ··· + v _W Tg _W However Ueshiki in v _1, v ₂ ··· v _W is Tg ₁ represents the weight fraction of the monomer in the copolymer, Tg ₂ ··· Tg _W each in the copolymer It represents the Tg (° K) of the homopolymer of the monomer.

Tg calculated according to the above equation is ± 5 ° C.
There is accuracy.

Regarding the method for synthesizing the polymer latex used in the present invention, US Pat.
Nos. 853,457, 3,411,911, 3,4
11,912, 4,197,127, Belgian Patents 688,882, 691,360, 712
No. 823, JP-B-45-5331, JP-A-60-18
No. 540, No. 51-130217, No. 58-1378
No. 31, No. 55-50240, and the like.

The average particle size of the polymer latex used in the present invention is preferably 0.5 to 300 nm, and any average particle size is particularly preferably 30 to 250 nm.

The particle size of the polymer latex used in the present invention can be determined by the electron micrograph described in “Chemistry of Polymer Latex” (Polymer Publishing Association, 1973),
It can be measured by a soap titration method, a light scattering method, or a centrifugal sedimentation method, but the light scattering method is preferably used. DLS700 (manufactured by Otsuka Electronics Co., Ltd.) was used as an apparatus for the light scattering method.

The molecular weight is not particularly limited, but is preferably 1,000 to 1,000,000, more preferably 2,000 to 500,000 in total molecular weight.

The polymer latex used in the present invention can be contained in the protective layer as it is or after being dispersed in water. The content of the polymer latex is preferably 5 to 70% by weight based on the binder of the protective layer.

Next, an example of a method for producing a polymer latex will be described, but the present invention is not limited to the following example.

(Production Method of Polymer Latex) Production Example 1 (Synthesis of Lx-1) A stirrer, a thermometer, a dropping funnel, a nitrogen inlet tube and a reflux condenser were applied to a 1,000 ml four-necked flask, and nitrogen gas was added. And 350 ml of distilled water was added while deoxidation was carried out, and the mixture was heated until the internal temperature reached 80 ° C. Sf-1 as a dispersant,
4.5 g are added, and 0.45 g of ammonium persulfate are further added as an initiator, and then 90 g of ethylhexyl acrylate are added dropwise using a dropping funnel over about 1 hour.
After the reaction is continued for 5 hours after the completion of the dropwise addition, unreacted monomers are removed by steam distillation. Thereafter, the mixture is cooled and adjusted to pH 6 with aqueous ammonia to obtain a polymer latex. Particle size is 1
It was 50 nm.

Production Example 2 (Synthesis of Lx-2) A stirrer, a thermometer, a dropping funnel, a nitrogen inlet tube and a reflux condenser were applied to a 1,000 ml four-necked flask, and nitrogen gas was introduced to perform deoxygenation. While adding 350 ml of distilled water, the mixture was heated until the internal temperature reached 80 ° C. 4.5 g of P-3 according to the present invention are added as a dispersing agent, 0.45 g of ammonium persulfate is further added as an initiator, and 90 g of ethylhexyl acrylate is added dropwise using a dropping funnel over about 1 hour. After the reaction is continued for 4 hours after the completion of the dropwise addition, unreacted monomers are removed by steam distillation. Thereafter, the mixture is cooled and adjusted to pH 6 with aqueous ammonia to obtain a polymer latex. The particle size was 200 nm.

Production Example 3 (Synthesis of Lx-10) 200 ml of dioxane was placed in a 500 ml three-necked flask.
And deoxygenated with nitrogen gas. Thereafter, 15 g of isononyl acrylate and 35 g of cyclohexyl acrylate
And 1.2 g of dimethyl azobisisobutyrate are further added as an initiator, and the reaction is continued at 60 ° C. for 6 hours. After completion of the reaction, the reaction solution was added to 3 l of distilled water with vigorous stirring.
White crystals are obtained. The white crystals are collected by filtration, dried, dissolved in 100 ml of ethyl acetate, added to 500 ml of distilled water to which 2 g of Sf-2 has been added while stirring vigorously, and then the ethyl acetate is removed to obtain a polymer latex. The particle size was 180 nm.

Production Example 4 (Synthesis of Comparative Latex L) To a liquid obtained by adding 0.25 kg of KMDS (dextran sulfate sodium salt) and 0.05 kg of ammonium persulfate to 40 liters of water at a liquid temperature of 81 ° C. Under a nitrogen atmosphere with stirring, n-butyl acrylate 4.5
1kg, styrene 5.49kg and acrylic acid 0.1k
g of the mixture was added over 1 hour, and then 0.005 kg of ammonium persulfate was added. After stirring for 1.5 hours, the mixture was cooled and adjusted to pH 6 with aqueous ammonia.

The obtained latex liquid was filtered through a GF / D filter manufactured by Whatman, and finished to 50.5 kg with water. Monodispersed latex (L) having an average particle size of 250 nm was used.
Was prepared.

