JPH07120861A - Silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To provide a silver halide photographic sensitive material having improved physical properties of the film without adversely affecting the photographic characteristics and causing no coating trouble. CONSTITUTION:This silver halide photographic sensitive material contains at least one kind of compd. having repeating structural units represented by the formula in at least one layer on the transparent base. In the formula, R1 is H or alkyl, R2 is H, 1-22C alkyl or aryl and R3 is H, 1-22C alkyl or aryl.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a silver halide photographic light-sensitive material, and more particularly to a silver halide photographic light-sensitive material having improved film properties without impairing photographic characteristics.

[0002]

2. Description of the Related Art Generally, each constituent layer of a photographic light-sensitive material, such as an undercoat layer or a hydrophilic colloid layer, does not have a bad influence on the photographic light-sensitive property, and also has a physical property such as an adhesive strength before and after development. Predetermined strength is also required in terms of dimensional stability before and after development, dimensional stability against heat and humidity, flexibility, pressure resistance, and dryness. Therefore, conventionally, when a hydrophilic colloid layer such as a silver halide emulsion layer, an intermediate layer or a protective layer is coated on a support, a water-soluble polymer or polymer obtained by polymerizing various monomers in the hydrophilic colloid layer. Various attempts have been made to improve the physical properties of a hydrophilic colloid film formed by incorporating a latex, such as dimensional stability, scratching strength, flexibility, pressure resistance and drying property.

From such a viewpoint, use of an acrylamide derivative in JP-A-61-69061 and JP-A-61-151527 and use of a vinyl acetate polymer latex in US Pat. No. 2,376,005
In U.S. Pat. No. 3,325,286, a polymer latex of alkyl acrylate is used, and in JP-B-45-5331, a polymer latex of n-butyl acrylate, ethyl acrylate, styrene, butadiene, vinyl acetate, acrylonitrile, etc. is used. 46
-22506 discloses the use of a polymer latex of alkyl acrylate, acrylic acid and sulfoalkyl acrylate, and JP-A-51-130217 discloses the use of a polymer latex of 2-acrylamido-2-methylpropane sulfonic acid, etc. Each has been proposed. Further, in US Pat. No. 3666470 and US Pat. No. 3779766, it is proposed to use it together with a fluorescent whitening agent.

However, these polymer latices and water-soluble polymers have poor compatibility with hydrophilic colloids, resulting in a decrease in adhesive strength between layers and the occurrence of coating failures due to agglomerates in the coating liquid. There is a problem that the quality of the photographic light-sensitive material is significantly deteriorated.

[0005]

SUMMARY OF THE INVENTION The present invention has been made in view of the above problems. A first object of the present invention is to improve the film physical properties without adversely affecting the photographic characteristics and to provide an excellent silver halide photographic light-sensitive material. The second object is to provide a silver halide photographic light-sensitive material in which coating failure does not occur.

[0006]

The above object of the present invention is to provide at least one compound having a repeating structural unit represented by the following general formula (1) on at least one layer on a transparent support.
It has been achieved by a silver halide photographic light-sensitive material characterized by containing a seed.

[0007]

[Chemical 2]

In the formula, R ₁ is a hydrogen atom or an alkyl group, R ₂ is a hydrogen atom, an alkyl group or an aryl group having 1 to 22 carbon atoms, and R ₃ is a hydrogen atom or 1 to 2 carbon atoms.
2 represents an alkyl group or an aryl group.

Examples of the transparent support used in the present invention include triacetyl cellulose (TAC), polyethylene terephthalate (PET) and polyethylene naphthalate (PEN).

The compound having the structural unit represented by the general formula (1) used in the present invention includes N-vinylformamide, N-vinylacetamide, N-vinylpropionamide, N-vinyl-N-methylformamide and N-vinyl. -N-methylacetamide, N-vinyl-N-methylpropionamide, N-vinyl-N-ethylformamide and the like can be mentioned. Many methods of polymerizing these in an aqueous solution or modifying them are known (Japanese Patent Laid-Open No. 5-97931, etc.).

The compound having a structural unit represented by the above general formula (1) according to the present invention is 99% by weight of another copolymerizable monomer (hereinafter referred to as "other monomer"). % Or less, preferably 1 to 98% by weight, more preferably 10 to 90% by weight.

The compound having a structural unit represented by the above general formula (1) according to the present invention may be a water-soluble polymer or a hydrophobic polymer particle, and other types of monomers may be used. By adjusting the content, it can be easily made into any form.

Other copolymerizable monomers include:
For example, acrylic acid esters, methacrylic acid esters, vinyl esters, olefins, styrenes, crotonic acid esters, itaconic acid diesters, maleic acid diesters, fumaric acid diesters, acrylamides, allyl compounds, vinyl ethers, Examples thereof include vinyl ketones, vinyl heterocyclic compounds, glycidyl esters, unsaturated nitriles, polyfunctional monomers, and monomer compounds selected from a combination of two or more kinds selected from various unsaturated acids.

More specific examples of these monomer compounds include acrylic acid esters such as methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, 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-
Methoxy polyethylene glycol acrylate (additional mol number n = 9), 1-bromo-2-methoxyethyl acrylate, 1,1-dichloro-2-ethoxyethyl acrylate and the like can be mentioned.

Examples of methacrylic acid esters are methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, amyl methacrylate, chlorobenzyl methacrylate, sulfopropyl methacrylate, N-ethyl-N-phenylaminoethyl methacrylate, 2- (3-phenylpropyloxy) ethyl methacrylate, dimethylaminophenoxyethyl methacrylate, furfuryl methacrylate,
Tetrahydrofurfuryl methacrylate, phenyl methacrylate, cresyl methacrylate, naphthyl methacrylate, 2-hydroxyethyl methacrylate, 4-hydroxybutyl methacrylate, triethylene glycol monomethacrylate, dipropylene glycol monomethacrylate, 2-methoxyethyl methacrylate, 3-methoxybutyl methacrylate , 2-acetoxyethyl methacrylate, 2-acetoacetoxyethyl methacrylate,
2-ethoxyethyl methacrylate, 2-iso-propoxyethyl methacrylate, 2-butoxyethyl methacrylate, 2- (2-methoxyethoxy) ethyl methacrylate, 2-
(2-Ethoxyethoxy) ethyl methacrylate, 2- (2-butoxyethoxy) ethyl methacrylate, ω-methoxypolyethylene glycol methacrylate (additional mol number n =
6), allyl methacrylate, dimethylaminoethyl methyl methacrylate salt of methacrylic acid and the like.

Examples of vinyl esters include vinyl acetate, vinyl propionate, vinyl butyrate,
Examples thereof include vinyl isobutyrate, vinyl capronate, vinyl chloroacetate, vinyl methoxyacetate, vinyl phenyl acetate, vinyl benzoate, vinyl salicylate and the like.

Examples of olefins include dicyclopentadiene, ethylene, propylene, 1-butene, 1-pentene, vinyl chloride, vinylidene chloride, isoprene, chloroprene, butadiene and 2,3-dimethylbutadiene. it can.

