JP3243668B2 - 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, and more particularly to a silver halide photographic material which prevents development unevenness and roller marks (pressure fog or pressure desensitization) caused by rapid processing by an automatic processor. It relates to a photographic material.

[0002]

2. Description of the Related Art In recent years, with the development of photographic technology, there is a strong demand for higher sensitivity and higher image quality of silver halide photographic materials. Further, as the consumption of photosensitive material increases, rapid processing in a short time has been strongly demanded.

In order to enable rapid processing, it is necessary to enhance the developability and reduce the drying load. For example, rapid processing is possible by increasing the developability by processing at a high pH and a high temperature (30 to 40 ° C.) in the development processing, and by reducing the amount of binder in the photosensitive material. However, there has been a problem that a so-called roller mark or the like is generated due to the pressure of the transport roller, thereby deteriorating the image quality, or a blackening of the pressure occurs during cutting of the film, handling during transport or diagnosis.

[0004] As means for improving roller mark and blackening of pressure, the structure of silver halide grains can be made high in internal iodine,
A method using latex has been reported, but increasing the iodine content of the silver halide causes pressure desensitization this time, and merely balances the opposing performances of pressure blackening and pressure desensitization. Not a complete solution. Also, when latex is used, the surface specific resistance of the film is increased, and there are drawbacks such as inducing static and developing unevenness.

[0005]

Accordingly, an object of the present invention is to prevent development unevenness and roller marks (pressure fog or pressure desensitization) which occur during rapid processing by an automatic developing machine, and to provide a high sensitivity and a high sensitivity without scratches. An object of the present invention is to provide a silver halide photographic light-sensitive material having high image quality.

[0006]

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 A light-sensitive silver halide emulsion containing at least one polymer latex having at least one monomer as a monomer unit and having a solubility in water at 25 ° C. of not more than 0.025% by weight in the other layer; The silver halide photographic material is characterized in that the difference between the matte degree on the side having the layer and the matte degree on the backing layer side is 50 mmHg or more.

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 not more than 0.025% by weight, preferably not more than 0.015% by weight. 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, 0.00% by weight for 2-ethylhexyl methacrylate, and 0.00% 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.

[0011] 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 the 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 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.

The acrylamides include acrylamide, methylacrylamide, ethylacrylamide, propylacrylamide, butylacrylamide, 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.

Also, 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 one 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 the natural water-soluble polymer, a comprehensive technical data collection of water-soluble polymer water-dispersible resins (for example, those described in detail in the Management Development Center, preferably lignin, starch, pullulan, cellulose, dextran) Dextrin, glycogen, alginic acid, gelatin, collagen, guar gum, gum arabic, laminaran, lichenin, nigran, etc. and derivatives of natural water-soluble polymers such as sulfonation, carboxylation, phosphorylation, sulfo Alkenylated, carboxyalkylated, alkylphosphorylated and salts thereof are preferably used, particularly preferably 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 10 to 50% by weight of a monomer and 0.05 to 5% by weight of a polymerization initiator and 0.1 to 20% by weight of a monomer are used. 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. In solution polymerization, which is preferably a combination of a water-soluble polymer and a nonionic or anionic activator, generally a mixture of monomers in a suitable solvent (eg, ethanol, methanol, water, etc.) at a suitable concentration (usually, An appropriate temperature (for example, benzoyl peroxide, azobisisobutyronitrile, ammonium persulfate, etc.) in the presence of a polymerization initiator (e.g., benzoyl peroxide, azobisisobutyronitrile, ammonium persulfate, etc.) at 40% by weight or less, preferably 10 to 25% by weight based on the solvent. The copolymerization reaction is carried out by heating to 40 to 120 ° C, preferably 50 to 100 ° C). 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 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.

[0037] 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 can be preferably used as long as it is 0.5 to 300 nm, and particularly preferably 30 to 250 nm.

