JPH06242532A - Silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To improve the physical properties of a film and to prevent defective coating without adversely affecting photographic characteristics by incorporating at least one kind of compd. having specified repeating structural units into at least one layer on a base. CONSTITUTION:At least one kind of compd. having repeating structural units represented by the formula is incorporated into at least one layer on a base. In the formula, R1 is H or -(CHOH)m-CH2OH, R2 is H, monohydroxyalkyl, polyhydroxyalkyl or 1-30C hydrocarbon, R3 is H or methyl, L is a divalent combining group, (m) is 0, 1 or 2 and (n) is an integer of 1-4. The compd. represented by the formula is synthesized by allowing an activated deriv. of acrylic acid or methacrylic acid to react with sugaralcohol having an N-substd. amino group or acrylic acid or methacrylic acid.

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.

However, these polymer latices and water-soluble polymers have poor compatibility with hydrophilic colloids, resulting in a decrease in the adhesive strength between layers and the occurrence of coating failures due to the formation of aggregates in the coating liquid. However, there has been 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, and a first object thereof is to provide a silver halide photographic light-sensitive material having improved film physical properties without adversely affecting photographic characteristics. A second object is to provide a silver halide photographic light-sensitive material that does not cause coating failure.

[0006]

The above objects of the present invention have been achieved by the following silver halide photographic light-sensitive materials.

(1) A silver halide photographic light-sensitive material characterized in that at least one layer on a support contains at least one compound having a repeating structural unit represented by the general formula (I) "Chemical formula 1". material.

(2) A silver halide photographic light-sensitive material, wherein the compound described in (1) is polymer particles.

(3) A silver halide photographic light-sensitive material, wherein the polymer particles described in (2) are hydrophobic polymer particles.

(4) (3) At least one layer on the support contains at least one kind of hydrophobic polymer particles produced in the presence of the compound having the repeating structural unit represented by the general formula (I). A silver halide photographic light-sensitive material as described in (1) above.

(5) At least one layer of a compound having a repeating structural unit represented by the general formula (I) and hydrophobic polymer particles are contained in at least one layer on a support (1) The described silver halide photographic light-sensitive material.

(6) The hydrophobic polymer particles described in (5) are characterized in that they are polymerized in the presence of a compound having a repeating structural unit represented by the general formula (I). (5) The silver halide photographic light-sensitive material described in (5).

(7) The halogenated halogenated polymer according to (5), wherein the hydrophobic polymer grain according to (5) is a hydrophobic polymer grain having a repeating structural unit represented by the general formula (I). Silver photographic light-sensitive material.

The present invention will be described in detail below.

In the general formula (I), examples of the monohydroxyalkyl group represented by R ₂ include 2-hydroxyethyl, 2-hydroxypropyl, 3-hydroxypropyl, 2-hydroxybutyl, 3-hydroxybutyl, 4 -Hydroxybutyl, 2-hydroxy-2-methyl-propyl, 2-hydroxypentyl, 4-hydroxypentyl, 5-hydroxypentyl, 2-hydroxy-2-methyl-butyl, 3-hydroxy-3-methyl-butyl, etc. Groups.

The polyhydroxyalkyl group represented by R ₂ is, for example, 2,3-dihydroxypropyl, 2,
3-dihydroxybutyl, 2,4-dihydroxybutyl, 3,4-
Dihydroxybutyl, 2,3,4-trihydroxybutyl, 2,
3-dihydroxypentyl, 2,4-dihydroxypentyl,
2,5-dihydroxypentyl, 3,4-dihydroxypentyl, 3,5-dihydroxypentyl, 4,5-dihydroxypentyl, 2,3,4-trihydroxypentyl, 2,4,5-trihydroxypentyl, 2, 3,5-trihydroxypentyl, 3,4,
5-trihydroxypentyl, 2,3,4,5-tetrahydroxypentyl, 2,3-dihydroxyhexyl, 2,4-dihydroxyhexyl, 2,5-dihydroxyhexyl, 2,6-dihydroxyhexyl, 3,4- Dihydroxyhexyl, 3,5-dihydroxyhexyl, 3,6-dihydroxyhexyl, 4,5-dihydroxyhexyl, 4,6-dihydroxyhexyl, 5,6-dihydroxyhexyl, 2,3,4-trihydroxyhexyl,
2,3,5-trihydroxyhexyl, 2,3,6-trihydroxyhexyl, 2,4,5-trihydroxyhexyl, 2,4,6-trihydroxyhexyl, 2,5,6-trihydroxyhexyl,
3,4,5-trihydroxyhexyl, 3,4,6-trihydroxyhexyl, 3,5,6-trihydroxyhexyl, 4,5,6-trihydroxyhexyl, 2,3,4,5-tetrahydroxy Hexyl, 2,4,5,6-tetrahydroxyhexyl, 2,3,5,6-tetrahydroxyhexyl, 2,3,4,6-tetrahydroxyhexyl, 3,4,5,6-tetrahydroxyhexyl, 2,3,4,5,6-
Examples include groups such as pentahydroxyhexyl.