Examples of styrenes include styrene,
Examples thereof include methylstyrene, dimethylstyrene, trimethylstyrene, ethylstyrene, isopropylstyrene, chloromethylstyrene, methoxystyrene, acetoxystyrene, chlorostyrene, dichlorostyrene, bromstyrene, trifluoromethylstyrene, and vinylbenzoic acid methyl ester.

Examples of crotonic acid esters include butyl crotonic acid and hexyl crotonic acid.

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

Examples of maleic acid diesters include diethyl maleate, dimethyl maleate, dibutyl maleate and the like.

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

Examples of acrylamides include acrylamide, methyl acrylamide, ethyl acrylamide, propyl acrylamide, butyl acrylamide, and tert-acrylamide.
Butylacrylamide, cyclohexylacrylamide, benzylacrylamide, hydroxymethylacrylamide, methoxyethylacrylamide, dimethylaminoethylacrylamide, phenylacrylamide,
Dimethyl acrylamide, diethyl acrylamide, β
-Cyanoethylacrylamide, N- (2-acetoacetoxyethyl) acrylamide and the like can be mentioned.

Examples of methacrylamides include methacrylamide, methyl methacrylamide, ethyl methacrylamide, propyl methacrylamide, butyl methacrylamide, tert-butyl methacrylamide, cyclohexyl methacrylamide, benzyl methacrylamide, hydroxymethyl methacrylamide, methoxy. Ethyl methacrylamide, dimethylaminoethyl methacrylamide, phenyl methacrylamide, dimethyl methacrylamide, diethyl methacrylamide, β-cyanoethyl methacrylamide, N- (2-acetoacetoxyethyl)
Methacrylamide and the like can be mentioned.

Examples of the allyl compound include allyl acetate, allyl caproate, allyl laurate, allyl benzoate and the like.

Examples of vinyl ethers include methyl vinyl ether, butyl vinyl ether, hexyl vinyl ether, methoxyethyl vinyl ether and dimethylaminoethyl vinyl ether.

Examples of vinyl ketones include methyl vinyl ketone, phenyl vinyl ketone, methoxyethyl vinyl ketone and the like.

Examples of the vinyl heterocyclic compound include vinyl pyridine, N-vinyl imidazole, N-vinyl oxazolidone, N-vinyl triazole, N-vinyl pyrrolidone and the like.

As the glycidyl esters, for example,
Examples thereof include glycidyl acrylate and glycidyl methacrylate.

Examples of unsaturated nitriles include acrylonitrile and methacrylonitrile.

Examples of polyfunctional monomers include divinylbenzene, 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 maleates such as monomethyl maleate, monoethyl maleate, monobutyl maleate, etc .; citraconic acid, styrene sulfonic acid, vinylbenzyl sulfonic acid, vinyl sulfone Acid, acryloyloxyalkyl sulfonic acid, for example, acryloyloxymethyl sulfonic acid, acryloyloxyethyl sulfonic acid, acryloyloxypropyl sulfonic acid, etc .; methacryloyloxyalkyl sulfonic acid, for example, methacryloyloxydimethyl sulfonic acid, methacryloyloxyethyl sulfonic acid, methacryloyl Oxypropyl sulfonic acid and the like; acrylamidoalkyl sulfonic acid, such as 2-acrylamide-2
-Methylethanesulfonic acid, 2-acrylamido-2-methylpropanesulfonic acid, 2-acrylamido-2-methylbutanesulfonic acid, etc .; methacrylamide alkylsulfonic acid, for example, 2-methacrylamido-2-methylethanesulfonic acid, 2 -Methacrylamido-2-methylpropanesulfonic acid, 2-methacrylamido-2-methylbutanesulfonic acid, etc .; acryloyloxyalkyl phosphates such as acryloyloxyethyl phosphate, 3-acryloyloxypropyl-2-phosphate, etc .; methacryloyloxyalkyl Phosphates such as methacryloyloxyethyl phosphate, 3-methacryloyloxypropyl-2-phosphate and the like; naphthyl 3-allyloxy-2-hydroxypropanesulfonate having two hydrophilic groups and the like can be mentioned. These acids may be salts of alkali metals (eg Na, K, etc.) or ammonium ions. Still other monomer compounds include U.S. Patents 3,459,790, 3,438,708 and 3,554,98.
7, 4,215,195, 4,247,673, JP-A-57-20573
The crosslinkable monomers described in the specification of Japanese Unexamined Patent Publication No. 5 can be used. Specific examples of such crosslinkable monomers include N- (2-acetoacetoxyethyl) acrylamide and N- {2- (2-acetoacetoxyethoxy) ethyl}.
Examples thereof include acrylamide.

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

Aromatic compounds such as styrene, α-methylstyrene, vinyltoluene and p-methylstyrene; methyl acrylate, ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, methyl methacrylate, 2-hydroxyethyl acrylate Acrylic acid such as 2-hydroxyethylmethacryl or alkyl esters of methacrylic acid; acrylic acid, methacrylic acid, crotonic acid,
Mono- or dicarboxylic acids such as maleic acid, fumaric acid, itaconic acid or anhydrides of dicarboxylic acids; butadiene,
Isoprene, 2-chloro-1,3-butadiene, 1-chloro-1,3
-Aliphatic conjugated dienes such as butadiene; vinyl cyanide compounds such as acrylonitrile and methacrylonitrile;
Vinyl chloride, vinylidene chloride, vinyl methyl ethyl ketone, vinyl methyl ether, vinyl acetate, vinyl formate,
Allyl acetate, methallyl acetate, acrylamide, methacrylamide, N-methylol acrylamide, glycidyl acrylate, glycidyl methacrylate, acrolein, and allyl alcohol are used.

The method of polymerizing the compound having the structural unit represented by the general formula (1) used in the present invention includes, for example, emulsion polymerization method, solution polymerization method, bulk polymerization method, suspension polymerization method, radiation polymerization method and the like. Is mentioned.

In solution polymerization, a mixture of monomers at a suitable concentration in a solvent (usually 40% by weight or less, preferably 10 to 25% by weight, based on the solvent) is added in an amount of about 10% in the presence of an initiator. ~
At a temperature of 200 ° C, preferably 30-120 ° C, about 0.5-48
It can be obtained by carrying out the polymerization for a time, preferably 2 to 20 hours.

Any initiator may be used as long as it is soluble in the polymerization solvent, and examples thereof include organic solvent initiators such as benzoyl peroxide, azobisisobutyronitrile (AIBN) and ditertiary butyl peroxide. Water-soluble initiators such as ammonium sulphate (APS), potassium persulfate, 2,2'-azobis- (2-amidinopropane) -hydrochloride, etc., combined with reducing agents such as Fe ²⁺ salts and sodium bisulfite A redox type polymerization initiator etc. can be mentioned.

Any solvent can be used as long as it can dissolve a mixture of monomers, and examples thereof include water, methanol, ethanol, dimethylsulfoxide, dimethylformamide, dioxane, and a mixed solvent of two or more thereof. be able to.

After completion of the polymerization, the unreacted mixture can be separated and removed by pouring the reaction mixture into a medium in which the produced copolymer is not dissolved, allowing the product to settle, and then drying.

