JP3191192B2 - Silver halide photographic materials - Google Patents

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 capable of improving the abrasion resistance of a film and the drying property during rapid processing, and obtaining a cold black tone without the developed silver having a yellow tint. About.

[0002]

2. Description of the Related Art In recent years, in the field of X-ray photographic light-sensitive materials, rapid processing at a high temperature has rapidly progressed, and the processing time has been greatly reduced. Elemental techniques for rapid processing include, for example, improvement in the developability and fixability of silver halide photographic materials and the drying property of drying in a short time after washing with water. On the other hand, in photographic light-sensitive materials, an improvement in covering power is indispensable for the purpose of reducing the amount of silver required for obtaining a certain optical density and improving sensitivity and developability. Many techniques have been proposed to obtain high covering power in X-ray photographic light-sensitive materials. For example, JP-A-61-116347 and JP-A-57-182732 in which the amount of gelatin in the light-sensitive material constituting layer is reduced. Or using polymers such as polyacrylamide, for example, US Pat.
No. 1,158 is disclosed.

In recent years, it is well known among those skilled in the art that the use of tabular silver halide grains can enhance the color sensitizing efficiency and covering power and improve the sharpness. For tabular grains, see, for example, JP-A-58-1
Nos. 13926, 58-113927 and 58-113928 disclose tabular grains having an aspect ratio of 8 or more.

[0004] However, each of the above-mentioned techniques has serious disadvantages. For example, when the amount of gelatin as a binder component is reduced, the silver / gelatin ratio becomes high, and scratches and fog are easily generated during handling and transport of the film. In addition, the use of polymers causes problems such as slow drying.

[0005] In addition, any of these techniques is that the color tone of the developed silver is yellowish.

For a direct observer of a silver image in a medical photographic light-sensitive material, a cool black tone silver image is preferable, and the yellow tint is disliked because it gives an unpleasant feeling.

Conventionally, as measures against abrasion, for example, JP-A-64-29834 using a water-soluble polyester in a layer, JP-A-62-21143 using a polyhydroxybenzene, or an adsorbing group to silver halide JP-A-4-177336 using a specific organic compound having However, these techniques are not only insufficient in prevention of abrasion fog but also unfavorable in terms of silver tone.

[0008]

SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to provide a silver halide photographic light-sensitive material having less scratches and high covering power. Furthermore,
A second object of the present invention is to provide a high-sensitivity, high-coverage silver halide photographic material in which the image after development processing is improved to a black tone.

[0009]

The object of the present invention is to provide a silver halide photographic material having at least one photosensitive silver halide emulsion layer on a support, wherein the silver halide emulsion layer and / or The other layer contains at least one polymer latex having a monomer unit of at least one monomer having a solubility in water at 25 ° C. of 0.025% by weight or less, and At least one of the silver halide emulsions contained in the material is
This is achieved by a silver halide photographic light-sensitive material comprising silver halide grains coagulated with a polymer coagulant at least once during its production.

The above-mentioned monomer is preferably an acrylate compound, particularly preferably when both an acrylate compound and a methacrylate compound are used. The particle size of the polymer latex of the present invention is preferably 300 nm or less.

The polymer latex of the present invention is preferably polymerized in the presence of a water-soluble polymer and / or a surfactant.

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, preferably 0.015% by weight or less. Such ethylenic monomers include, for example, hexyl acrylate, 2
-Acrylates such as ethylhexyl acrylate, octyl acrylate, tert-octyl acrylate, nonyl acrylate, iso-nonyl acrylate, cyclohexyl acrylate, n-stearyl acrylate, lauryl acrylate, tridecyl acrylate, butyl methacrylate, iso-butyl methacrylate, tert -Butyl methacrylate, hexyl methacrylate, 2-ethylhexyl methacrylate, octyl methacrylate, iso-octyl methacrylate, tert-octyl methacrylate, nonyl methacrylate, iso-nonyl methacrylate, cyclohexyl methacrylate, n-stearyl methacrylate, lauryl Examples include methacrylates such as methacrylate and tridecyl methacrylate, 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% by weight for 2-ethylhexyl acrylate, 0.01% by weight for 2-ethylhexyl methacrylate, and 0.01% by weight for cyclohexyl methacrylate. The comparative monomer was 0.03% by weight for styrene, 0.32% by weight for butyl acrylate, and 0.03% by weight for butyl methacrylate.

The polymer latex used in the present invention may be copolymerized with other monomer compounds other than the above monomer compounds.
For example, acrylic esters, methacrylic esters, vinyl esters, olefins, styrenes, crotonic esters, 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 monomeric compounds are exemplified by methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, and sec-butyl acrylate. , Tert-butyl acrylate, 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-
Examples include methoxypolyethylene glycol acrylate (additional mole number n = 9), 1-bromo-2-methoxyethyl acrylate, 1,1-dichloro-2-ethoxyethyl acrylate, and the like.

Examples of the methacrylates include methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, amyl methacrylate, chlorobenzyl methacrylate, sulfopropyl methacrylate, N-ethyl-N-phenylaminoethyl methacrylate, (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-butoxyethoxy) ethyl methacrylate, ω-methoxy polyethylene glycol methacrylate (additional mole number n =
6), allyl methacrylate, dimethylaminoethyl methyl methacrylate chloride salt 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-butene, 1-pentene, vinyl chloride, vinylidene chloride, isoprene, chloroprene, butadiene, and 2,3-dimethylbutadiene. it can.