Specific examples of the polymer latex according to the present invention and the dispersant used in the synthesis thereof are shown below. The suffix of the monomer unit indicates the content percentage of each. In the present invention, the amount of the polymer latex used is 10% or more and 300%
Or less, preferably 30% or more and 200% or less. If the amount of the polymer latex is too small, the effect of the present invention is not sufficiently exerted. If the amount of the polymer latex is too large, sufficient film strength cannot be obtained.

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[0112]

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The compound represented by formula (1) used in the silver halide photographic light-sensitive material of the present invention will be described.

In the general formula (1), among the substituents represented by R ₁ and R ₂ , an alkyl group is a group such as methyl, ethyl, hexyl, octyl and the like, and an aryl group is a phenyl group and the like. No. The alkoxy group represented by at least one of R ₁ and R ₂ includes methoxy,
Groups such as butoxy, hexyloxy, octoxy and the like, and the aryloxy groups include a phenoxy group.
These groups may be linear, branched or cyclic, and may be further substituted by other substituents. Further, a plurality of substituents may be bonded to each other to form a ring. X ₁ and X ₂
Examples of the halogen atom represented by include atoms such as fluorine, chlorine, and bromine.

Next, typical compounds represented by the general formula (1) according to the present invention will be described, but are not limited thereto.

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[0117]

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Next, the compound represented by formula (2) used in the silver halide photographic light-sensitive material of the present invention will be described.

In the compound represented by the general formula (2),
The alkyl group represented by R ₁₁ and R ₁₂ has 1 to 1 carbon atoms.
Eighteen are preferred, and they may be linear, branched, or cyclic. The alkoxy group has 1 to 18 carbon atoms
Are preferred, and may be linear, branched, or cyclic. The aryl group is preferably a phenyl group, and the aryloxy group is preferably a phenoxy group. These alkyl group, alkoxy group, aryl group and aryloxy group may be substituted by other substituents. At least one of R ₁₁ and R _12, it is particularly preferred that it include a 2-hydroxyphenyl group. The alkoxy group represented by R ₁₃ may be linear, branched, or cyclic. The alkoxy group and the aryloxy group represented by R ₁₃ may be substituted with another substituent.

Next, typical compounds represented by the general formula (2) according to the present invention will be exemplified, but not limited thereto.

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The compounds represented by formula (1) or (2) of the present invention include all of water-soluble compounds, oil-soluble compounds and latex compounds. As a method applied in the constituent layer, after dissolved in water or an organic solvent such as methanol, ethanol, acetone, dimethylacetone, dioxane, methyl ethyl ketone, acetonitrile, methyl acetate, ethyl acetate or a mixed solvent of water and the organic solvent Is added to the emulsion. In some cases, the following surfactant for dispersion may be used in combination.

When the compound of the present invention is oil-soluble,
The low-boiling organic solvent and the water-soluble and high-boiling organic solvent (for example, butyl phthalate, dioctyl phthalate, tricresyl phosphate, trihexyl phosphate,
Trioctyl phosphate, tricyclohexyl phosphate, triphenyl phosphate, dioctyl phenyl phosphate, hexyl oleate, dihexyl glutarate, butyl citrate, butyl myristate, butanediol dibenzoate, N, N-diethyl lauryl amide, behen Acid, octadecyl alcohol,
Chlorinated polyethylene), and a dispersing surfactant (anionic, nonionic, cationic or amphoteric surfactant such as sulfonic acid type, sulfate type, carboxylic acid type, malic acid type, boric acid type polyalkylene oxide) system,
Polyglycerin, carboxybetaine, sulfobetaine, ammonium, pyridinium, etc.) may be used for solubilization or emulsification and dispersion and then added to the emulsion.

The compound represented by formula (1) or (2) of the present invention is contained in the hydrophilic colloid layer farther from the support than the silver halide emulsion layer. The protective colloid layer includes a protective layer, an intermediate layer, a filter layer, and the like, and is particularly preferably contained in a protective layer farthest from the support. Without limitation on the addition amount is preferably 0.01 to 10 g / m ^2, more preferably from 0.05 to 2 g / m ^2.