The particle size of the polymer latex used in the present invention is determined by the following formula: “Polymer latex chemistry” (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 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 supplied. While introducing and deoxidizing, 350 cc of distilled water was added and heated until the internal temperature reached 80 ° C. 4.5 g of Sf-1 was added as a dispersant, and 0.45 g of ammonium persulfate was further added as an initiator, and then 90 g of ethylhexyl acrylate was added dropwise over about 1 hour using a dropping funnel. 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 performed 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 containing 2 g of Sf-2 was added.
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 liters 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 GF manufactured by Whotman.
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.

[0053]

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[0054]

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[0055]

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[0056]

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[0057]

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[0058]

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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 exhibited, and 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 10
It is 0.5% or more and 30% or less, preferably 1% or more and 15% or less by weight with respect to 0.

In the present invention, the matte degree indicates the roughness of the film surface, and can be measured as follows.

That is, in this specification, the degree of mat is
For unexposed photosensitive material (so-called raw film) that was conditioned for 4 hours at a temperature of 23 ° C. and a humidity of 48% RH,
After humidity control, the suction pressure is measured under the same conditions, and the value is expressed in mmHg. The larger the value, the higher the matte degree. In the examples described below, a smoother (manufactured by Toei Denshi Kogyo (Iron)) was used to measure the suction pressure.

Usually, a matting agent is used to impart a matte degree to a light-sensitive material. The matting agent is generally fine particles of a water-insoluble organic or inorganic compound. Any matting agent can be used, and for example, those well known in the art can be used. For example, organic matting agents include U.S. Pat. Nos. 1,939,213 and 2,322,
037, 2,701,245, 3,262,782
Nos. 3,539,344 and 3,767,488 can be used.

As the inorganic matting agent, the same as the first, 260, 7
No. 72, No. 2, 192, 241 and No. 3, 257, 206
Nos. 3,370,951, 3,523,022, and 3,769,020 can be used.

For example, specific examples of organic compounds that can be used as a matting agent include polymethyl acrylate, polymethyl methacrylate, polyacrylonitrile, and acrylonitrile-α-methylstyrene as examples of water-dispersible vinyl polymers. Copolymers, polystyrene, styrene-divinylbenzene copolymer, polyvinyl acetate, polyethylene carbonate, polytetrafluoroethylene, etc., as examples of cellulose derivatives, methyl cellulose, ethyl cellulose, cellulose acetate, cellulose acetate propionate, etc., of starch derivatives Examples include carboxy starch, carboxynitrilophenyl starch, urea-formaldehyde-starch reactants, etc.
Gelatin hardened with a known hardener, hardened gelatin coacervated into microcapsule hollow particles, and the like can be preferably used. Examples of the inorganic compound include silicon dioxide, titanium dioxide, magnesium dioxide, aluminum oxide, barium sulfate, calcium carbonate, silver chloride desensitized by a known method, silver bromide, glass, and diatomaceous earth. .

The above matting agents can be used by mixing different kinds of substances as necessary.

The size and shape of the matting agent are not particularly limited, and those having an arbitrary particle size can be used. In practicing the present invention, it is preferable to use one having a particle size of 0.1 μm to 15 μm.

The particle size distribution of the matting agent used may be narrow or wide, and may be monodisperse or polydisperse. Here, the monodisperse matting agent refers to one in which the number of particles having a particle diameter within ± 20% of the average particle diameter is 90% or more of the total number of particles.

In the present invention, the matte degree of the photosensitive emulsion layer is lower than the matte degree of the backing layer side, and the difference is 50 m.
The difference may be at least mHg, but preferably there is a difference of at least 60 mmHg, and more preferably at least 70 mmHg. Specifically, the following matte degree can be obtained for each surface.

That is, the matte degree on the photosensitive emulsion layer side is 0 to 0.
90 mmHg, preferably 0 to 70 mmHg
And more preferably 0 to 50 mmHg.