As the styrenes, for example, styrene,
Examples include methylstyrene, dimethylstyrene, trimethylstyrene, ethylstyrene, isopropylstyrene, chloromethylstyrene, methoxystyrene, acetoxystyrene, chlorostyrene, dichlorostyrene, bromostyrene, trifluoromethylstyrene, and methyl vinyl benzoate.

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

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.

The acrylamides include acrylamide, methyl acrylamide, ethyl acrylamide, propyl acrylamide, butyl acrylamide, tert-
Butylacrylamide, cyclohexylacrylamide, benzylacrylamide, hydroxymethylacrylamide, methoxyethylacrylamide, dimethylaminoethylacrylamide, phenylacrylamide,
Dimethyl acrylamide, diethyl acrylamide, β
-Cyanoethylacrylamide, N- (2-acetoacetoxyethyl) acrylamide and the like; methacrylamides, for example, methacrylamide, methyl methacrylamide, ethyl methacrylamide, propyl methacrylamide, butyl methacrylamide, tert-butyl methacrylamide, cyclohexyl methacrylamide , Benzyl methacrylamide, hydroxymethyl methacrylamide, methoxyethyl methacrylamide, dimethylaminoethyl methacrylamide, phenyl methacrylamide, dimethyl methacrylamide, diethyl methacrylamide, β-cyanoethyl methacrylamide, N- (2-acetoacetoxyethyl) methacrylamide Allyl compounds such as allyl acetate, allyl caproate, allyl laurate, allyl benzoate and the like; Le, such as, for example,
Methyl vinyl ether, butyl vinyl ether, hexyl vinyl ether, methoxyethyl vinyl ether, dimethylaminoethyl vinyl ether, etc .; vinyl ketones, for example, methyl vinyl ketone, phenyl vinyl ketone, methoxyethyl vinyl ketone, etc .; vinyl heterocyclic compounds, for example, vinyl pyridine, N -Vinylimidazole, N-vinyloxazolidone, N-vinyltriazole,
N-vinylpyrrolidone and the like; glycidyl esters such as glycidyl acrylate and glycidyl methacrylate; unsaturated nitriles such as acrylonitrile and methacrylonitrile; and polyfunctional monomers such as divinylbenzene and methylenebisacrylamide;
Ethylene glycol dimethacrylate and the like.

Further, acrylic acid, methacrylic acid, itaconic acid, maleic acid, monoalkyl itaconate, for example,
Monomethyl itaconate, monoethyl itaconate, monobutyl itaconate, etc .; monoalkyl maleate such as monomethyl maleate, monoethyl maleate, monobutyl maleate, etc .; citraconic acid, styrene sulfonic acid, vinylbenzyl sulfonic acid, vinyl sulfonic acid, acryloyl Oxyalkylsulfonic acid, for example,
Acryloyloxymethylsulfonic acid, acryloyloxyethylsulfonic acid, acryloyloxypropylsulfonic acid and the like; methacryloyloxyalkylsulfonic acid such as methacryloyloxydimethylsulfonic acid, methacryloyloxyethylsulfonic acid and methacryloyloxypropylsulfonic acid; acrylamidoalkylsulfonic acid For example, 2-acrylamido-2-methylethanesulfonic acid, 2-acrylamido-2-methylpropanesulfonic acid, 2-acrylamido-2-methylbutanesulfonic acid and the like; methacrylamidoalkylsulfonic acid, for example, 2-methacrylamido- 2-methylethanesulfonic acid, 2-methacrylamido-2-methylpropanesulfonic acid, 2-methacrylamido-2-methylbutanesulfonic acid, etc .; acryloyloxyalkyl phos Phosphates, for example, acryloyloxyethyl phosphate, 3-acryloyloxypropyl-2-phosphate, etc .; methacryloyloxyalkyl phosphates, for example, methacryloyloxyethyl phosphate, 3-methacryloyloxypropyl-2-phosphate, etc .; 3 having two hydrophilic groups -Naphthyl allyloxy-2-hydroxypropanesulfonate and the like. These acids may be salts of alkali metals (eg, Na, K, etc.) or ammonium ions. Still other monomer compounds, U.S. Pat.Nos. 3,459,790, 3,438,708, 3,554,987,
Crosslinkable monomers described in JP-A-4,215,195, JP-A-4,247,673 and JP-A-57-205735 can be used. Specific examples of such a crosslinkable monomer include N- (2-acetoacetoxyethyl) acrylamide, N- {2- (2-acetoacetoxyethoxy) ethyl} acrylamide and the like.

Among 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.

As the natural water-soluble polymer, 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
0.05 g or more should be dissolved 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-dispersible resins (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 dispersion medium, and a monomer is used in an amount of 10 to 50% by weight based on water and a polymerization initiator of 0.05 to 5% by weight based on the monomer; Using a dispersant, about 3
It is obtained by polymerizing under stirring at 0 to 100 ° C, preferably 60 to 90 ° C for 3 to 8 hours. The concentration of the monomer, the amount of the initiator, the reaction temperature, the time and the like can be widely and 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.).

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 solution polymerization, a mixture of monomers (usually 40% by weight or less, preferably 10 to 25% by weight, based on the solvent) in a suitable solvent (eg, ethanol, methanol, water, etc.) at a suitable concentration. Mixture) in the presence of a polymerization initiator (for example, benzoyl peroxide, azobisisobutyronitrile, ammonium persulfate, etc.) at an appropriate temperature (for example, 40 to 120).
C., preferably 50-100.degree. C.) to carry out the copolymerization reaction. 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 which dissolves the copolymer 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 forming 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).
Year) (Wiley & Sons, Inc.)
The Tg (° K) of the copolymer is represented by the following formula.