In the emulsion polymerization method, water is used as a dispersion medium, and 10 to 50% by weight of the monomer is contained in the water and 0.05 to 50% by weight of the monomer.
It is obtained by polymerizing under stirring at about 30 to 100 ° C., preferably 60 to 90 ° C. for 3 to 8 hours using 5% by weight of a polymerization initiator and 0.1 to 20% by weight of a dispersant. The concentration of the monomer, the amount of the initiator, the reaction temperature, the time, etc. can be changed widely and easily.

As the initiator, water-soluble peroxides (eg potassium persulfate, ammonium persulfate, etc.), water-soluble azo compounds (eg 2,2'-azobis- (2-amidinopropane)-) are used.
Hydrochloride, etc.) N, N, N ′, N′-tetramethyl-ethylenediamine, or a redox-based polymerization initiator in which these are combined with a reducing agent such as Fe ²⁺ salt or sodium bisulfite.

Examples of the dispersant include anionic surfactants, nonionic surfactants, water-soluble polymers and the like.
In the suspension polymerization method, the raw material vinyl compound is obtained as an aqueous solution dispersed in a hydrocarbon dispersion medium. The aqueous solution concentration of the raw material monomer is polymerized at any concentration in the range of 5 to 95% by weight.

The hydrocarbon-based dispersion medium is preferably a hydrocarbon azeotropic with water. For example, n-hexane, n-heptane, n-
Chain saturated hydrocarbons such as octane, nonane, decane, undecane and dodecane, petroleum fractions with a boiling point of 65 to 250 ° C, preferably petroleum fractions with a boiling point of 80 to 180 ° C, alicyclic hydrocarbons such as cyclohexane and methylcyclohexane ,benzene,
Aromatic hydrocarbons such as toluene, xylene and ethylbenzene can be mentioned. The dispersion medium is usually used in an amount of 0.5 to 10 times by weight, preferably 1 to 5 times by weight, the aqueous solution of the raw material vinyl compound.

In the above suspension polymerization, a specific surfactant is used as a dispersion stabilizer. The surfactant used in the present invention is HLB (Hydrophilic Lipophilic Balance).
Is a nonionic surfactant having a molecular weight of 9 to 20, preferably 12 to 19, and is polyoxyethylene alkyl ether, polyoxyethylene alkylphenyl ether, sorbitol alkyl ester, sucrose alkyl ester, or the like, preferably polyoxyethylene octyl. Fel ether and polyoxyethylene alkylfel ether. Specifically, polyoxyethylene octyl ferrether, polyoxyethylene octyl phenyl ether, polyoxyethylene lauryl ether, polyoxyethylene oleyl ether, polyoxyethylene tridecyl ether, polyoxyethylene cetyl ether, polyoxyethylene stearyl ether, poly Examples include compounds such as oxyethylene phenyl ether, polyoxyethylene laurate, polyoxyethylene oleate, polyoxyethylene stearate, polyoxyethylene sorbitan laurate, polyoxyethylene sorbitan oleate, and polyoxyethylene sorbitan stearate. .

The amount of the above surfactant used is appropriately selected from the range of 0.01 to 5% by weight, preferably 0.05 to 1% by weight, based on the dispersion medium. A general radical polymerization initiator can be used as the polymerization initiator, but an azo compound is preferable. Particularly preferred is a water-soluble azo compound,
2'-azobis-2-amidinopropane hydrochloride, sulfate and acetate, azobis-N, N'-dimethyleneisobutylamidine hydrochloride, sulfate and acetate, 4,4'-azobis
Examples thereof include alkali metal salts and ammonium salts of 4-cyanovaleric acid. The radical polymerization initiator is 100 to 1000 ppm by weight based on the raw vinyl compound, preferably 50
Used in the range of 0-5000ppm. The method for adding the radical polymerization initiator is not particularly limited, but it is preferable to dissolve the radical polymerization initiator in an aqueous solution containing the raw material vinyl compound, and then disperse this in a hydrocarbon-based dispersion medium for polymerization. Further, in some cases, additives such as ammonium chloride and calcium chloride are used as a polymerization stabilizer. The additive is usually used in an amount of 0.1 to 20% by weight, preferably 1 to 15% by weight, based on all the monomers.

The polymerization temperature is usually 30 to 100 ° C., preferably 50.
~ 80 ° C. The polymerization time is usually 0.5 to 10 hours,
It is preferably 1 to 8 hours. In order to carry out the polymerization, the dispersion medium containing the surfactant is kept at the polymerization temperature, and the monomer aqueous solution containing the polymerization initiator is kept in a nitrogen gas stream. The method by adding to the dispersion medium under stirring is exemplified,
The mixing order of the monomer, the solvent and the auxiliary is not particularly limited.

The hydrous N-vinylcarboxylic acid amide polymer thus obtained is heated with stirring by using a hydrocarbon compound which is azeotropic with water as a dispersion medium, and dispersed by boiling distillation of water and the hydrocarbon dispersion medium. Water is removed in the state
N-vinyl carboxylic acid amide polymers can be produced. The polymer does not contain fine powder, and usually has a particle size of 0.1 to 3.0 mm,
In particular, it shows a bead-like shape with a uniform particle size of about 0.5 to 2.0 mm.

The N-vinylcarboxylic acid amide polymer obtained by the above method may be modified by hydrolysis in water under acidic or basic conditions, or in a hydrophilic solvent such as alcohol containing water. Examples of the method include hydrolysis and alcohol addition. The alcohol used for the addition of alcohol can be an alcohol having 1 to 4 carbon atoms, preferably methanol. The specifically modified portion is the second N-vinylcarboxylic acid amide.
A part of the amide, which is modified to form a primary amide group. Further, in the case of a copolymer, a part of the structure of the water-soluble vinyl compound used may be subject to modification.
For example, the nitrile group may become an amide group or a carboxyl group. The number average molecular weight of the compound having a repeating structural unit represented by the general formula (1) thus obtained cannot be uniquely determined depending on the intended use, but is usually calculated by GPC in terms of polystyrene or polyethylene oxide. About 500-5,000,000, preferably
It is 1,000 to 500,000.

Next, an example of a method for producing polymer particles having a repeating structural unit represented by the general formula (1) according to the present invention will be described.

(Production Method of Polymer Particles) Production Example 1 (Synthesis of P-1) A 1000 ml four-necked flask is equipped with a stirrer, a thermometer, a dropping funnel, a nitrogen introducing pipe and a reflux condenser to introduce nitrogen gas. Then, while deoxidizing, 400 g of toluene and 2 g of polyoxyethylene oleyl ether (HLB = 14.0) were added as a dispersion medium, and the temperature was raised to 60 ° C. with stirring. N-vinyl formamide 76
g, 53 g of acrylonitrile, and 0.2 g of 2,2'-azobis-2-amidinopropane dihydrochloride were added to water to make a total amount of 210 g. A solution was added dropwise over 3 hours into a dispersion medium kept at 60 ° C under stirring. . Then, the reaction was carried out by stirring at 60 ° C. for 3 hours. Next, an azeotropic distillation tube for esterification reaction was attached between the cooling tube and the 4-necked flask, the bath temperature was raised to 90 ° C., and water-toluene azeotropic distillation was carried out with stirring to remove water in the polymer. It was After cooling to 40 ° C, the product was filtered with Nuttier and dried by ventilation with toluene.