Further, the hydrocarbon group represented by R ₂ represents an aliphatic group, a cycloaliphatic group or an aromatic group (a fatty acid or a cyclic fatty acid-substituted aromatic group or an aromatic-substituted fatty acid or cyclic group). Including fatty acid groups).

When they have several isomers, all stereoisomeric forms are included. Illustrative hydrocarbon radicals include ethyl, propyl, butyl,
Pentyl, hexyl, benzyl, phenylethyl, cyclopentyl, cyclohexyl, methylcyclopentyl,
Any group capable of forming an activated derivative capable of reacting with an amine group such as octyl, decyl, dodecyl, octadecyl, naphthyl may be used.

L may be a divalent linking group, particularly preferably a carbonyl group, but may be any group capable of forming an activated derivative capable of reacting with an amino group such as chloromethylstyrene.

The compound having the repeating unit represented by the general formula (I) used in the present invention is synthesized by reacting an activated derivative of acrylic acid or methacrylic acid with a sugar alcohol having an N-substituted amino group. . It is also synthesized by reacting with acrylic acid or methacrylic acid. Examples of the activated derivative of acrylic acid or methacrylic acid include acryloyl chloride, methacryloyl chloride, acrylic acid anhydride, methacrylic acid anhydride, and N-hydroxysuccinimide ester of acrylic acid or methacrylic acid. N-substituted amino sugar alcohols can be synthesized in several ways. The most widely used method is the reduction of monosaccharides with amines to synthesize N-alkyl sugar amino alcohols. The N-substituted alditol amines serve as starting materials for the synthesis of the compounds of general formula (I) used in the present invention.

Acylation of amines with activated derivatives of acrylic acid or methacrylic acid can be carried out in various solvents. The choice of solvent is the solubility of the amine,
It is determined by the reactivity of the activated derivative of acrylic acid or methacrylic acid and the potential sites for reaction.
For example, alcohol solvents are not suitable when using acryloyl chloride or methacryloyl chloride due to their high reactivity with solvents and reagents. If the amine dissolves, something like dioxane or acetonitrile is also applicable. The potential sites of reaction in such solvents are one or several hydroxyl groups (which are esterified). If the acid is liberated through an acylation reaction, neutralizing the acid with a base is an effective means. The base is
It is possible to use inorganic and organic bases, and particularly effective are LiOH, NaOH, KOH, Ca (OH) ₂ and tertiary amines. Two moles of amine are provided, one mole capable of reacting with the activated acrylic acid or methacrylic acid derivative, and the acid liberated therefrom being neutralized with one mole of amine.