[0041] Tg _{(copolymer) = v 1 Tg 1 + v} 2 Tg 2 + ... + vWTgW However Ueshiki in v _1, v ₂ ... vW represents the weight fraction of the monomer in the copolymer, Tg _1, Tg ₂ ... TgW represents the Tg (° K) of the homopolymer of each monomer in the copolymer.

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. 2,852,386 and 2,853,457,
No. 3,411,911, No. 3,411,912, No. 4,197,127, Belgian Patent No. 688,882, No. 691,360, No. 712,823, JP-B No. 45-5331, JP-A No. 60-18540, No. 51-130217, No.
It is described in detail in 58-137831 and 55-50240.

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

The particle size of the polymer latex used in the present invention may be determined according to “chemistry of polymer latex” (Polymer Publishing Association,
1973), which can be measured by an electron micrograph, a soap titration method, a light scattering method, or a centrifugal sedimentation method. The light scattering method is preferably used. As an apparatus for the light scattering method, D
LS700 (manufactured by Otsuka Electronics Co., Ltd.) was used.

Although there is no particular limitation on the molecular weight, the total molecular weight is preferably 1,000 to 1,000,000, more preferably 2,000.
0 to 500,000.

The polymer latex used in the present invention can be contained in the photographic constituent 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 photographic constituent layer. The location of addition may be a photosensitive layer or a non-photosensitive layer.

The polymer latex used in the present invention includes a case where a functional polymer such as a polymer coupler or a polymer ultraviolet absorber is added in the form of a latex.

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 1,000 ml four-necked flask was equipped with a stirrer, a thermometer, a dropping funnel, a nitrogen inlet tube, and a reflux condenser, and nitrogen gas was supplied. While introducing and deoxidizing, 350 cc of distilled water was added and the internal temperature was 80 ° C.
Until heated. 4.5 g of Sf-1 was added as a dispersant, and 0.45 g of ammonium persulfate was further added as an initiator.
Is added, and then 90 g of ethylhexyl acrylate is 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. The particle size was 150 nm.

Production Example 2 (Synthesis of Lx-2) A stirrer, a thermometer, a dropping funnel, a nitrogen inlet tube, and a reflux condenser were provided to a 1,000 ml four-necked flask, and nitrogen gas was introduced to perform deoxygenation. 350 cc of distilled water was added, and the mixture was heated until the internal temperature reached 80 ° C. P-3 according to the present invention as a dispersant,
4.5 g of ammonium persulphate as initiator and 0.45 g of ethyl hexyl acrylate
90 g is dropped with 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. After cooling, pH 6 with ammonia water
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 deoxygenation was carried out with nitrogen gas. Then isononyl acrylate
15 g and 35 g of cyclohexyl acrylate were added, and 1.2 g of dimethyl azobisisobutyrate was added as an initiator.
Continue the reaction at 0 ° C. for 6 hours. After the reaction is completed, 3 l of the reaction solution is added.
Of distilled water with vigorous stirring to give white crystals.

The white crystals were collected by filtration, dried, dissolved in 100 ml of ethyl acetate, and distilled water 5 added with 2 g of Sf-2.
Add to 00 ml with vigorous stirring and then remove the ethyl acetate to obtain a polymer latex. The particle size was 180 nm.

Production Example 4 (Synthesis of Comparative Latex L) 0.25 kg of KMDS (dextran sulfate sodium salt) and ammonium persulfate in 40 l of water
A mixture of 4.51 kg of n-butyl acrylate, 5.49 kg of styrene and 0.1 kg of acrylic acid was added to the liquid containing 0.05 kg over 1 hour under a nitrogen atmosphere while stirring at a liquid temperature of 81 ° C., and then ammonium persulfate was added. After adding 0.005 kg and further stirring for 1.5 hours, the mixture was cooled and the pH was adjusted to 6 with aqueous ammonia.

The obtained latex solution was washed with Whotman GF.
The mixture was filtered with a / D filter, and finished to 50.5 kg with water to prepare a monodisperse latex (L) having an average particle size of 250 nm.

Hereinafter, specific examples of the polymer latex according to the present invention and the dispersant used in the synthesis thereof will be shown. The suffix of the monomer unit indicates the content percentage of each.

[0057]

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[0058]

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[0059]

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[0060]

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[0061]

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[0062]

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In the present invention, the amount of the polymer latex used is at least 10% by weight based on 100 gelatin.
It is 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. Further, the water-soluble polymer used in the present invention is a polymer latex 100
The weight ratio is 0.5% or more and 30% or less, preferably 1% or more and 15% or less.

The emulsion of the silver halide photographic light-sensitive material according to the present invention is silver halide grains which have been coagulated at least once during the production thereof with a polymer flocculant.

In general, in the production process of a photographic silver halide emulsion, a silver halide emulsion which has been physically ripened is subjected to a desalting step for removing excess halides and soluble salts such as alkali nitrate and ammonium. It is common to do

As the desalting method, for example, a noodle method, a dialysis method or a coagulation sedimentation method is known. Among them, the coagulation sedimentation method is widely used because it is superior to other methods. .

As the agglomerated gelatin agent used in the present invention, a modified gelatin obtained by substituting 50% or more of amino groups of a gelatin molecule is advantageously used. Examples of substitution of amino groups in gelatin are described in U.S. Pat. Nos. 2,691,582, 2,614,928 and 2,525,753.