The average particle size of the colloidal silica (colloidal silica) used in the silver halide photographic light-sensitive material of the present invention is preferably 3 nm to 1000 nm, and 5 nm to 50 nm.
0 nm is more preferred. The main component is silicon dioxide, and may contain alumina or sodium aluminate as a small component. Further, these colloidal silicas may contain, as a stabilizer, an inorganic base such as sodium hydroxide, potassium hydroxide, lithium hydroxide, or ammonia, or an organic base such as tetramethylammonium ion. These colloidal silicas are disclosed in
No. 112732, Japanese Patent Publication No. 57-9051, Japanese Patent Publication No. 5
No. 7-51653. Specific examples of the colloidal silica include Snowtex 20 (SiO ₂ / N
a ₂ O ≧ 57), Snowtex 30 (SiO ₂ / Na ₂₎
O ≧ 50), Snowtex C (SiO ₂ / Na ₂ O ≧ 1)
00), Snowtex O (SiO ₂ / Na ₂ O ≧ 50)
0) and the like which are commercially available from Nissan Chemical. Here, SiO ₂ / Na ₂ O is the content ratio by weight of silicon dioxide (SiO ₂ ) to sodium hydroxide in terms of sodium hydroxide converted to Na ₂ O, and is a value described in a catalog. It is. The amount of colloidal silica to be added is preferably from 0.01 to 1.0, more preferably from 0.05 to 0.7, by weight ratio to gelatin in the hydrophilic colloid layer containing the silver halide emulsion.

The fluorinated anionic surfactant and fluorinated cationic surfactant used in the present invention will be described.

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.

[0128] Formula [F2] Rf'-L-X ⁺ Z ^- wherein, Rf 'represents a hydrocarbon group having 1 to 20 carbon atoms, 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-based 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 d1) - or -SO ₂ N (R _d1) - represents a composed combine at least one divalent group having 1 to 12 carbon atoms. R _d1 represents an alkyl group having 1 to 5 carbon atoms, 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.

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Next, the fluorinated cationic activator used in the present invention will be described.

In the 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. -C example as _{Rf 'k F k + 1 (} k = 1~20, particularly 3 to 12 is _{preferred), - C m F 2m,} -C m F 2m-1 (m = 2~20, especially 3
To 12 are preferable).

Examples of L include —SO ₂ N (R ¹ ) (CH
_{2) p -, - CON (} R 1) (CH 2) p -, - OSO 2 N
(R ¹ ) (CH ₂ ) _p- , -OCON (R ¹ ) (CH ₂ )
_{p -, - O (CH 2} ) p -, - O (CH 2) p -, - O (C
_{H 2 CH 2 O) q (} CH 2) p -, - O (CH 2) p -, - N
(R ¹ ) (CH ₂ ) _p —, —SO ₂ N (R ¹ ) (CH ₂ ) _p O
_{(CH 2) r -, -} CON (R 1) (CH 2) p O (CH 2)
_{r -, - OSO 2 N (} R 1) (CHR 1) p O -, - (C
_{H 2) p (CHOH) s} (CH 2) r - , and the like.

Examples of X include -N ⁺ (R ¹ ) ₃ , -N
_{^{+ (CH 2 CH 2 OCH 3}} ) 3, -N + C 4 H 8 O (R 1), -
^{N + (R 1) (R} 2) (CH 2 CH 2 OCH 3), - N + C 5 H
₅ , -N ⁺ (R ¹ ) (R ² ) (CH ₂ ) _p C ₆ H ₅ , -N
⁺ (R ¹ ) (R ² ) _{2 and the} like. Where R ¹
And R ² each represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms (which may have a substituent), and p, r and s
Are each 0 to 6 and q is 1 to 20.

[0141] 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.

The following are specific examples of the fluorine-based cation activator preferably used in the present invention, but the present invention is not limited to these.

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In the present invention, particularly poorly 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 agitation for 24 hours and standing at 23 ° C. for 24 hours, a precipitate is formed, or when a floating substance is observed, it 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. Org. Chem.), Vol. 30, p. 3524 (196).
5 years).

Certain of these fluorine-based activators are available from Dainippon Ink and Chemicals, Inc.
gafac) F under the trade name Minnesota Mining
And Manufacturing Company under the trade name Fluorad FC, Imperial Chemical Industries 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 fluorine-based cation activator and the fluorine-based anion-activator used in the present invention is preferably from 0.1 to 1000 mg / m ² , more preferably from 0.5 to 3 mg / m ^2.
00 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 fluorinated anionic activator to the fluorinated cation activator of the present invention is 1: 10-1.
0: 1 is preferable, and 3: 7 to 7: 3 is more preferable.

Next, a fluorine-containing betaine activator and a fluorine-containing nonionic activator which can be used in the present invention are 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.

When used together, two or more of them may be used in combination. Further, other fluorine-based nonionic activators, fluorine-based betaine activators, and hydrocarbon-based activators may be used in combination.

Next, the polyalkylene oxide-based 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).

[0154] In the general formula _{(3) R 31 -A- (B} ) n-R expression, R represents a hydrogen atom, an alkyl group (e.g. methyl group having 1 to 4 carbon atoms, an ethyl group, a hydroxyethyl group, an isopropyl group, ), An alkylcarbonyl group having 1 to 5 carbon atoms (eg, acetyl group, chloroacetyl group, carboxymethylcarbonyl group, etc.).