Water is the solvent of choice for the acylation of many alditol amines. Because they are almost insoluble in other solvents. Further, water is more suitable as the solvent because esterification of the hydroxyl group does not easily occur in water. The disadvantage is the hydrolysis of activated acrylic acid derivatives or activated methacrylic acid derivatives. However, by carefully controlling the reaction state,
High production of alditol acrylamide or alditol methacrylamide can be obtained. The compound of the general formula (I) used in the present invention can be synthesized by the same method. The acylation reaction is selectively carried out in a two-phase (predominantly water-methylene chloride) system at a slightly alkaline pH (7.5-11) and at low temperature (0-15 ° C). Alditol acrylamide and alditol methacrylamide are selectively separated and purified from by-products and unreacted starting materials by a combination of anion and cation ion exchange agents.
The ion exchange agents may be used in sequence or mixed. It has been found that a combination of a strong cation ion exchange agent such as Dowex 50 or Amberlite IR120 and a weak anion exchange agent such as Amberlite IRA-68 is particularly suitable. . As a result, the aqueous solution of the compound of general formula (I) used in the present invention is either poured into a crystallization dish or first partially concentrated by rotary evaporation. It is effective to add a small amount of a polymerization control agent (p-methoxyphenol, phenothiazine, sodium nitride, etc.) prior to water evaporation. Some of the compounds of general formula (I) used in the present invention, which were crystallized after evaporation of water, were solidified into some hard masses and some remained as viscous liquids. The solidified ones were usually recrystallized and the ones left in solution were treated with mixed ion exchangers and charcoal prior to polymerization.

The compound having a repeating unit represented by the above general formula (I) according to the present invention is
It is also possible to copolymerize another monomer copolymerizable with this (hereinafter referred to as "other monomer") in an amount of 99% by weight or less, preferably 1 to 98% by weight, more preferably 10 to 90% by weight.

The compound according to the present invention, which has a repeating unit represented by the above general formula (I), is
It may be a water-soluble polymer or hydrophobic polymer particles, and any form can be easily obtained by adjusting the type and content of other monomers.

The 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 and 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 caproate, 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:
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. Examples thereof include ethyl methacrylamide, dimethylaminoethyl methacrylamide, phenyl methacrylamide, dimethyl methacrylamide, diethyl methacrylamide, β-cyanoethyl methacrylamide, and N- (2-acetoacetoxyethyl) methacrylamide.

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 and N-vinyl pyrrolidone.

Examples of glycidyl esters include:
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, as the monomer compound, acrylic acid, methacrylic acid, itaconic acid, maleic acid, monoalkyl itaconate, such as monomethyl itaconate, monoethyl itaconate, monobutyl itaconate, etc .; Monoalkyl maleate, such as malein Acid monomethyl, monoethyl maleate, monobutyl maleate, etc .; citraconic acid, styrenesulfonic acid, vinylbenzylsulfonic acid, vinylsulfonic acid, acryloyloxyalkylsulfonic acid, for example, acryloyloxymethylsulfonic acid, acryloyloxyethylsulfonic acid, acryloyloxy Propyl sulfonic acid and the like; methacryloyloxyalkyl sulfonic acid, such as methacryloyloxydimethyl sulfonic acid, methacryloyloxyethyl sulfonic acid, methacryloyl Royloxypropyl sulfonic acid and the like; acrylamidoalkyl sulfonic acid, such as 2-acrylamido-2-methylethanesulfonic acid, 2-acrylamido-2-methylpropanesulfonic acid, 2-acrylamido-2-methylbutanesulfonic acid and the like; methacrylamido Alkyl sulfonic acids, such as 2-methacrylamide-2-
Methylethanesulfonic acid, 2-methacrylamido-2-methylpropanesulfonic acid, 2-methacrylamido-2-methylbutanesulfonic acid, etc .; acryloyloxyalkyl phosphates such as acryloyloxyethyl phosphate, 3-acryloyloxypropyl-2- Phosphate and the like; methacryloyloxyalkyl phosphate,
For example, methacryloyloxyethyl phosphate, 3-
Methacryloyloxypropyl-2-phosphate etc .;
Examples thereof include naphthyl 3-allyloxy-2-hydroxypropanesulfonate having two hydrophilic groups. 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 and 3,438,708.
No., No. 3,554,987, No. 4,215,195, No. 4,247,673,
The crosslinkable monomers described in JP-A-57-205735 can be used. Specific examples of such crosslinkable monomers include N- (2-acetoacetoxyethyl) acrylamide, N- {2- (2-acetoacetoxyethoxy) ethyl} acrylamide and the like.

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

The monomer compounds preferably used will be exemplified below.