Examples of useful substituents include (1) an alkyl group such as alkylacyl, arylacyl, acetyl and substituted or unsubstituted benzoyl; (2) a carbamoyl group such as alkylcarbamoyl and arylcarbamoyl; and (3) an alkylsulfonyl group. Sulfonyl groups such as arylsulfonyl, (4) thiocarbamoyl groups such as alkylthiocarbamoyl and arylthiocarbamoyl, (5) linear or branched alkyl groups having 1 to 18 carbon atoms, (6) substituted and unsubstituted phenyl, And aryl groups such as aromatic or heterocyclic rings such as naphthyl and pyridyl and furyl.

Among these, preferred flocculated gelatin agents are those based on acyl groups (—COR ′) and carbamoyl groups (—CON (R ¹ ) (R ² )).

R ¹ is a substituted or unsubstituted aliphatic group (for example, an alkyl group having 1 to 18 carbon atoms, an allyl group), an aryl group or an aralkyl group (for example, a phenethyl group).
² is a hydrogen atom, an aliphatic group, an aryl group, or an aralkyl group. Particularly preferred is a case where R ¹ is an aryl group and R ² is a hydrogen atom.

Hereinafter, specific examples of the aggregating gelatin agent will be exemplified by amino group substituents.

[0072]

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The amount of the flocculant gelatin agent used for desalting is not particularly limited, but is suitably 0.3 to 10 times (by weight) the gelatin contained as protective colloid at the time of desalting, and particularly preferably 1 to 1. ５5 times (weight).

Next, examples of the flocculant used in the present invention include a polymer flocculant represented by the following general formula [I].

[0075]

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R ¹ and R ² in the formula each represent an alkyl group having 1 to 8 carbon atoms which may be the same or different.

Z and Y each represent a —COOM group, a —COOR ³ group or a —CON (R ⁴ ) (R ⁵ ) group.

M represents a hydrogen atom, an alkali metal atom or an ammonium group, R ³ represents an alkyl group having 1 to 20 carbon atoms,
Represents an aryl group.

R ⁴ and R ⁵ are a hydrogen atom, an alkyl group having 1 to 20 carbon atoms or an aryl group, and R ⁴ and R ⁵ may be bonded to each other to form a heterocyclic ring. n represents an integer of 10 to 10 ^4.

In the above general formula (I), the alkyl group of R ¹ and R ² has 1 to 8 carbon atoms, more preferably 1 to 5 carbon atoms.
For example, methyl group, ethyl group, propyl group, butyl group,
And a pentyl group.

These alkyl groups may have a substituent. R ³ is an alkyl group having 1 to 20 carbon atoms, preferably having 1 to 12 carbon atoms, such as a methyl group, an ethyl group, a butyl group, a pentyl group, a heptyl group, an octyl group, a dodecyl group, etc. It may have a possible substituent.

The aryl group is, for example, a phenyl group. R ^4, R ⁵ represents an alkyl group of R ³ as defined, Examples of the heterocyclic ring R ⁴ and R ⁵ are bonded to each other to form, for example a pyridyl group, a morpholino group, and the like imidazole group.

Hereinafter, specific examples of the polymer compound represented by the general formula [I] will be shown.

[0084]

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[0085]

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[0086]

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The above compounds are known as polymer flocculants and can be easily obtained as commercial products.

The high molecular coagulant represented by the above general formula (I) has a molecular weight of 10 ³ to 10 ^6, preferably 3 × 10 ³ to 2 × 10 ⁵ , and the amount of addition depends on the gelatin contained in the emulsion. The weight ratio is 1/50 to 1/4, preferably 1/40 to 1/10.

In the embodiment of the present invention, the AgX emulsion is coagulated by adjusting the pH after the addition of the polymer flocculant. The pH at which coagulation is performed is 2.0 to 5.5, preferably 3.8 to 5.0.

The acid used for pH adjustment is not particularly limited, but organic acids such as acetic acid, citric acid and salicylic acid, and inorganic acids such as hydrochloric acid, nitric acid, sulfuric acid and phosphoric acid are preferably used. A heavy metal ion such as magnesium ion, cadmium ion, lead ion, zirconium ion or the like may be added in combination with the polymer flocculant.

The desalting may be repeated once or several times. In the case of repeating several times, a polymer flocculant may be added every time of desalting, or only the polymer flocculant may be added first.

The silver halide composition of the emulsion used in the present invention may be any silver halide such as silver iodobromide and silver iodochlorobromide, but silver iodobromide is preferred in that high sensitivity can be obtained. It is preferred that Silver halide grains are cubic, 8
All isotropically grown, such as tetrahedron, tetrahedron, or polyhedral crystal, such as sphere, twins with plane defects, or a mixture or composite thereof It may be a type.

The emulsion used in the silver halide photographic light-sensitive material of the present invention can be produced by a known method. For example, Research Disclosure (RD) No. 17643 (December 1978), 22
~ 23, or the method described in (RD) No. 18716 (November 1979), page 648, described in "Emulsion Preparation and Types".

Emulsions used in the silver halide photographic light-sensitive material of the present invention are described, for example, in "The Theory of the
Photographic process ”4th edition, published by Macmillan (1977
The method described on pages 38-104, GFDuffin, “Photograph
ic Emulsion Chemistry ”, Focal Press (1966),
P. Glafkides, “Chimie et Physique Photographi-qu
e ”Paul Montel (1967) or VLZelikman et al.“ Ma
king And CoatingPhotographic Emulsion "Focal Press
It can be prepared by the method described in the company publication (1964).