R ₃₁ represents a substituted or unsubstituted alkyl group, alkenyl group or aryl group having 1 to 30 carbon atoms.

A represents -O-, -S-, -COO-, -N
_{(R 32) -, - CO} -N (R 32) -, - SO 2 -N (R
₃₂ )-, wherein R ₃₂ 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, and is a natural number of 2 to 50.

Next, compounds having a polyoxyalkylene group preferably used in the present invention will be exemplified.

3-1 C ₈ H ₁₇ O (CH ₂ CH ₂ O) ₇ H 3-2 C ₁₁ H ₂₃ O (CH ₂ CH ₂ O) ₈ H 3-3 C ₁₂ H ₂₅ O (CH ₂ CH _{2 O) 10 H 3-4 C 16 H} 33 O (CH 2 CH 2 O) 12 H 3-5 C 20 H 41 O (CH 2 CH 2 O) 20 H 3-6 C 18 H 37 O (CH 2 CH (OH) CH ₂ O)
_{2 (CH 2 CH 2 O)} 10 H 3-7 C 16 H 33 O (CH 2 CH 2 O) 4 (CH 2 CH (O
_{H) CH 2 O) 2 (} CH 2 CH 2 O) 4 H 3-8 C 11 H 23 COO (CH 2 CH 2 O) 8 H 3-9 C 15 H 31 COO (CH 2 CH 2 O) 13 H _{3-10 C 16 H 33 COO (CH} 2 CH 2 O) 15 H 3-11 C 18 H 35 COO (CH 2 CH 2 O) 15 H 3-12 C 12 H 25 S (CH 2 CH 2 O) 15 H

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The addition amount of the nonionic activator having a polyoxyalkylene group according to the present invention is 1 to 500 mg /
m ² is preferred, and more preferably ⁵ to 250 mg / m ² .

The matte degree of the silver halide photographic light-sensitive material of the present invention is 50 to 300 mmHg (0.70 to 4.0 mmHg).
× 10 ³ Pa), but preferably 150 to 250 m
mHg (2.0 to 3.33 × 10 ³ Pa). In the present specification, the term "mat degree" refers to a value obtained by expressing the amount of air inflow that varies depending on the smoothness (mat degree) of the film surface as a change in pressure using a vacuum air micrometer. This is a numerical value expressed in mmHg by measuring the suction pressure of an unexposed photosensitive material (so-called raw film) that has been conditioned for 3 hours under the condition of% RH and under the same conditions. The larger the value, the higher the matte degree. In the examples described below, the suction pressure was measured using a smoother (manufactured by Toei Electronics Co., Ltd.). The polymer particles in the present invention are preferably contained in the outermost surface layer of the photosensitive material or a layer functioning as the outermost surface layer, or a layer close to the outer surface, and are contained in a layer acting as a so-called protective layer. Preferably. The content of the polymer particles is preferably from 50 to 600 mg / 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. Further, two or more layers may contain the same or different kinds of polymer particles. In this case, the layer to which the polymer particles are added may be any of an emulsion layer, a protective layer, an undercoat layer and an intermediate layer provided as necessary. But it is good.

The silver halide grains used in the present invention may be in 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 of the area-converted particle diameter to the particle thickness (aspect ratio = equivalent 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 from 0.1 to 10.0 μm, more preferably from 0.2 to 5.0 μm, and particularly preferably from 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 / average value of volume-converted particle size) Similarly, from the above measurement, the variation coefficient of the area-converted particle size of silver halide grains can be determined. it can. 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 grain size = (standard deviation of area-converted grain size / average value of area-converted grain size) The silver halide emulsion related to the present invention is a silver halide emulsion contained in the silver halide emulsion. 50% of the total projected area of the grain
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 related to the present invention.

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, but 50% of the tabular silver halide grains related to the present invention. 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. In particular, the average silver iodide content of the silver halide emulsion is preferably 2 mol% or less, and silver iodobromide is preferred.
Further, the average silver iodide content is preferably at most 1 mol%, particularly preferably at most 0.5 mol%. 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 silver halide grains for photography are microcrystals composed of silver chloride, silver bromide, silver iodide or a solid solution thereof, and two or more phases having different silver halide compositions are contained in the crystal. 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. Adding method, adding only solution containing iodide ion,
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 times or less. Specifically, the value of the average interparticle distance at the time of dislocation line introduction is preferably controlled to 3.2 μm or less, more preferably 2.8 μm or less, and controlled to 0.90 μm or more and 2.0 μm or less. It is particularly preferred to do so.

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 at least any one of the layer containing the photosensitive silver halide emulsion of the present invention and the constituent layers other than the emulsion layer contains a dye capable of decoloring and / or flowing out during development processing, A photosensitive material having high sensitivity, 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. Dyes used in the light-sensitive material of the present invention,
It is substantially insoluble in water at a pH of 7 or less, is at a pH of 8 or more, and is substantially water-soluble. The amount added can be varied depending on the sharpness goal. Preferably 0.2 mg /
m ² ~20mg / m ^2, more preferably 0.8 mg / m ²
１５15 mg / 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 support 28 XVII 1009 XVII Supports that can be used in the light-sensitive material of the present invention As the body, for example, the aforementioned RD-17643, page 28 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.