Specific examples of the compound having the structural unit represented by the general formula (1) according to the present invention are shown below, but the present invention is not limited thereto.

[0052]

[Chemical 3]

[0053]

[Chemical 4]

The Tg (glass transition temperature) of the polymer forming the hydrophobic polymer particles used in the present invention is preferably higher than the developing temperature, and particularly 5 ° C. higher than the developing temperature.
It is preferably higher than the above.

The Tg of many polymers of ethylenic monomers used in the present invention are described in Brand Wrap et al., "Polymer Handbook", pages III-139 to III-179 (1966, Wiley and Sun). The Tg (° K) of the copolymer is represented by the following formula.

Tg (copolymer) = v ₁ Tg ₁ + v ₂ Tg ₂ +
... + v _W Tg _W However, in the above formula, v ₁ , v ₂ ... v _W represent the weight fraction of the monomers in the copolymer, and Tg ₁ , Tg ₂ ... Tg _W represent the respective monomers in the copolymer. Represents the Tg (° K) of a homopolymer. The Tg calculated according to the above equation has an accuracy of ± 5 ° C.

Regarding the method for synthesizing the hydrophobic polymer particles of the present invention, US Pat. Nos. 2,852,386, 2,853,457 and 3,41
1,911, 3,411,912, 4,197,127, Belgian Patents 688,882, 691,360, 712,823, Japanese Patent Publication No. 45-53
31, JP-A-60-18540, JP-A-51-130217, JP-A-58-137831
No. 55-50240 and the like.

The average particle diameter of the hydrophobic polymer particles of the present invention is particularly preferably 0.01 to 0.8 μm, and any one having an average particle diameter of 0.005 to 2.0 μm can be preferably used.

The hydrophobic polymer particles of the present invention can be contained in the photographic constituent layers as they are or after being dispersed in water. The content of the hydrophobic polymer particles is preferably 5 to 60% by weight based on the binder of the photographic constituent layer. The addition place may be a photosensitive layer or a non-photosensitive layer.

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

Next, an example of the method for producing the hydrophobic polymer particles will be described.

(Production Method of Hydrophobic Polymer Particles) Production Example 2 (Synthesis of Lx-1) A 1,000 ml four-necked flask was provided with a stirrer, a thermometer, a dropping funnel, a nitrogen introduction tube, and a reflux condenser, and nitrogen was added. While introducing gas and performing deoxidation, 350 cc of distilled water was added and heated until the internal temperature reached 80 ° C. P-1 according to the present invention was used as a dispersant.
4.5g was added, and ammonium persulfate was used as an initiator.
0.45 g is added, and then 90 g of methyl methacrylate is added dropwise with a dropping funnel over about 1 hour. After the completion of dropping, the reaction is continued for 4 hours as it is, and then unreacted monomers are removed by steam distillation. Then, it is cooled and adjusted to pH 6 with aqueous ammonia to obtain hydrophobic polymer particles. Tg was 105 ° C.

Production Example 3 (Synthesis of Lx-2) 200 ml of dioxane was placed in a 500 ml three-necked flask and deoxidized with nitrogen gas. Then, 40 g of N-vinylformamide according to the present invention and 80 g of methyl methacrylate were added, and further 1.2 g of dimethyl azobisisobutyrate as an initiator.
Add and continue the reaction at 60 ° C for 6 hours. After completion of the reaction, the reaction solution is added to 3 l of distilled water with vigorous stirring to obtain white crystals.

The white crystals were collected by filtration, dried, dissolved in 100 ml of ethyl acetate, added to 500 ml of distilled water containing 2 g of sodium dodecylbenzenesulfonate (SF-1) with vigorous stirring, and then ethyl acetate was removed. Then, hydrophobic polymer particles are obtained. Tg was 62 ° C.

Specific examples of the hydrophobic polymer particles according to the present invention are shown below.

[0066]

[Chemical 5]

[0067]

[Chemical 6]

[0068]

[Chemical 7]

As the binder for the silver halide emulsion layer, it is advantageous to use gelatin or a gelatin derivative.

Examples of gelatin include lime-processed gelatin, Bulletin of the Society of Scientific Photography of Japan (Bull. Soc. Sci. Phot. Japan) No. 16, p. 30. (1966)
The acid-treated gelatin as described in 1. may be used, and a hydrolyzate or an oxygen hydrolyzate of gelatin can also be used. As the gelatin derivative, various compounds such as acid halides, acid anhydrides, isocyanates, bromoacetic acid, alkane sultones, vinyl sulfonamides, maleinimide compounds, polyalkylene oxides, epoxy compounds are added to gelatin. What is obtained by reaction is used. Specific examples thereof are U.S. Patents 2,614,928 and 3,13.
2,945, 3,186,846, 3,312,553, British patent 86
1,414, 1,033,189, 1,005,784, Japanese Patent Publication 42-26
It is described in No. 845, etc.

The silver halide emulsion used in the present invention is used as a silver halide in a usual silver halide emulsion such as silver bromide, silver iodobromide, silver iodochloride, silver chlorobromide, and silver chloride. Any of the above can be used.

The silver halide grains may be those having a uniform silver halide composition distribution within the grain, or may be core / shell grains in which the silver halide composition is different between the inside of the grain and the surface layer. Further, the particles may be such that the latent image is mainly formed on the surface, or the particles are mainly formed inside the particles.

The silver halide grains used in the silver halide emulsion used in the present invention may have a regular crystal form such as a cube, an octahedron or a tetradecahedron, or may have a spherical or plate shape. It may have an irregular crystal form. In these grains, any ratio of {100} plane to {111} plane can be used. Further, it may have a composite form of these crystal forms, and particles of various crystal forms may be mixed.

The average grain size of silver halide grains (grain size represents the diameter of a circle having an area equal to the projected area) is
The thickness is preferably 5 μm or less, and particularly preferably 3 μm or less.

The silver halide emulsion used in the present invention may have any grain size distribution. An emulsion having a wide grain size distribution (referred to as a polydisperse emulsion) may be used, or an emulsion having a narrow grain size distribution (referred to as a monodisperse emulsion. The monodisperse emulsion referred to here is the standard deviation of the grain size distribution. When divided by the average grain size, the value is 0.20 or less, where the grain size is the diameter in the case of spherical silver halide and the projected image in the case of grains other than spherical. The diameter when converted to a circular image of the same area is shown). Further, a polydisperse emulsion and a monodisperse emulsion may be mixed and used.

The silver halide emulsion used in the present invention may be a mixture of two or more kinds of silver halide emulsions formed separately.

The silver halide emulsion used in the present invention can be chemically sensitized by a conventional method. That is, the sulfur sensitization method,
A selenium sensitization method, a reduction sensitization method, a noble metal sensitization method using gold or other noble metal compound can be used alone or in combination.

The silver halide emulsion layer may contain a dye-forming coupler to prepare a color light-sensitive material.