That is, mixing conditions such as a forward mixing method, a reverse mixing method, a double jet method and a control double jet method under solution conditions such as an acidic method, an ammonia method, and a neutral method;
The particles can be produced using particle preparation conditions such as a conversion method and a core / shell method, and a combination thereof.

A preferred embodiment of the emulsion used in the silver halide photographic light-sensitive material of the present invention is a monodisperse emulsion in which silver iodide is localized inside the grains. Monodisperse here means, when the average particle diameter is measured by an ordinary method,
At least 95% of the grains by number or weight are silver halide grains within ± 40%, preferably ± 30% of the average grain size.

The grain size distribution of silver halide may be either a monodisperse emulsion having a narrow distribution or a polydisperse emulsion having a wide distribution. The crystal structure of silver halide may have a different silver halide composition inside and outside,
For example, a core / shell type monodisperse emulsion having a clear two-layer structure in which a core portion of high silver iodide is covered with a shell layer of low silver iodide may be used.

The method for producing the above-mentioned monodispersed emulsion is known.
J. Phot. Sci, 12.242-251, (1963), JP-A-48-36890,
Nos. 52-16364, 55-142329, 58-49938, British Patent 1,413,748, U.S. Pat. Nos. 3,574,628, and 3,655,394. The emulsion used in the silver halide photographic light-sensitive material of the present invention is obtained by, for example, using a seed crystal as a method for obtaining the above-mentioned monodispersed emulsion, and supplying and growing silver ions and halide ions using the seed crystal as a growth nucleus. May be used.

The method for producing the above-mentioned core / shell type emulsion is known, and is described, for example, in J. Phot. Sci, 24.198. (1976), US Pat.
Nos. 250, 3,505,068, 4,210,450, 4,444,877 and JP-A-60-143331 can be referred to.

The emulsion used in the silver halide photographic light-sensitive material of the present invention has an aspect ratio (ratio of particle diameter / grain thickness).
Three or more tabular grains may be used. The advantages of such tabular grains are disclosed in, for example, British Patent No. 2,112,157, U.S. Pat.No. 4,414,310, and U.S. Pat.No. 4,434,226, as they can improve spectral sensitization efficiency and improve the graininess and sharpness of images. Emulsions can be prepared by the methods described in these publications.

The emulsions described above are either of a surface latent image type in which a latent image is formed on the grain surface, an internal latent image type in which a latent image is formed inside the grain, or a latent image type in which a latent image is formed on both the surface and inside. It may be an emulsion.

These emulsions are prepared at the stage of physical ripening or grain preparation, for example, using cadmium salt, lead salt, zinc salt, thallium salt, iridium salt or its complex salt, rhodium salt or its complex salt, iron salt or its complex salt and the like. You may.

In the silver halide photographic light-sensitive material of the present invention,
Various photographic additives can be used before and after physical ripening or chemical ripening. As the compound used in such a step, for example, the aforementioned (RD) No. 17643, (RD) No. 18
716 and (RD) No. 308119 (December 1989) can be used. The types and locations of the compounds described in these three (RD) Research Disclosures are listed below.

Additives RD-17643 RD-18716 RD-308119 page classification page page classification Chemical sensitizer 23 III 648 upper right 996 III sensitizing dye 23 IV 648-649 996-8 IV desensitizing dye 23 IV 998 B dye 25 ~ 26 VIII 649 ~ 650 1003 VIII Development accelerator 29 XXI 648 Upper right fog inhibitor / stabilizer 24 IV 649 Upper right 1006 ~ 7 VI Brightener 24 V 998 V Hardener 26 X 651 Left 1004 ~ 5 X Surfactant 26-27 XI 650 right 1005-6 XI 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 Halogenation of the present invention Examples of the support used for the silver photographic light-sensitive material include those described in the above RD,
A suitable support may be a plastic film or the like, and the support surface may be provided with an undercoat layer to improve the adhesiveness of the coating layer, or may be subjected to corona discharge or ultraviolet irradiation.

The process for developing a silver halide light-sensitive material according to the present invention comprises the steps of developing, fixing, washing with water (or stabilizing) and drying when the processing is performed by an automatic developing machine. Preferably, it is completed within 90 seconds.

That is, the time from when the tip of the photosensitive material starts to be immersed in the developing solution to when the tip comes out of the drying zone through the processing step (so-called dry-to-dry time).
Is less than 90 seconds, more preferably, this Dry to
Dry time must be within 60 seconds.

The developer used in the present invention is based on containing 1,4-dihydroxybenzenes or, if necessary, p-aminophenol compounds and / or pyrazolidone compounds as developers.

The 1,4-dihydroxybenzenes include hydroquinone, chlorohydroquinone, bromohydroquinone, isopropylhydroquinone, methylhydroquinone, 2,3-dichlorohydroquinone, 2,5-dichlorohydroquinone, 2,3-dibromohydroquinone, 2, There are 5-dimethylhydroquinone and hydroquinone monosulfonate, but hydroquinone is particularly preferred. N-methyl-p-aminophenol, p-aminophenol, N- (β-hydroxyethyl) as a p-aminophenol developing agent
There are -p-aminophenol, N- (4-hydroxyphenyl) glycine, 2-methyl-p-aminophenol and p-benzylaminophenol, among which N-methyl-p-aminophenol is preferable.