When the silver halide emulsion layer and the crossover cut layer are provided on both sides of the support of the photographic light-sensitive material of the present invention, a light-sensitive material having high sensitivity, high sharpness and excellent processability can be obtained.

The amount of gelatin in the silver halide emulsion layer, the surface protective layer and the other layers is from 0.5 to 0.5 in total on one side of the support.
It is preferably in the range of 3.5 g / m ² , especially 1.
The range of 0 to 3.0 g / m ² is preferred.

Preferred developers 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 preservatives may include sulfites, for example, potassium sulfite, sodium sulfite, reductones, for example, piperidinohexose redatonone,
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 aid may contain diethylene glycol, triethylene glycols and esters thereof, and the sensitizer may contain, for example, a development accelerator such as a quaternary ammonium salt, a surfactant and the like.

The silver sludge inhibitor is disclosed in JP-A-56-1981.
No. 106244, silver stain inhibitor, JP-A-3-518
The sulfides and disulfide compounds described in JP-A No. 44, and the cysteine derivatives or triazine compounds described in JP-A-5-289255 are preferably used.

As organic inhibitors, azole organic antifoggants such as indazole, imidazole, benzimidazole, triazole, benztriazole, tetrazole, thiadiazole and 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," Published by Focal Press (19
66), pages 226-229, U.S. Pat.
No. 15,2,592,364, JP-A-48-649
No. 33 may be used. As a chelating agent for concealing calcium ions mixed in tap water used for the treatment liquid, JP-A-Hei.
The chelate stabilization constant with iron described in US Pat.
The above chelating agents are preferably used. 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 preferably 50 to 150 ml, more preferably 65 to 130 ml, per m ² of the light-sensitive material.

Preferred fixing solutions may 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 form an acidic hardening film. 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, potassium alum and the like.

The fixing solution may further contain a preservative such as phosphite and bisulfite, a pH buffer such as acetic acid and boric acid, a mineral acid (sulfuric acid, nitric acid) and an organic acid (citric acid, citric acid, etc.), if desired. Various acids such as oxalic acid and malic acid), hydrochloric acid and the like, pH adjusters such as metal hydroxides (potassium hydroxide and sodium hydroxide), and chelating agents having a softening property of hard water 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, more preferably 65 to 130 ml, per m ² of the light-sensitive material.

As the treatment method of the present invention, a method using a solid treating agent is preferable. 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 of granulating a powdery solid processing agent and then performing 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.

[0208] Granulation methods for tablet formation include known methods such as tumbling granulation, extrusion granulation, compression granulation, pulverization granulation, stirring granulation, fluidized bed granulation, and spray drying granulation. Can be done.
For tablet formation, the average particle size of the obtained granulated product is 100 to 800 μm in that, when the granulated product is mixed and compressed under pressure, the components become non-uniform, so-called segregation is unlikely to occur.
It is preferred to use
７750 μm. Furthermore, the particle size distribution is
Preferably, 0% or more is within a deviation of ± 100 to 150 μm. 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 the tablet processing agent is described in, for example, 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.

[0211] 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 when the tip of the photosensitive material to be processed is immersed in the developing tank liquid of the automatic developing machine to 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 contact with the washing tank liquid (stabilizing liquid)
When the immersion time in the rinsing tank liquid is referred to as “rinsing time” and the time in the drying zone of the automatic processor 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.

[0213]

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 in 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 using 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 9.92 g H ₂ O 12938.0 ml (S-101) Silver nitrate 50.43 g H ₂ O 225.9 ml (X- 101) 35.33 g of potassium bromide 224.7 ml of H ₂ O [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 at 20 ° C. for 20 minutes. 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) (Compound A) 10% by weight methanol solution 4.64 ml H ₂ O 3266.0 ml [Grain growth step-1] After completion of the ripening, the S-102 solution was subsequently obtained by using a double jet method. And X-102 solution while accelerating the flow rate (the ratio of the addition flow rate at the end to the addition at the start is about 12 times)
Added in 38 minutes. After completion of the addition, the G-102 solution was added, the stirring speed was adjusted to 550 rpm, and then the S-103 solution and the X-103 solution were 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 639.8 g H ₂ O 2866.2 ml (X-102) Potassium bromide 448.3 g H ₂ O 2850.7 ml (G-102) Alkali-treated inert gelatin (average molecular weight 100,000) ) 203.4 g the 10 wt% methanol [compound a] solution _{6.20ml H 2 O 1867.0ml (S-} 103) Silver nitrate _{989.8g H 2 O 1437.2ml (X-} 103) potassium bromide 679.6g Potassium iodide 19.35 g H ₂ O 1412.0 ml [Grain growth step-2] After completion of the addition, the temperature of the solution in the reaction vessel was lowered to 40 ° C. over 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).