That is, the silver halide photographic light-sensitive material of the present invention is specifically, for example, an X-ray light-sensitive material, a lith light-sensitive material,
It can be applied to black-and-white photographic light-sensitive materials, color negative light-sensitive materials, color reversal light-sensitive materials, color photographic papers, etc., and when applied to color photographic light-sensitive materials, it can also be used as a single color light-sensitive material, and multicolor color light-sensitive materials Can also be used as A multicolor color light-sensitive material usually has a dye image-forming constituent unit having photosensitivity in each of the three primary color regions of the spectrum, and each constituent unit is a single-layer emulsion layer or a multilayer emulsion having sensitivity to a certain region of the spectrum. It may be composed of layers (in this case, it is preferable that the respective emulsion layers have different sensitivities), and may have layers such as a filter layer, an intermediate protective layer and an undercoat layer.

The layers of the light-sensitive material, including the layers of the image-forming units, can be applied in various orders as known in the art.

For example, as a subbing layer, an antihalation layer, a cyan-colored red-sensitive emulsion layer, an intermediate layer, a magenta-colored green-sensitive emulsion layer, an intermediate layer, a yellow-colored blue-sensitive emulsion layer and a protective layer in this order from the support. The matting agent of the present invention may be contained in the protective layer which is the surface layer, and the latex of the present invention may be contained in each layer. Each color-developing layer can have a two-layer structure with high sensitivity and low sensitivity.

When embodied in a typical multicolor color light-sensitive material, it is a cyan dye image-forming structural unit consisting of at least one red-sensitive silver halide emulsion layer having at least one cyan dye-forming coupler, at least A magenta dye image-forming structural unit comprising at least one green-sensitive silver halide emulsion layer having one magenta dye-forming coupler, and a yellow comprising at least one blue-sensitive silver halide emulsion layer having at least one yellow dye-forming coupler. It comprises a dye image-forming structural unit coated on a support together with a non-photosensitive layer.

In the multicolor color light-sensitive material, an open-chain ketomethylene compound such as a pivaloylacetanilide type or benzoylacetanilide type yellow coupler may be used as a yellow coupler.

As the magenta coupler, 5-pyrazolone type couplers, pyrazolobenzimidazole type couplers, pyrazoloazole type couplers such as pyrazolotriazole type couplers and open chain acylacetonitrile type couplers can be preferably used.

As the cyan dye-forming coupler, a naphthol type coupler and a phenol coupler can be preferably used.

Further, in order to improve the photographic characteristics, a coupler which forms a colorless dye, which is a so-called competing coupler, can be contained.

In the silver halide emulsion layer, a so-called DI that releases a development inhibitor or its precursor in addition to the coupler is used.
An R substance, for example, a diffusible DIR substance, a timing DIR substance, or a hydroquinone derivative may be contained in order to prevent unnecessary fog and contamination due to air oxidation of the developing agent.

Further, these silver halide photographic light-sensitive materials may contain a compound obtained by hydrolyzing the compound represented by the general formula (1).

[0089]

【Example】

Example 1 On a subbed polyethylene terephthalate support, a backing layer (coating gelatin amount: 2.0 g / m ² ) was prepared using the following coating solution for backing layer, and a backing protective layer (coating was prepared using the coating solution for backing layer protective film layer). Gelatin amount 1.5g / m ² )
On the other side of the undercoat layer on the opposite side of the support, using the following silver halide photographic material coating solution formulation, an emulsion layer (coating gelatin amount 2.0 g / m ² ) and an emulsion protective layer (coating gelatin amount 1.0). g
/ M ² ), four layers are coated at the same time and dried, and then photographic material sample 1
~ 24 were made.

[Preparation of coating solution for backing layer] Gelatin
After swelling 36 g in water, heating and dissolving, 1.6 g of compound (C-4), 310 mg of compound (C-5), compound (C
-6) An aqueous solution of 1.9 mg and compound (N) 2.9 g was added, then 11 ml of a 20% saponin aqueous solution and 5 g of compound (C-7) as a physical property modifier were added, and further compound (C-
8) 63 mg of methanol solution was added.

To this solution, 800 g of a water-soluble styrene-maleic acid copolymer was added as a thickening agent to adjust the viscosity, and then a pH of 5.4 was adjusted using an aqueous citric acid solution to react polyglycerol with epichlorohydrin. 1.5g product
Add 144 mg of glyoxal, add water and add 960
The coating solution for the backing layer was prepared by finishing to a milliliter.

[Preparation of Coating Solution for Protective Layer of Backing Layer] After swelling 50 g of gelatin in water and dissolving with heating, 340 mg of 2-sulfonate-bis (2-ethylhexyl) succinate ester sodium salt was added, and sodium chloride was added. Of glyoxal (1.1 g) and mucochloric acid (540 mg) were added. To this, spherical polymethylmethacrylate having an average particle diameter of 4 μm was added as a matting agent so as to have a concentration of 40 mg / m ² ,
Water was added to make 1 liter and a protective film coating solution was prepared.

[Preparation of Silver Halide Emulsion Coating Solution] After adding 9 mg of the compound (A) to the following emulsion, the pH was adjusted to 6.5 using 0.5N sodium hydroxide solution, and then 360 mg of the compound (T). In addition, 5 ml of a 20% saponin aqueous solution, 180 mg of sodium dodecylbenzene sulfonate, 80 mg of 5-methylbenztriazole, and 43 mg of latex (L) for emulsion addition below were added per mol of silver halide.
The compound (M) was added in an amount of 60 ml, styrene-maleic acid copolymer water-soluble polymer (280 mg) as a thickening agent, and the compound of the present invention (described in Table 1) were sequentially added, followed by addition of 47 with water.
The silver halide emulsion coating solution was prepared by finishing to 5 ml.

[Preparation of Emulsion] A silver chlorobromide emulsion having a silver bromide content of 2 mol% was prepared as follows.

23.9 mg of pentabromorhodium potassium salt per 60 g of silver nitrate, an aqueous solution containing sodium chloride and potassium bromide, and an aqueous solution of silver nitrate were stirred in an aqueous gelatin solution at the same time for 25 minutes at 40 ° C. and averaged. Particle size 0.
A 20 μm silver chlorobromide emulsion was prepared.

After adding 200 mg of 6-methyl-4-hydroxy-1,3,3a, 7-tetrazaindene as a stabilizer to this emulsion,
It was washed with water and desalted.

To this was added 20 mg of 6-methyl-4-hydroxy-1,3,
After adding 3a, 7-tetrazaindene, it was sensitized with sulfur.
After sulfur sensitization, gelatin was added and 6-methyl was added as a stabilizer.
An emulsion was prepared by adding 4-hydroxy-1,3,3a, 7-tetrazaindene and then making up to 260 ml with water.

[Preparation of Latex (L) for Emulsion Addition] Water
To 40 liters, 0.25 kg of KMDS (dextran sulfate sodium salt) manufactured by Meito Sangyo and ammonium persulfate 0.
To a liquid containing 05 kg, a mixture of 4.51 kg of n-butyl acrylate, 5.49 kg of styrene and 0.1 kg of acrylic acid was added over 1 hour in a nitrogen atmosphere while stirring at a liquid temperature of 81 ° C., and then 0.005 of ammonium persulfate was added. kg was added, and the mixture was further stirred for 1.5 hours, cooled, and adjusted to pH 6 with aqueous ammonia.