Examples of the pyrazolidone compound which can be used in the present invention include 1-phenyl-3-pyrazolidone, 1-phenyl-4,4-dimethyl-3-pyrazolidone, 1-phenyl-4-ethyl-3-pyrazolidone 1,1-phenyl-5-methyl-3-pyrazolidone, 1-phenyl-4-methyl-3-pyrazolidone, 1-phenyl-4-methyl-4-hydroxymethyl-3-pyrazolidone, 1-phenyl-4,4- Dihydroxymethyl-3-pyrazolidone, 1,5-diphenyl-3-pyrazolidone, 1-p-tolyl-3-pyrazolidone, 1-phenyl-2-acetyl-4,4-dimethyl-3-pyrazolidone, 1-p-hydroxy Phenyl-4,4-
Dimethyl-3-pyrazolidone, 1- (2-benzothiazolyl) -3-
Examples include pyrazolidone-based compounds such as pyrazolidone and 3-acetoxy-1-phenyl-3-pyrazolidone.

The developing solution of the present invention may contain a hardening agent which undergoes a hardening reaction with gelatin in the light-sensitive material during development processing to enhance film properties. As hardening agents, for example, glutaraldehyde, α-methylglutaraldehyde, β-methylglutaraldehyde, maledialdehyde, succindialdehyde, methoxysuccindialdehyde, methylsuccindialdehyde, α-methoxy-β-ethoxyglutaraldehyde, α-n-butoxyglutaraldehyde,
α, α-Dimethoxysuccindialdehyde, β-isopropylsuccindialdehyde, α, α-diethylsuccindialdehyde, butylmaledialdehyde, or a bisulfite adduct thereof are used.

In the developer used in the present invention, a sulfite (for example, sodium sulfite or potassium sulfite) can be used as a preservative of the developing agent.

In addition to the above components, additives used include development inhibitors such as sodium bromide and potassium iodide, ethylene glycol, diethylene glycol, triethylene glycol, dimethylformamide, methyl cellosolve, hexylene glycol, ethanol, Antifoggants such as organic solvents such as methanol or mercapto compounds such as 1-phenyl-5-mercaptotetrazole, sodium salt of 2-mercaptobenzimidazole-5-sulfonic acid, and benzotriazole compounds such as 5-methylbenztriazole And, if necessary, a color tone agent, a surfactant, an antifoaming agent, and the like.

The pH of the developer may be from 9.0 to 12, preferably from 9.0 to 11.5. Examples of the alkaline agent or buffer used for setting the pH include pH adjusting agents such as sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, boric acid, sodium tertiary phosphate and potassium tertiary phosphate.

The replenishing amount of the developer in the present invention is preferably not more than 330 ml, more preferably from 200 ml to 300 ml, per m ² of the light-sensitive material.

[0115]

Next, the present invention will be described in detail with reference to examples, but the present invention is not limited to these examples.

Example 1 Preparation of Emulsion 1 Preparation of Seed Emulsion 1 An iodine odor containing 2 mol% of silver iodide having an average grain size of 0.2 μm by a double jet method while controlling at 60 ° C., pAg = 8 and pH = 2.0. Monodisperse cubic silver halide particles were prepared.

The reaction liquid containing the obtained particles was divided into three parts, and desalting of soluble salts was carried out by a coagulation method as shown below, and three kinds of seed crystals (T-1, T-2 and T-3) were obtained. ) Was prepared.

(Method of desalting T-1)
At 0 ° C., desalting was performed using an aqueous solution of Demol N (aldehyde condensate of naphthalenesulfonic acid sodium salt) and magnesium sulfate manufactured by Kao Atlas Co., Ltd., and then redispersed in an aqueous gelatin solution to prepare seed emulsion T-1. I got

(Method of Desalting T-2)
At 0 ° C., 38 g / mol AgX of Exemplified Compound G-8 (amino group modification rate 92%) was added as a coagulating gelatin agent, and after stirring for 3 minutes, KOH (0.13 g / mol AgX) was added to adjust the pH to 4.0. Standing still,
Decantation was performed.

Thereafter, 2.1 liter / mol AgX of H ₂ O at 40 ° C. was added, 0.25 g / mol AgX of KOH was added, pH was set to 5.8, and after stirring for 5 minutes, 1.5 ml of HNO ₃ (1.7N) / mol AgX was added. And add pH
= 4.3 and allowed to stand and decant. Thereafter, gelatin and KOH 0.2 g / mol AgX were added, and the mixture was redispersed at pH = 5.8 to obtain a seed emulsion T-2.

(Desalting method of T-3)
8.0 g of Exemplified Compound PF-1 as a polymer flocculant at 0 ° C.
/ Mol AgX and stirred for 3 minutes, then KOH (0.13 g / mol Ag)
X) was added thereto, the mixture was allowed to stand at pH = 4.0, and decantation was performed.

Then, after adding 2.1 liter / mol AgX of H ₂ O at 40 ° C., 0.25 g / mol AgX of KOH was added, the pH was adjusted to 5.8, and the mixture was stirred for 5 minutes. Then, 1.5 ml of HNO ₃ (1.7N) / mol AgX was added. And add pH
= 4.3 and allowed to stand and decant. Thereafter, gelatin and KOH 0.2 g / mol AgX were added, and the mixture was redispersed at pH = 5.8 to obtain a seed emulsion T-3.