(S-104) Silver nitrate 672.0 g H ₂ O 975.8 ml (X-104) Potassium bromide 470.8 g H ₂ O 959.4 ml The entire area of the particle growing step-1 and the particle growing step-2 was 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) Gelatin 3
2000 ml of an aqueous solution containing 5 g was kept at 40 ° C. and stirred. After adjusting the silver potential to −150 mV with respect to the saturated calomel electrode using an aqueous KI solution, AgNO ₃ (178
g) The aqueous solution and the KI (174 g) aqueous solution were added over 13 minutes while accelerating the flow rate by the double jet method. After desalting, gelatin was added, pH 6.8 at 50 ° C., pAg
Adjusted to 9. 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 to disperse 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.

Then, the above emulsion was heated to 60 ° C., and 10 minutes after the addition of the spectral sensitizing dye (the following compound and amount) as a dispersion of solid fine particles, adenine, ammonium thiocyanate, chloroauric acid And a dispersion of triphenylphosphine selenide and a mixed solution of sodium thiosulfate and triphenylphosphine selenide were further added. After 30 minutes, silver iodide fine grain emulsion a was added, and ripening was performed 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 anhydride 100 mg adenine 10 mg ammonium thiocyanate 90 mg chloroauric acid 20 mg sodium thiosulfate 2.0 mg triphenylphosphine selenide 0. 2 mg silver iodide fine grain emulsion a Equivalent to 0.3 mmol 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 was previously
It was obtained by adding to water adjusted to ° C. and stirring at 3,500 rpm with high speed stirring (dissolver) for 30 to 120 minutes.

A 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.
Stir to dissolve completely. On the other hand, photographic gelatin 3.8k
g was dissolved in 38 kg of pure water, and 93 g of a 25% by mass aqueous solution of sodium dodecylbenzenesulfonate was added thereto. Next, these two liquids were mixed and dispersed by a high-speed stirring type disperser having a dissolver having a diameter of 10 cm at 50 ° C. at a peripheral speed of 40 m / sec for 30 minutes. Then, immediately under reduced pressure, the residual concentration of ethyl acetate was reduced to 0.3.
Ethyl acetate was removed while stirring until the amount became equal to or less than mass%. Then, this dispersion is diluted with pure water to 80 kg.
Finished. 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 of the above-obtained emulsions (per mole of silver halide).

1,1-Dimethylol-1-bromo-1-nitromethane 7 mg t-butyl-catechol 130 mg polyvinylpyrrolidone (molecular weight 10,000) 1.0 g sodium polystyrenesulfonate 2.0 g trimethylolpropane 7.0 g nitrophenyl- Triphenyl-phosphonium chloride 20 mg Sodium 1,3-dihydroxybenzene-4-sulfonate 400 mg 2-Sodium 2-mercaptobenzimidazole-5-sulfonate 10 mg nC ₄ H ₉ OCH ₂ CH (OH) CH ₂ N (CH ₂ COOH ₂ ) 600 mg (Preparation of coating solution for protective layer) Gelatin 0.8 g / m ² Polymer particles of the present invention (particles described in Tables 1 to 4) Adjusted to an amount that gives a matte degree of Tables 1 to 4 Hardening agent (CH _{2 = CHSO 2 CH 2 CONHCH 2 -} ) 2 swelling There amount adjusting compound added to a 150% (S-1) 7mg / m 2 nonionic activator (Compound 3-16) The amount general formula shown polymer latex Table 1-4 50 mg / m ² the present invention ( 1) or (2) compound (exemplary compound) Amount shown in Tables 1 to 4 Colloidal silica Amount shown in Tables 1 to 4 Fluorine anion activator of the present invention (exemplary compound) Amount shown in Tables 1 to 4 Fluorinated cationic activator (exemplary compound) Amount shown in Tables 1 to 4 The amount of the material applied was 1 m ² per side, and the amount of silver applied was adjusted to 1.6 g / m ² per side.

(Preparation of Filter Layer) Glycidyl methacrylate 50% by mass, methyl acrylate 10% by mass,
A copolymer dispersion liquid obtained by diluting a copolymer comprising three kinds of monomers of 40% by mass of butyl methacrylate to 10% by mass was applied as a subbing liquid to a thickness of 17%.
On both sides of a blue colored polyethylene terephthalate support of 5 [mu] m, 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 dispersion dye (AH) 50 mg Gelatin 0.2 g Sodium dodecylbenzenesulfonate 2 mg Compound (I) 5 mg Colloidal silica (average particle diameter 0.014 μm) 10 mg Potassium polystyrene sulfonate 50 mg

[0232]

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 1.6 g / m ² per side. Simultaneous application on both sides of body sample for 2 minutes 2
It dried in 0 second and the application sample was produced.