The matting degree on the backing layer side is 50 to
300 mmHg, preferably 50 to 250 m
mHg, more preferably 50 to 200 mHg.
Particularly preferred is mHg.

However, the value of the matting degree on the side of the photosensitive emulsion layer and the backing layer depends on the particle size (type) of the matting agent used,
And the amount used may be appropriately adjusted.

In the present invention, the matting agent is preferably contained in the outermost surface layer of the light-sensitive material, a layer functioning as the outermost surface layer, or a layer near the outer surface, and acts as a so-called protective layer. It is preferably contained in a layer. That is, in the photosensitive emulsion layer, it is preferably contained in a protective layer which is a non-photosensitive layer, and on the backing layer side, it is preferably contained in a backing layer. (Upper layer side).

The content of the matting agent is determined so that the difference in the matting degree of the photosensitive emulsion layer and the backing layer is within the range of the present invention, and the matting agent is contained such that the preferable matting degree is obtained for each surface. Is good.

The same or different matting agent may be contained in two or more layers. In this case, the layer to which the matting agent is added may be an emulsion layer, a protective layer, or an undercoat layer provided as necessary. Or an intermediate layer.

The silver halide emulsion used in the silver halide photographic light-sensitive material of the present invention includes silver bromide, silver iodobromide,
Alternatively, it may be a silver iodochlorobromide emulsion containing a small amount of silver chloride.
The halogenated grains may be of any crystal type as long as they have the constitution of the present invention, for example, cubic, octahedral, 14
It may be a single crystal such as a face crystal or a polytwin particle having various shapes.

The emulsion used for 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.

The emulsion used in the silver halide photographic light-sensitive material of the present invention is preferably a monodisperse emulsion in which silver iodide is localized inside the grains. The term “monodispersion” as used herein means that at least 95% of the particles in terms of the number or weight of the particles are within ± of the average particle diameter when the average particle diameter is measured by an ordinary method.
The silver halide grains are within 40%, preferably within ± 30%.

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 silver ions and halide ions using the seed crystal as a growth nucleus to grow. May be used. The method for producing the above-mentioned core / shell type emulsion is known, for example, J. Phot. Sci, 24.198. (1976), U.S. Pat. Nos. 2,592,250, 3,505,068, 4,210,450,
No. 4,444,877 or JP-A-60-143331 can be referred to.

The emulsion used in the silver halide photographic light-sensitive material of the present invention may be tabular grains having an aspect ratio (ratio of grain diameter / grain thickness) of 3 or more. 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 can be prepared at the stage of physical ripening or grain preparation by using, for example, 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.

The emulsion may be subjected to a Nudel washing method or a flocculation sedimentation method to remove soluble salts. Preferred examples of the washing method include aromatic hydrocarbons containing a sulfo group described in JP-B No. 35-16086. Examples thereof include a method using a system aldehyde resin, and a desalting method using G-3, G-8, etc., which are polymer flocculants described in JP-A-63-158644.

The emulsion used in the silver halide photographic light-sensitive material of the present invention can use various photographic additives before and after physical ripening or chemical ripening. As the compound used in such a step, for example, the aforementioned (RD) No. 1
7643, Nos. 18716 and 308119 (December 1989) can be used. The locations of these three (RD) are listed below.

Additive 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 is a plastic film or the like, and the surface of the support improves the adhesion of the coating layer. For this purpose, an undercoat layer may be provided, or corona discharge or ultraviolet irradiation may be applied.

The photographic processing of the light-sensitive material of the present invention can be carried out, for example, by the methods described in (RD) -17643, XX to XXI, pp. 29 to 30, or XX of 308119.
Treatment with a treatment solution as described in XXI, pp. 1011-1012 may be performed. This process may be a black and white photographic process for forming a silver image. Processing temperature is usually between 18 ° C and 50
Processed in the range of ° C.