Growth from Seed Emulsion 1 Using the above-described seed emulsion T-1, grains were grown as follows. First, a seed emulsion was dispersed in an aqueous gelatin solution maintained at 40 ° C., and the pH was adjusted to 9.7 with aqueous ammonia and acetic acid. An aqueous solution of ammonium silver nitrate and an aqueous solution of potassium bromide and potassium iodide were added to this solution by a double jet method. During the addition, pAg = 7.3 and pH = 9.7 were controlled to form a layer having a silver iodide content of 35 mol%. Next, an aqueous ammonium nitrate solution and an aqueous potassium bromide solution were added by a double jet method. Up to 95% of the target particle size, keep pAg = 9.0, pH is
Continuously changed from 9.0 to 8.0. Then, pAg = 11.
It was grown to the target particle size while adjusting to 0 and maintaining pH = 8.0. Subsequently, the pH was lowered to 6.0 with acetic acid and 5,5′-dichloro-9-
Ethyl-3,3'-di- (3-sulfopropyl) oxacarbocyanine sodium salt anhydrous 400 mg / mol AgX was added,
After desalting using the above-mentioned Demol N aqueous solution and magnesium sulfate aqueous solution, an aqueous gelatin solution was added and redispersed.

According to this method, the apexes having an average silver iodide content of 2.0 mol% having a rounded apex and an average grain size of 0.40 μm, 0.6
5 μm, 1.00 μm, coefficient of variation (σ / γ) 0.17,
0.16, 0.16 monodispersed silver iodobromide emulsions (A-1), (B-1),
(C-1) was prepared.

Further, (A-2), (B-2) and (C-2) were prepared by growth from seed emulsion T-2 in the same manner, and seed emulsion T-3 was prepared in the same manner. By growth, (A-3), (B-3), (C-
3) was prepared.

Preparation of Emulsion 2 Preparation of Seed Emulsion Including Hydrogen Peroxide-treated Gelatin Stirred Vigorously at 40 ° C.
To a 0.05N aqueous potassium bromide solution, add an equimolar aqueous potassium bromide solution containing a silver nitrate aqueous solution and hydrogen peroxide-treated gelatin by a double jet method, and after 1.5 minutes, add
After lowering the liquid temperature to 5 ° C, 80ml per mole of silver nitrate
Ammonia water (28%) was added and stirring was continued for 5 minutes. Thereafter, the reaction solution adjusted to pH = 6.0 with acetic acid was divided into three parts,
Desalting was carried out in the same manner as in (T-1), (T-2) and (T-3) to obtain three kinds of seed crystals (T-4, T-5 and T-6).

Growth from Seed Emulsion 2 Using the above-described seed emulsion T-4, grains were grown as follows. An aqueous solution of potassium bromide and potassium iodide and an aqueous solution of silver nitrate were added to an aqueous solution containing ossein gelatin and propyleneoxy-polyethylene oxydisuccinate disodium salt vigorously stirred at 75 ° C by a double jet method. During this time, pH = 5.8 and pAg = 9.0 were maintained. After the addition is complete, p
H was adjusted to 6.0, and 5,5'-dichloro-9-ethyl-3,3'-di-
Anhydrous (3-sulfopropyl) oxacarbocyanine sodium salt was added at 400 mg / mol AgX. After desalting at 40 ° C. using an aqueous solution of Demol-Na and an aqueous solution of magnesium sulfate manufactured by Kao Atlas Co., an aqueous solution of gelatin was added and redispersed.

By this method, tabular silver iodobromide (D) having an average silver iodide content of 1.5 mol%, a projected area diameter of 0.96 μm, and a variation coefficient of 0.25 aspect ratio (projected area diameter / grain thickness) of 4.0.
-1) was prepared.

Further, (D-2) was prepared by growing from seed emulsion T-5 by the same method, and (D-3) was prepared by growing from seed emulsion T-6 by the same method.

Preparation of Silver Halide Fine Particles While controlling pAg = 9.7 at 40 ° C., silver iodide fine particles having an average particle size of 0.05 μm and a mixture of β-type and γ-type were prepared by a double jet method.

Preparation of Samples The obtained emulsions (A-1, 2, 3), (B-1, 2, 3), (C-
1,2,3) and (D-1,2,3) at 55 ° C
5'-Dichloro-9-ethyl-3,3-di- (3- (sulfopropyl) oxacarbocyanine sodium anhydride and 5,5'-di- (butoxycarbonyl) -1,1'-diethyl-3 2,3 '-(4-Sulfobutyl) benzimidazolocarbocyanine sodium salt anhydrous at a weight ratio of 200: 1, per mole of silver halide
(A-1,2,3) 980mg, (B-1,2,3) 600mg,
390 mg of (C-1,2,3) and 500 mg of (D-1,2,3) were added.

After 10 minutes, appropriate amounts of chloroauric acid, sodium thiosulfate and ammonium thiocyanate were added to carry out chemical ripening. 20 minutes before the completion of ripening, silver iodide fine grains 5 × 10 ^-2 mol /
Molar AgX was added. Then 4-hydroxy-6-methyl-1,3,3
a, 7-Tetrazaindene is added in an amount of 3 × per mole of silver halide.
10 ^-3 mol was added and dispersed in an aqueous solution containing 70 g of gelatin.

Of the eight kinds of ripened emulsions, (A-1)
(B-1) and (C-1) were mixed at a weight ratio of 10:70:20 to prepare emulsion-I, and (A-2), (B-2) and (C-2) were prepared in the same manner. 1
Emulsion-II, (A-3), (B-
3) and (C-3) were similarly mixed at a ratio of 10:70:20 to prepare Emulsion-III. Also, (D-1) was used alone as Emulsion-IV,
(D-2) was Emulsion-V and (D-3) was Emulsion VI.