The obtained latex liquid was used as GF manufactured by Whotman.
The mixture was filtered with a / D filter and the weight was adjusted to 50.5 kg with water to prepare a monodisperse latex (L) having an average particle diameter of 0.25 μ.

[Preparation of Coating Solution for Emulsion Protective Film] Water was added to gelatin to swell it and dissolve it at 40 ° C., then as a coating aid,
A 1% aqueous solution of the compound (Z), a 1% aqueous solution of the compound (Y), the compound (N) as a filter dye, and the compound (D) were sequentially added, and the pH was adjusted to 6.0 with citric acid. A matting agent (amorphous silica having a particle size of 4.0 μm) was added, and the compound of the present invention was further added as shown in Table 1 to prepare a coating solution for emulsion protective film.

[0101]

[Chemical 8]

[0102]

[Chemical 9]

[0103]

[Chemical 10]

Each of the obtained samples was exposed to white light through a step wedge for measuring sensitometry, and then a sample subjected to the following treatment and a sample subjected to the following treatment without exposure were prepared.

[Processing Conditions] Process Temperature (° C.) Time (sec) Development 34 15 Fixing 34 15 Washing with water Normal temperature 10 Drying 40 9 [Developer formulation] (Composition A) Water 150 ml Ethylenediaminetetraacetic acid disodium salt 2 g Diethylene glycol 50 g Sulfurous acid Potassium (55% w / v aqueous solution) 100 ml Potassium carbonate 50 g Hydroquinone 15 g 5-Methylbenzotriazole 200 mg 1-Phenyl-5-mercaptotetrazole 30 mg Potassium hydroxide Amount to bring the pH of the used solution to 10.9 Potassium bromide 4.5 g (composition B) Water 3 ml Diethylene glycol 50 g Ethylenediaminetetraacetic acid disodium salt 25 mg Acetic acid (90% w / w aqueous solution) 0.3 ml 5-Nitroindazole 110 mg 1-Phenyl-3-pyrazolidone 500 mg When the developer is used, the above composition is added to water 500 ml. Melt product A and composition B in this order, add water and add 1 liter. It was used to finish in Le.

[Fixer Formulation] (Composition A) Ammonium thiosulfate (72.5% w / v aqueous solution) 230 ml Sodium sulfite 9.5 g Sodium acetate trihydrate 15.9 g Boric acid 6.7 g Sodium citrate dihydrate 2 g Acetic acid (90 % W / v aqueous solution) 8.1 ml (Composition B) Water 17 ml Sulfuric acid (50% w / w aqueous solution) 5.8 g Aluminum sulphate (Al2O3 equivalent content is 8.1% w / w aqueous solution) 26.5 g Water when using fixer 500 The above composition A in milliliters,
The composition B was melted in this order, and water was added to make 1 liter. The pH of this fixer was about 4.3.

The above% w / w is (% weight) / (weight)
And% w / v represents (% weight) / (volume).

The obtained samples 1 to 6 were evaluated by the evaluation methods shown below. The results are shown in Table 1.

[Evaluation Method] (Haze) The unexposed sample treated in the above treatment step was measured using a turbidimeter Model T-2600DA manufactured by Tokyo Denshoku Co., Ltd., and haze was shown in%.

(Coating Finish) The number of lumps existing in 100 cm ^{2 of the} unexposed sample treated in the above-mentioned treatment step was visually counted.

(Photographic Performance) The exposed sample processed in the above-mentioned processing step was measured with a Konica sensitometer KS-1 type. The reciprocal of the exposure amount giving the density of fog +0.7 was taken as the sensitivity, and the sensitivity was shown as the specific sensitivity with the same day sensitivity of the control sample as 100.

(Scratch) After developing, fixing and washing with water in the above-mentioned processing step, the minimum metal that is scratched by scratching the film surface with a weighted metal needle while still immersed in the developing solution at the specified developing temperature. The weight of the needle (scratch strength) was determined.

The results are shown in Table 1.

[0114]

[Table 1]

From the results shown in Table 1, the photographic properties (sensitivity), film physical properties [haze (turbidity, transparency), coating finish (tailing coating failure due to solidification), scratches, and scratches were observed in all cases using the compound of the present invention. It can be seen that (scratch) strength] is excellent.

Example 2 One side (surface) of triacetyl cellulose film support
Was subjected to a subbing process, and then a back layer having the following composition was sequentially formed from the support side on the surface (back layer) opposite to the surface subjected to the subbing process while sandwiching the support.

Back Layer First Layer The following back layer first layer coating liquid was applied at a rate of 20 ml / m ² and dried at 80 ° C. for 5 minutes.

Alumina sol AS-100 (manufactured by Nissan Kagaku Kogyo Co., Ltd.) 40 g Acetone 500 ml Methanol 400 ml Dimethylformamide 100 ml Back layer second layer 20 ml of the following back layer second layer coating liquid on the back layer first layer It was coated so as to have a surface area of m ² and dried at 80 ° C. for 5 minutes.

Diacetylcellulose 1 g SiO ₂ fine particles (average particle size 3.0 μm) 0.02 g Acetone 500 ml Ethyl acetate 500 ml Back layer 3rd layer The following back layer 3rd layer coating liquid is applied on the back layer 2nd layer.
It was applied at 20 ml / m ² and dried at 90 ° C. for 5 minutes.

Toluene 700 ml Methyl ethyl ketone 300 ml Carnauba wax 1 g Next, each layer having the composition shown below was sequentially formed on the surface side (emulsion layer side) of the support provided with a back layer from the support side to obtain a multilayer color photographic light-sensitive material sample No. 25 created. In addition, the addition amount of the composition indicates the number of grams per 1 m ² unless otherwise specified. Also, silver halide and colloidal silver are shown in terms of silver.

First layer; antihalation layer (HC) Black colloidal silver 0.15 UV absorber (UV-1) 0.20 Colored cyan coupler (CC-1) 0.02 High boiling point solvent (Oil-1) 0.20〃 (Oil-2) 0.20 Gelatin 1.6 Second layer; Intermediate layer (IL-1) Gelatin 1.3 Third layer; Low-sensitivity red-sensitive emulsion layer (RL) Silver iodobromide emulsion (average grain size 0.3 μm, average iodine content 2.0 mol%) 0.4 Silver iodobromide emulsion (average grain size 0.4 μm, average iodine content 8.0 mol%) 0.3 Sensitizing dye (S-1) 3.2 × 10 ⁻⁴ (mol / silver 1 mol) 〃 (S-2) 3.2 × 10 ^-4 (〃) 〃 (S-3) 0.2 × 10 ^-4 (〃) Cyan coupler (C-1) 0.50 〃 (C-2) 0.13 Colored cyan coupler (CC-1) 0.07 DIR compound ( D-1) 0.006 〃 (D-2) 0.01 High boiling point solvent (Oil-1) 0.55 Additive (SC-1) 0.003 Gelatin 1.0 Fourth layer; High-sensitivity red-sensitive emulsion layer (RH) Silver iodobromide Agent (average particle size 0.7 [mu] m, an average iodide content of 7.5 mol%) 0.9 Sensitizing dye (S-1) 1.7 × 10 -4 ( mol / 1 mol of silver) 〃 (S-2) 1.6 × 10 -4 ( 〃 ) 〃 (S-3) 0.1 × 10 ^-4 (〃) Cyan coupler (C-2) 0.23 Colored cyan coupler (CC-1) 0.03 DIR compound (D-2) 0.02 High boiling point solvent (Oil-1) 0.25 added Agent (SC-1) 0.003 Gelatin 1.0 Fifth layer; Intermediate layer (IL-2) Gelatin 0.8 Sixth layer; Low-sensitivity green-sensitive emulsion layer (GL) Silver iodobromide emulsion (average grain size 0.4 μm, average Iodine content 8.0 mol%) 0.6 Silver iodobromide emulsion (average grain size 0.3 μm, average iodine content 2.0 mol%) 0.2 Sensitizing dye (S-4) 6.7 × 10 ^-4 (mol / silver 1 mol) 〃 (S-5) 0.8 × 10 ^-4 (〃) Magenta coupler (M-1) 0.17 〃 (M-2) 0.43 Colored magenta coupler (CM-1) 0.10 DIR compound (D-3) 0.02 High boiling point solvent (Oil-2) 0.70 Additive (SC- 1) 0.003 gelatin 1.0 seventh layer; high-sensitivity green-sensitive emulsion layer (GH).