As a developer in black-and-white photographic processing, dihydroxybenzenes (for example, hydroquinone), 3-pyrazolidones (for example, 1-phenyl-3-pyrazolidone), and aminophenols (for example, N-methyl-P-aminophenol) Etc. can be used alone or in combination. In the developer, for example, known preservatives, alkali agents, pH buffering agents, antifoggants, hardeners, development accelerators, surfactants,
An antifoaming agent, a color tone agent, a water softener, a dissolution aid, a viscosity imparting agent, and the like may be used as necessary.

The fixing solution contains a fixing agent such as thiosulfate or thiocyanate, and may further contain a water-soluble aluminum salt such as aluminum sulfate or potassium alum as a hardening agent. In addition, it may contain a preservative, a pH adjuster, a water softener and the like.

[0091]

Embodiments of the present invention will be described below. However, needless to say, the present invention is not limited to the embodiments described below.

Example 1 Preparation of Grains Monodisperse grains of silver iodobromide containing 2.0 mol% of silver iodide having an average grain diameter of 0.2 μm were used as nuclei, and silver iodobromide containing 30 mol% of silver iodide was adjusted to pH 9 .8, grown at pAg7.8, then pH8.2, pAg9.1
The average grain size is obtained by adding equimolar amounts of potassium bromide and silver nitrate to obtain silver iodobromide grains having an average silver iodide content of 2.2 mol%.
Monodisperse emulsion grains of 0.395 μm were prepared.

The emulsion was subjected to desalting of excess salts by a usual coagulation method. That is, while maintaining the temperature at 40 ° C., a formalin condensate of sodium naphthalene sulfonate and an aqueous solution of magnesium sulfate were added to cause aggregation. After removing the supernatant, further at 40 ° C
Was added, and an aqueous solution of magnesium sulfate was added again to cause aggregation, and the supernatant was removed.

The dispersibility of the silver halide grains thus obtained was 0.15, and the silver halide grains had good monodispersity.

Preparation, Processing and Evaluation of Samples The silver halide grains thus obtained were added with pure water so that the volume per mole was 500 ml, and then brought to 55 ° C., and the following spectral sensitizing dyes A and B and 200: 1 by weight in a total amount of 300 mg per mole of silver halide, and after 10 minutes, ammonium thiocyanate is added in an amount of 2.6 × 10 ⁻³ mole per mole of silver and an appropriate amount of chloride. Gold acid and hypo were added to initiate chemical ripening.

At this time, the pH was 6.15 and the silver potential was 50 mV.

Fifteen minutes before the completion of chemical ripening (70 minutes after the start of chemical ripening), 200 mg of potassium iodide was added per mole of silver, and five minutes later, 10% (wt / Vol) acetic acid was added thereto. The value
The pH was lowered to 5.6 and the pH was maintained for 5 minutes, after which a 0.5% (wt / Vol) solution of potassium hydroxide was added to bring the pH to 6.15.
After that, 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene was added, and the chemical ripening was completed to obtain a photographic emulsion coating solution. The pH after preparation of the photographic emulsion coating solution was 6.1.
0, the silver potential was 81 mV (35 ° C.).

Using this emulsion coating solution, a sample was prepared as follows. That is, the amount of gelatin in the photographic emulsion layer is shown in Table 1 as the amount of gelatin.
So that the stated amounts, amount of silver such that a 3.0 g / m ² in terms of silver value and a protective layer solution was prepared using additives described subsequently herein, the protective layer is a quantity with gelatin The coating was performed so that the amount was as shown in Table 1.

The spectral sensitizing dye is as follows: Sensitizing dye (A) 5,5'-dichloro-9-ethyl-3,3'-di- (3
-Sulfopropyl) oxacarbocyanine sodium salt sensitizing dye (B) 5,5'-di- (butoxycarbonyl) -1,
Anhydrous 1'-diethyl-3,3'-di- (4-sulfobutyl) benzimidazolocarbocyanine sodium salt Additives used in emulsion (photosensitive silver halide coating solution) are as follows. . 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 g styrene-maleic anhydride copolymer 2.5 g trimethylolpropane 10 g diethylene glycol 5 g nitrophenyl- Triphenylphosphonium chloride 50mg Ammonium 1,3-hydroxybenzene-4-sulfonate 4g 2-Sodium mercaptobenzimidazole-5-sulfonate 1.5mg

[0101]

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The additives used in the protective layer solution are as follows. The amount of addition is shown as an amount per 1.0 liter of the coating solution.