<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 stirred 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 product (B)] Potassium carbonate 9500
g and 6.0 g of potassium iodide are each pulverized in a commercially available bantam mill to an average of 10 μm. These fine powder, DTPA-Na 170 g, sodium sulfite 425
g, 5-mercapto- (1H) -tetrazolylacetic acid Na
8.3 g salt, 40 g 1- (3-sulfophenyl) -5-tetrazole-Na salt, binder mannitol 1500
g and 600 g of D-Sorbit 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. After drying at 40 ° C. for 2 hours, the water content of the granules is almost completely removed.

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%
C., and added and mixed in a room conditioned at 40% RH or less. Further, for the granulated product (B), 1.2% of the total weight of sodium 1-octanesulfonate and methyl-β-cyclodextrin of the total weight were added. In a room conditioned at 25 ° C. and 40% RH or less, and mixed with Kikusui Seisakusho's Tough Press Collect 1
527HU was subjected to compression tableting using a modified tableting machine 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.
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 Material (C)] In a commercially available bantam mill, 14580 g of ammonium thiosulfate / sodium thiosulfate (90/10 weight ratio) 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
20 g, 5-mercapto-tetrazole 50 g, binder pine flow 900 g were added, mixed in a commercially available stirring granulator at room temperature for about 3 minutes, and granulated by adding 150 ml of water over 1 minute. The granules are dried at 40 ° C. in a fluidized bed drier to remove water almost completely.

[Granulated product (D)] Boric acid 250 g, aluminum sulfate octahydrate 1500 g, succinic acid 1150 g, tartaric acid 2
50g, Mannit 208g, D-Sorbit 100g
, And mixed at room temperature for about 3 minutes in a commercially available stirring granulator, and granulated 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.

The granulated product (C) thus obtained, 1400 g of sodium acetate and 2.5% of the total weight of sodium 1-hexanesulfonate were mixed in a room conditioned at 25 ° C. and 40% RH or less. Then, 1400 g of sodium acetate was added to the granulated product (D), and sodium 1-hexanesulfonate was further added to 3.0% of the total weight at 25 ° C and 40%.
The mixture was added and mixed in a room humidified to RH or less, and compression tableting was performed using a tableting machine modified from Tough Press Collect 1527HU manufactured by Kikusui Seisakusho Co., Ltd. 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 Finished with pure water 67 ml As an automatic developing machine, TCX-701 (manufactured by Konica Corporation) was used. 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. 5.6 liters of a fixing solution prepared in the same manner was used in TCX-70.
No. 1 was used as a start solution in the fixing processing tank.

In each of the developing and fixing steps, each of the packaging bags was opened by hand at the inlet of each solid agent, and the tablets were dropped into the built-in chemical mixer.
(0 ° C.) and dissolving with stirring for 25 minutes while dissolving with stirring.
Adjust to 0 liters. This was used as a developing and fixing replenisher.

The pH when the developing solution was dissolved was 10.15,
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 so that the replenisher is supplied so that the replenisher does not enter a 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 ), fixing temperature 35 ° C. (replenishment rate 100 ml / m ² ), water 18 ° C. (replenishment rate 5 liter / min), drying temperature 55
The evaluation was performed at 30 ° C. for 30 seconds.

<Evaluation of Sensitometry> The prepared sample was sandwiched between two fluorescent intensifying screens XG-S (manufactured by Konica Corporation), and X was measured under the conditions of a tube voltage of 90 kVp, a current of 100 mA and a time of 0.05 second. After irradiating with light and developing, a sensitometric curve was prepared by a distance method, and sensitivity and fog were determined. 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.

<Evaluation of scratch resistance> The unexposed sample film was allowed to stand at 23 ° C and a relative humidity of 40% for 2 hours.
Under the same conditions, 100 g / c using a commercially available nylon scourer
After rubbing with a load of m ² , processing was performed with an automatic developing machine under the above conditions, and the evaluation was made by visual observation.

A: Almost no scratch B: Level that has no practical problem, but some scratches C: Scratch occurs to the extent of being noticeable and is a practical problem D: Very large 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 automatic 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.