Silver iodobromide emulsion (average particle size: 0.7 μm, average iodine content: 7.5 mol%) 0.9 Sensitizing dye (S-6) 1.1 × 10 ⁻⁴ (mol / silver 1 mol) Sensitizing dye (S- 7) 2.0 × 10 ^-4 (〃) 〃 (S-8) 0.3 × 10 ^-4 (〃) Magenta coupler (M-1) 0.03 〃 (M-2) 0.13 Colored magenta coupler (CM-1) 0.04 DIR compound (D-3) 0.004 High boiling point solvent (Oil-2) 0.35 Gelatin 1.0 Eighth layer; Yellow filter layer (YC) Yellow colloidal silver 0.1 Additive (HS-1) 0.07 Additive (HS-2) 0.07 High boiling point solvent (Oil-2) 0.15 Gelatin 1.0 Ninth layer; Low-sensitivity blue-sensitive emulsion layer (BL) Silver iodobromide emulsion (average grain size 0.3 μm, average iodine content 2.0 mol%) 0.25 Silver iodobromide emulsion ( Average particle size 0.4 μm, average iodine content 8.0 mol%) 0.25 Sensitizing dye (S-9) 5.8 × 10 ^-4 (mol / silver 1 mol) Yellow coupler (Y-1) 0.60 〃 (Y-2) 0.32 DI Compound (D-1) 0.003 〃 (D-2) 0.006 High boiling point solvent (Oil-2) 0.18 Gelatin 1.3 10th layer; High-sensitivity blue-sensitive emulsion layer (BH) Silver iodobromide (average particle size 0.8 μm , Average iodine content 8.5 mol%) 0.5 Sensitizing dye (S-10) 3.0 × 10 ^-4 (mol / silver 1 mol) 〃 (S-11) 1.2 × 10 ^-4 (〃) Yellow coupler (Y-1 ) 0.18 〃 (Y-2) 0.10 High boiling point solvent (Oil-2) 0.05 Gelatin 1.0 11th layer; 1st protective layer (PRO-1) Silver iodobromide (average particle size 0.08 μm, average iodine content 0.08 mol) %) 0.3 UV absorber (UV-1) 0.07 〃 (UV-2) 0.1 Additive (HS-1) 0.2 Additive (HS-2) 0.1 High boiling solvent (Oil-1) 0.07 〃 (Oil-3) 0.07 Gelatin 0.8 12th layer; 2nd protective layer (PRO-2) Polymethylmethacrylate (average particle size 3 μm) 0.02 Methylmethacrylate: ethylmethacrylate: methacrylic acid = 3: 3: 4 (weight ratio) Polymer (average particle size 3 [mu] m) 0.13 Gelatin 0.5 Silver iodobromide grain emulsion used in the 10th layer was prepared in the following manner.

A silver iodobromide emulsion was prepared by the double jet method using monodispersed silver iodobromide grains having an average grain size of 0.33 μm (silver iodide content: 2 mol%) as seed crystals. Solution <G-1>
While maintaining the temperature at 70 ° C., pH 7.8 and pH 7.0, 0.34 mol of seed emulsion was added while stirring well.

(Formation of Internal High Iodity Phase-Core Phase) After that, the solution <H-1> and the solution <S-1> were accelerated at a flow rate of 1: 1 while maintaining the flow rate ratio of 1: 1. The flow rate was 3.6 times the initial flow rate) and was added over 86 minutes.

(Formation of External Low Iodity Phase-Shell Phase) Subsequently, while maintaining the pH at 10.1 and the pH at 6.0, the solution <H-2> and the solution <S-2> were mixed at a flow rate ratio of 1: 1. Was added over 65 minutes at a flow rate accelerated by (the flow rate at the end was 5.2 times the initial flow rate). PAg and pH during particle formation are 5
Controlled with 6% aqueous acetic acid. After the particles were formed, they were washed with water by a conventional flocculation method, and then gelatin was added to redisperse them, and pH and pAg were adjusted to 5.8 and 8.06 at 40 ° C., respectively. The resulting emulsion had an average grain size of 0.80 μm, a distribution of 12.4% and a silver iodide content of 8.5.
It was a monodisperse emulsion containing mol% octahedral silver iodobromide grains.

<G-1> Ocein gelatin 100.0 g 10% by weight compound- [I] solution in methanol 25.0 ml 28% aqueous ammonia solution 440.0 ml 56% acetic acid aqueous solution 660.0 ml water 5000.0 ml <H-1> ossein gelatin 82.4g Potassium bromide 151.6g Potassium iodide 90.0g Finish with water 1030.5ml <S-1> Silver nitrate 309.2g 28% ammonia solution Equivalent Finish with water 1030.5ml <H-2> Ocein gelatin 302.1g Potassium bromide 770.0g Potassium iodide 33.2g Finished with water 3776.8ml <S-2> Silver nitrate 1130.0g 28% aqueous ammonia solution Equivalent finished with water 3776.8ml In the same manner, average particle size of seed crystal, temperature, pAg, pH,
The emulsions having different average grain sizes and different silver iodide contents were prepared by changing the flow rate, addition time, and halide composition.

All were core / shell type monodisperse emulsions having a distribution of 20% or less. Each emulsion was subjected to optimum chemical ripening in the presence of sodium thiosulfate, chloroauric acid and ammonium thiocyanate to obtain a sensitizing dye, 4-hydroxy-6-
Methyl-1,3,3a, 7-tetrazaindene and 1-phenyl-5-
Mercaptotetrazole was added.

The above-mentioned photosensitive material sample was further prepared by using the compound S.
u-1, Su-2 Viscosity modifier, Hardener H-1, H-
2, stabilizer ST-1, antifoggant AF-1, AF-2
(Weight average molecular weight 10,000 and 1,100,000),
Dyes AI-1, AI-2 and Compound DI-1 (9.4 mg / m
² ) is included.