Silicon dioxide particles (matting agent having an area average particle size of 1.2 μm) Added so as to have a matting degree shown in Table 1 Ludox AM (colloidal silica manufactured by DuPont) Added so as to have a matting degree shown in Table 1 4-Dichloro-6-hydroxy-1,3,5-triazine sodium salt aqueous solution 2% 12ml Formalin 35% 2ml Glyoxal aqueous solution 40% 2.0ml

[0104]

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The emulsion coating solution contains, in addition to the above additives,
The following compound (1) was dissolved in an oil composed of compound (2) and dispersed in a hydrophilic colloid solution according to the method described in Example 1 (3) of JP-A-61-285445. Were added in the following amounts per mole of silver halide.

[0106]

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(2) 0.6 g of tricresyl phosphate The following solutions were prepared and used for the backing layer.

(Backing layer) (Backing lower layer solution) Lime-treated gelatin 70 g Acid-treated gelatin 5 g Trimethylolpropane 1.5 g Backing dye A 1.0 g Backing dye B 1.0 g Grioxal aqueous solution (40%) 8 ml per liter of coating solution (Backing upper layer solution) Lime-treated gelatin 70 g acid-treated gelatin 5 g trimethylolpropane 1.5 g backing dye A 1.0 g backing dye B 1.0 g KNO ₃ 0.5 g 2,4-dichloro-6-hydroxy-1,3,5-triazine sodium per liter of coating solution 2% aqueous solution of salt 20 ml Polymethyl methacrylate particles having an area average particle size of 4.0 μm Added so as to have the matte degree shown in Table 1 C ₁₁ H ₂₃ CONH (CH ₂ CH ₂ O) ₅ H 1.0 g

[0109]

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The backing lower layer solution had a gelatin content of 3.0 g.
/ m ² and an upper layer solution of 1.2 g / m ² to obtain a sample. Coating is performed every minute with two slide hopper type coaters
At a speed of 80m, glycidyl methacrylate 50wt%,
Methyl acrylate 10wt%, butyl acrylate 40wt%
An aqueous dispersion of the copolymer obtained by diluting the copolymer consisting of the three types of monomers to a concentration of 10% by weight was simultaneously coated on a 175 μm polyethylene terephthalate film base provided as an undercoat liquid. , Dried in 2 minutes 20 seconds,
A sample was obtained.

The polymer latex according to the present invention was added as shown in Table 1.

Evaluation method of roller mark A sample was cut into a size of 127 mm x 305 mm, and the density after development was about 1.0,
An exposed sample and an unexposed sample were prepared in advance so as to have three levels of density of 0.6 and 0.4. These samples
Dry to Dr using XD-SR and XF-SR with SRX-502 automatic processor
y Processed in 45 seconds. (All manufactured by Konica Co., Ltd.) The occurrence of spot marks on the obtained samples was evaluated in the following five stages.

◎: Not generated at all ：: Slightly generated △: Generated but practically acceptable ×: Many occurred, practically unacceptable ×: Notablely generated Development Evaluation method for unevenness ：: No unevenness was generated at all. ○: Slightly generated unevenness. ：: Unevenness was generated but practically acceptable. X: Many unevenness was generated, and practically impossible. XX: A sample in which unevenness occurs remarkably Evaluation method for abrasion A sample is cut into a size of 50 mm x 305 mm, and two samples conditioned at 25 ° C and 50% RH for 2 hours are stacked. 10 on it
A 0 g weight was placed on the upper film, and the upper film was dragged three times to the front. Thereafter, the film was subjected to a developing treatment, and the obtained abrasion-like blackening was evaluated in the following five stages.