[0250]

[Table 1]

[0251]

[Table 2]

[0252]

[Table 3]

[0253]

[Table 4]

[0254]

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 Valve for fine grain addition

Claims (14)

[Claims] 1. A silver halide photographic light-sensitive material comprising at least one silver halide emulsion layer on both sides of a support and a non-light-sensitive colloid layer above the silver halide emulsion layer. In the photosensitive colloid layer, spherical polymer particles having an average particle diameter of 1 to 10 μm and a relative standard deviation of 10% or less, and at least one kind of single particles having a solubility in water at 25 ° C. of 0.025% by weight or less are used. A silver halide photographic material comprising a polymer latex having a monomer as a monomer unit. 2. A silver halide photographic light-sensitive material comprising, on both sides of a support, at least one silver halide emulsion layer and a non-light-sensitive colloid layer above the silver halide emulsion layer. The photosensitive colloid layer contains at least one of spherical polymer particles having an average particle diameter of 1 to 10 μm and a relative standard deviation of 10% or less and a compound represented by the following general formula (1). Characteristic silver halide photographic material. Embedded image [Wherein, R ₁ and R ₂ each represent a substituent. Where R ₁
And at least one of R ₂ represents an alkoxy group or an aryloxy group. X ₁ and X ₂ each represent a halogen atom. m, n, p and q each represent an integer of 0-4. However, the sum of m and n and the sum of p and q are each an integer of 0 to 4, and both m and n are not 0. Also, m, n,
When p or q is 2 or more, a plurality of R ₁ , R ₂ , X ₁ or X ₂
May be the same or different. ] 3. A silver halide photographic light-sensitive material comprising at least one silver halide emulsion layer on each side of a support and a non-light-sensitive colloid layer above the silver halide emulsion layer. The photosensitive colloid layer contains at least one of spherical polymer particles having an average particle diameter of 1 to 10 μm and a relative standard deviation of 10% or less and a compound represented by the following general formula (2). Characteristic silver halide photographic material. Embedded image Wherein R ₁₁ and R ₁₂ each represent an alkyl group, an aryl group,
R ₁₃ represents an alkoxy group or an aryloxy group, and R ₁₃ represents an alkoxy group or an aryloxy group. ] 4. A silver halide photographic material having at least one silver halide emulsion layer on each side of a support and a non-photosensitive colloid layer above the silver halide emulsion layer. The photosensitive colloid layer comprises a spherical polymer particle having an average particle diameter of 1 to 10 μm and a relative standard deviation of 10% or less, and a colloidal silica having an average particle diameter of 100 nm or less. Silver photographic photosensitive material. 5. A silver halide photographic light-sensitive material comprising at least one silver halide emulsion layer on each side of a support and a non-light-sensitive colloid layer above the silver halide emulsion layer. The photosensitive colloid layer contains spherical polymer particles having an average particle diameter of 1 to 10 μm and a relative standard deviation of 10% or less, a fluorinated cationic surfactant, and a fluorinated anionic surfactant. Silver halide photographic light-sensitive material. 6. A silver halide photographic light-sensitive material comprising at least one silver halide emulsion layer on each side of a support and a non-light-sensitive colloid layer above the silver halide emulsion layer. In the photosensitive colloid layer, at least one kind of polymer particles having an average particle diameter of 1 to 10 μm, containing 5 to 15 mol% of an acidic monomer, and having a solubility in water at 25 ° C. of 0.025 wt% or less is used A silver halide photographic material comprising a polymer latex having a monomer as a monomer unit. 7. A silver halide photographic material comprising at least one silver halide emulsion layer on each side of a support and a non-light-sensitive colloid layer above the silver halide emulsion layer. The photosensitive colloid layer contains at least one kind of polymer particles having an average particle diameter of 1 to 10 μm, containing 5 to 15 mol% of an acidic monomer, and a compound represented by the general formula (1). Characteristic silver halide photographic material. 8. A silver halide photographic light-sensitive material comprising at least one silver halide emulsion layer on each side of a support and a non-light-sensitive colloid layer above the silver halide emulsion layer. The photosensitive colloid layer contains at least one kind of polymer particles having an average particle size of 1 to 10 μm, containing 5 to 15 mol% of an acidic monomer, and a compound represented by the general formula (2). Characteristic silver halide photographic material. 9. A silver halide photographic material having at least one silver halide emulsion layer on both sides of a support and a non-photosensitive colloid layer above the silver halide emulsion layer. The photosensitive colloid layer has an average particle diameter of 1 to 10 μm, and contains polymer particles containing 5 to 15 mol% of an acidic monomer, a fluorinated cationic surfactant and a fluorinated anionic surfactant. Silver halide photographic light-sensitive material. 10. The silver halide according to claim 1, which contains at least one of the compounds represented by the general formulas (1) and / or (2). Photosensitive material. 11. The matte degree is 150 to 250 mmHg.
(2.0 to 3.3 × 10 ³ Pa). The silver halide photographic light-sensitive material according to claim 1, wherein 12. The silver halide photographic light-sensitive material according to claim 1, further comprising a polyalkylene oxide-based nonionic surfactant. 13. A silver halide photographic light-sensitive material, wherein the spherical polymer particles according to claim 1 contain a crosslinkable monomer as a monomer unit. 14. A silver halide photographic light-sensitive material, wherein the spherical polymer particles according to claim 1 are synthesized by a seed polymerization method.