[0129]

[Chemical 11]

[0130]

[Chemical 12]

[0131]

[Chemical 13]

[0132]

[Chemical 14]

[0133]

[Chemical 15]

[0134]

[Chemical 16]

[0135]

[Chemical 17]

[0136]

[Chemical 18]

[0137]

[Chemical 19]

[0138]

[Chemical 20]

Next, as shown in Table 2, the second, third, fifth,
The same procedure as in Sample No. 25 except that the following Comparative Compounds 1 and 2 and a compound having a repeating structural unit represented by the above general formula (1) used in the present invention were added to Layers 6, 9 and 12 Samples No. 26 to No. 39 were produced.

(Evaluation of Coating Finish) The number of lumps existing in 100 cm ^{2 of} the sample treated in the following treatment step was visually counted.

(Measurement Method of Pressure Fog) Sample 35 mm × in a dark room
It was cut into a size of 111 mm, stored in a cartridge having an inner diameter of 22 mm, and forcibly deteriorated (at 23 ° C., 80% RH for 1 day) while being loaded in a camera FT-1 manufactured by Konica Corporation. Thereafter, the photosensitive material samples were all wound up and developed according to the following processing steps to evaluate the pressure fog. The yellow density of the spotted fog that occurred and the non-fogged portion on the sample tip side were measured with a microdensitometer, and the density difference ΔD was determined and evaluated according to the following criteria.

◯: 0 to 0.06 Δ: 0.07 to 0.12
×: 0.12 to 0.19 ×: 0.20 or more (Evaluation of photographic performance) Each of the samples prepared as described above was
After wedge exposure using white light, the following development processing was performed.

Treatment step A Treatment time Treatment temperature Complementary amount Color development 3 minutes 15 seconds 38 ° C. 780 ml Bleach 45 seconds 38 ° C. 150 ml Settling 1 minute 30 seconds 38 ° C. 830 ml Stabilization 60 seconds 38 ° C. 830 ml Dry 1 minute 55 ° C- (The amount of replenishment is the value per 1 m ² of the light-sensitive material.) However, the stabilizing process was carried out by the 3-tank cascade method.

Color developer Water 800 ml Potassium carbonate 30 g Sodium hydrogen carbonate 2.5 g Potassium sulfite 3.0 g Sodium bromide 1.3 g Potassium iodide 1.2 mg Hydroxylamine sulfate 2.5 g Sodium chloride 0.6 g 4-Amino-3-methyl-N- Ethyl-N- (β-hydroxylethyl) aniline sulfate 4.5g Diethylenetriaminepentaacetic acid 3.0g Potassium hydroxide 1.2g Add water to make 1 liter and add potassium hydroxide or 20%
Adjust to pH 10.06 with sulfuric acid.

Color developing replenisher liquid 800 ml Potassium carbonate 35 g Sodium hydrogen carbonate 3 g Potassium sulfite 5 g Sodium bromide 0.4 g Hydroxylamine sulphate 3.1 g 4-Amino-3-methyl-N-ethyl-N- (β-hydroxylethyl) Aniline sulfate 6.3 g Potassium hydroxide 2 g Diethylenetriaminepentaacetic acid 3 g Add water to make 1 liter, and adjust to pH 10.18 with potassium hydroxide or 20% sulfuric acid.

Bleaching solution Water 700 ml 1,3-Diaminopropanetetraacetic acid ammonium ferric acid 175 g Ethylenediaminetetraacetic acid disodium 2 g Sodium nitrate 50 g Ammonium bromide 150 g Glacial acetic acid 40 g Water was added to make 1 liter, and ammonia water or glacial acetic acid was added. Use it to adjust pH appropriately to 4.4.

Bleaching Replenishing Solution Water 700 ml 1,3-Diaminopropanetetraacetic acid Ammonium ferric acid 180 g Ethylenediaminetetraacetic acid disodium 2 g Sodium nitrate 50 g Ammonium bromide 200 g Glacial acetic acid 56 g pH 4.0 using ammonia water or glacial acetic acid After the adjustment, add water to make 1 liter.

Fixing solution 800 ml Ammonium thiosulfate 150 g Ammonium thiocyanate 120 g Sodium sulfite 15 g Ethylenediaminetetraacetic acid disodium 2 g After adjusting the pH to 6.2 using acetic acid and ammonia water, add water to make 1 liter.

Fixing replenisher liquid 800 ml Ammonium thiosulfate 180 g Ammonium thiocyanate 150 g Sodium sulfite 20 g Ethylenediaminetetraacetic acid disodium 2 g After adjusting the pH to 6.5 using acetic acid and aqueous ammonia, add water to make 1 liter.

Stabilizer and stable replenisher Paraoctylphenol ethylene oxide 10 mol adduct 2.0 g Dimethylol urea 0.5 g Hexamethylenetetramine 0.2 g 1,2-Benzisothiazolin-3-one 0.1 g Siloxane (UC-L-77) 0.1 g Ammonia Water 0.5 ml Water was added to make 1 liter, and the pH was adjusted to 8.5 with aqueous ammonia and 50% sulfuric acid.

The exposed sample treated in the above treatment step was measured with a photometer KS-1 manufactured by Konica Corporation. The reciprocal of the exposure amount that gives a density of fog +0.7 was defined as the sensitivity, and the sensitivity of Sample No. 25 was defined as 100, and the specific sensitivity was shown.

(Evaluation of Scratch) The unexposed sample was developed, fixed and washed with water in the above-mentioned processing steps, and then, while still immersed in the developing solution at the specified developing temperature, the surface of the film was scratched with a heavy metal needle. The minimum weight (scratch strength) of the metal needle that is scratched by scratches was determined.

The results are shown in Table 2.

[0154]

[Table 2]

[0155]

[Chemical 21]

From the results shown in Table 2, all of those using the compounds of the present invention are excellent in photographic performance (sensitivity), film physical properties [coating finish (tail coating failure due to solidification), scratch (scratch) strength]. I understand.

[0157]

According to the present invention, a silver halide photographic light-sensitive material having improved film physical properties without adversely affecting photographic characteristics and free from coating failure can be obtained.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Chiaki Otani Konica Stock Company, 1 Sakura-cho, Hino-shi, Tokyo In-house

Claims (4)

[Claims] 1. A silver halide photographic light-sensitive material characterized in that at least one layer on a transparent support contains at least one compound having a repeating structural unit represented by the following general formula (1). [Chemical 1] In the formula, R ₁ represents a hydrogen atom or an alkyl group, R ₂ represents a hydrogen atom, an alkyl group having 1 to 22 carbon atoms or an aryl group, and R ₃ represents a hydrogen atom, an alkyl group having 1 to 22 carbon atoms, or Represents an aryl group. 2. The silver halide photographic light-sensitive material according to claim 1, wherein the compound represented by the general formula (1) is polymer particles. 3. The silver halide photographic light-sensitive material according to claim 1, wherein the compound represented by the general formula (1) is water-soluble. 4. At least one layer of a transparent support containing at least one compound having a repeating structural unit represented by the general formula (1) and hydrophobic polymer particles. The described silver halide photographic light-sensitive material.