◎: Not generated at all ○: Slightly generated Δ: Generated but practically acceptable ×: Many occurred, practically unacceptable ××: Extremely generated The results obtained are shown in Table 1 below. As is clear from the table, the sample of the present invention containing the polymer latex in the backing layer produced a clear image with no occurrence of roller marks and development unevenness and little abrasion.

[0115]

[Table 1]

Example 2 Preparation of Particles A 1.5% gelatin solution containing 0.17 mol of potassium bromide 5.5
While stirring the mixture at 80 ° C. and a pH of 5.9, 2.1 mol of potassium bromide and 2.0 mol of a silver nitrate solution were added thereto over 2 minutes by the double jet method. pBr was maintained at 0.8.
(Consumption of 0.53% of total silver nitrate used) The addition of the potassium bromide solution was stopped and the silver nitrate solution was continued to be added for 4.6 minutes.
(Consuming 8.6% of total silver nitrate used) Then, potassium bromide solution and silver nitrate solution were added simultaneously for 13 minutes. During this time p
The Br was maintained at 1.2, and the addition flow rate was accelerated so that the completion time was 2.5 times the start time. (43.6% of total silver nitrate used
(Consumption%) The addition of the potassium bromide solution was stopped and the silver nitrate solution was added for 1 minute. (Consumption of 4.7% of total silver nitrate used) A 2.0 mol solution of potassium bromide containing 0.55 mol of potassium iodide was added together with the silver nitrate solution over 13.3 minutes. During this time
The pBr was maintained at 1.7 and the flow rate was accelerated at completion to 1.5 times the starting rate. (Consumes 35.9% of the total silver nitrate used) 1.5 g of sodium thiocyanate / mol Ag
Was added and held for 25 minutes. 0.60 mol of potassium iodide solution and silver nitrate are pBr for about 5 minutes at the same flow rate by the double jet method.
Until 3.0 was reached. (Approximately 6.6 of total silver nitrate used
% Consumed) was about 11 moles of total silver nitrate consumed.

Thus, an emulsion containing tabular silver iodobromide grains having an average grain diameter of 1.62 μm and an aspect ratio of about 16: 1 was prepared. The grains account for at least 80% of the total projected area of the silver iodobromide grains. However, before desalting, the above-mentioned spectral sensitizing dyes A and B were added at a weight ratio of 200: 1 in a total amount of 1000 mg per mol of silver halide.

When a spectral sensitizing dye is added, the pH is adjusted to 7.60 and 1
After 5 minutes, add phenylcarbamylated gelatin and p with acetic acid
The H was lowered and the supernatant was removed by aggregation.

Preparation, Processing and Evaluation of Samples Chemical ripening was carried out in the same manner as in Example 1, and coating and drying were carried out in the same manner as in Example 1 using the same emulsion additives and protective layer solutions to obtain samples. .

The results of evaluation of the obtained sample for roller marks and development unevenness in the same manner as in Example 1 are shown in Table 2 below. According to the method of the present invention, the silver halide emulsion was converted to a flat plate having a high aspect ratio. Even when the particles were in the form of particles, a clear image was obtained without the occurrence of roller marks, uneven development and scratches.

[0121]

[Table 2]

[0122]

According to the present invention, high-sensitivity, high-quality silver halide photographic light-sensitive materials can be obtained by preventing development unevenness, roller marks, and abrasions caused by rapid processing by an automatic developing machine.

Continuation of the front page (58) Field surveyed (Int. Cl. ⁷ , DB name) G03C 1/76 501 G03C 1/76 502 G03C 1/04 501 G03C 1/053

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. Matting degree on the side having a photosensitive silver halide emulsion layer 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 the backing layer side A silver halide photographic light-sensitive material, wherein the difference from the matte degree is 50 mmHg or more.