The following additives and the polymer latex shown in Table 1 were added to each of the emulsions I to VI. The amount of addition is shown in an amount per mole of silver halide.

1,1-Dimethylol-1-bromo-1-nitromethane 70 mg t-butyl-catechol 400 mg polyvinylpyrrolidone (molecular weight 10,000) 1.0 mg styrene-maleic anhydride copolymer 2.5 g nitrophenyl-triphenylphosphonium chloride 50 mg 2 -Anilino-4,6-dimercaptotriazine 60 mg ammonium 1,3-dihydroxybenzene-4-sulfonate 4 g 2-mercaptobenzimidazole-5-sodium sulfonate 15 mg C ₄ H ₉ OCH ₂ CH (OH) CH ₂ N ( (CH ₂ COOH) ₂ 1g 1-phenyl-5-mercaptotetrazole 10mg

[0136]

Embedded image

The additives used in the protective layer solution are as follows. The amount of addition is indicated by the amount per liter of the coating solution.

Lime-treated inert gelatin 68 g Acid-treated gelatin 2 g Polyacrylamide (average molecular weight 50,000) 20 g Sodium-i-amyl-n-decylsulfosuccinate 0.3 g Polymethyl methacrylate (matting agent having an area average particle size of 3.5 μm) 1.1 g Silicon dioxide (matting agent with an area average particle size of 1.2 μm) 0.5 g Ludox AM (colloidal silica manufactured by DuPont) 30 mg Glyoxal 40% aqueous solution 1.5 ml (CH ₂ = CHSO ₂ CH ₂ ) ₂ O 500 mg

[0139]

Embedded image

The compositions of the developer and fixer used are shown below.

(Developer) Potassium sulfite 70 g Hydroxyethylethylenediamine 15 g Trisodium triacetate 8 g 1,4-dihydroxybenzene 28 g Boric acid 10 g 5-methylbenzotriazole 0.04 g 1-phenyl-5-mercaptotetrazole 0.01 g Sodium metabisulfite 5 g Acetic acid (90%) 13 g Triethylene glycol 15 g 1-Phenyl-3-pyrazolidone 1.2 g 5-Nitroindazole 0.2 g Potassium bromide 4 g 5-Nitrobenzimidazole 1 g
Solution. As a working solution, a solution was used in which 1.0 g of this solution was added as a starter at a ratio of 3 g of potassium bromide and 4 ml of glacial acetic acid, and the developing tank was filled at the start of running.

(Fixing solution) Ammonium thiosulfate 130 g Anhydrous sodium sulfite 7.3 g Sodium acetate trihydrate 25.8 g Aluminum sulfate 18 hydrate 14.6 g Sulfuric acid (50 wt%) 6.77 g Boric acid 7 g Acetic acid 15.0 g With sodium hydroxide
H was set to 4.40.

The film was developed by the following processing steps using a roller transport type automatic developing machine (SRX-502, manufactured by Konica Corporation) having a total processing time of 45 seconds.

Processing Step Processing Temperature (° C) Processing Time (seconds) Replenishment Amount Insertion-1.2 Development + Migration 35 14.6 260 ml / m ² Fixation + Migration 33 8.2 600 ml / m ² Rinse + Migration 25 7.2 3.5 l / min Squeeze 40 5.7 Drying 45 8.1 Total-45.0 [Sensitometry] Fluorescent intensifying screen KO-
250 (made by Konica Corporation), tube voltage 90KVP, 20mA
Then, X-rays were irradiated for 0.05 seconds, and a sensitometric curve was created by a distance method to determine the sensitivity. Sensitivity value is fog +1.0
Was determined as the reciprocal of the X-ray dose required to obtain the concentration of The results were expressed as relative sensitivities when the sensitivity of sample No. 1 was set to 100.

[Evaluation of Scratch Resistance]
After adjusting the humidity for 1 hour under the condition of 30 ° C and 30% RH, weight 100g on the area of 2cm ² using a commercially available nylon scourer under the same condition.
And rubbed at a speed of 2 cm per second. After performing the above-mentioned automatic development processing in an unexposed state, the number of blackened scratches was counted.

[Evaluation of Silver Tone] The prepared sample was exposed so that the transmission density after development was 1.2, and then developed using the automatic developing machine. Obtained developed sample
After 7 days at a temperature and humidity of 50 ° C. and 80% RH, the mixture was observed with a Schaukasten, and the silver tone due to the transmitted light was visually evaluated.

Evaluation 1. Pure black 2. 2. A slightly reddish black color 3. Reddish black Yellowish black The obtained results are shown in Table 1 below.

[0148]

[Table 1]

As is clear from Table 1, according to the present invention, excellent performance was obtained in all of sensitivity, scratch resistance and color tone of developed silver.

[0150]

According to the present invention, it is possible to obtain a silver halide photographic light-sensitive material having less scratching and a high covering power, and further has a high sensitivity and high covering power in which the image after development processing is improved to a black tone. Can be provided.

Claims (1)

(57) [Claims] 1. A silver halide photographic light-sensitive material having at least one photosensitive silver halide emulsion layer on a support, wherein said silver halide emulsion layer and / or other layers are exposed to water at 25 ° C. A silver halide emulsion containing at least one polymer latex having at least one monomer having a solubility of not more than 0.025% by weight as a monomer unit, and at least one silver halide emulsion of the silver halide photographic material; Is a silver halide photographic light-sensitive material comprising silver halide grains coagulated at least once with a polymer coagulant during the production thereof.