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 for polymerizing the compound having the repeating unit of the general formula (I) used in the present invention is as follows:
Examples thereof include emulsion polymerization method, solution polymerization method, bulk polymerization method, suspension polymerization method and radiation polymerization method.

In solution polymerization, a mixture of monomers having a suitable concentration in a solvent (usually 40% by weight or less, preferably 10 to 25% by weight with respect to the solvent) is added in an amount of about 10% in the presence of an initiator. ~
The polymer is obtained by carrying out the polymerization at a temperature of 200 ° C., preferably 30 to 120 ° C. for about 0.5 to 48 hours, preferably 2 to 20 hours.

Any initiator may be used as long as it is soluble in the polymerization solvent, and examples thereof include benzoyl peroxide, azopis isobutyronitrile (AIBN), ditertiary butyl peroxide, and other organic solvent-based initiators, and peroxides. Water-soluble initiators such as ammonium sulphate (APS), potassium persulfate, 2,2'-azobis- (2-amidinopropane) -hydrochloride, etc., and redox combining these with reducing agents such as Fe ²⁺ salts and sodium sulfite. Examples include a system polymerization initiator and the like.

As the solvent, any solvent capable of dissolving a mixture of monomers may be used, and examples thereof include water, methanol, ethanol, dimethylsulfoxide, dimethylformamide, dioxane, and a mixed solvent of two or more thereof. You can

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.
The polymer is obtained by polymerizing with 5% by weight of a polymerization initiator and 0.1 to 20% by weight of a dispersant at about 30 to 100 ° C., preferably 60 to 90 ° C. for 3 to 8 hours with stirring. 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′-tetra-methylethylenediamine or a redox type polymerization initiator in which these are combined with a reducing agent such as Fe ²⁺ salt or sodium sulfite.

Examples of the dispersant include anionic surfactants, nonionic surfactants, water-soluble polymers and the like.

The above-mentioned general formula (I) thus obtained
The molecular weight of the compound having a repeating structural unit represented by can not be uniquely determined by the application used, but is usually about 500 to 5,000,000, preferably 1,000 to 500,0 in terms of polystyrene or polyethylene oxide.
00.

Next, an example of a method for producing polymer particles having a repeating structural unit represented by the general formula (I) 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 was equipped with a stirrer, a thermometer, a dropping funnel, a nitrogen introducing tube and a reflux condenser to introduce nitrogen gas. Then, while denitrifying, add 350 ml of distilled water and the internal temperature is 80 ° C.
It is dripped with a heating funnel for about 1 hour until it becomes. After the dropping was completed, the reaction was continued for 5 hours. 0.45 g of ammonium persulfate was added as an initiator and then according to the invention
After 90 g of N-acryloyl-N-ethyl-1-amino-1-deoxy-D-galactitol are dropped, by-products and unreacted starting materials are removed by steam distillation. Then cool down and poly-N
-Acryloyl-N-ethyl-1-amino-1-deoxy-D-galactitol (P-1) is obtained.

Production Example 2 (Synthesis of N-acryloyl-N-ethyl-1-amino-1-deoxy-D-galactitol) N-ethyl-1-amino-1-deoxy-D-galactitol (63
g) was mixed with about 300 ml of water and 1 g of sodium nitride. To it was added 100-150 ml methylene chloride and the solution was cooled in an ice bath. Potassium hydroxide was dissolved in water and cooled further. The two-layer reaction mixture was well agitated, methylene chloride of pH 7.5 to 9.5 and the same volume of acryloyl chloride and KOH solution were added, and the mixture was stirred for 1 hour. The two layers were separated by a separating funnel, the lower organic layer was removed, the aqueous layer was treated with charcoal and filtered. Further, the filtrate was treated with an ion exchange agent. A portion of Amberlite IR-120, H ⁺ and IRA-68 was added to this solution until the silver reaction to chloride became negative. The resin is then
Removed, the filtrate was treated with activated charcoal and poured into a crystallization dish. A small amount of p-methoxyphenol or sodium nitrite was added to the monomer solution and evaporated for 1-2 weeks. Recrystallized from ethanol-acetone. The monomer was a white solid and had a yield of 72% and a melting point of 80 to 84 ° C.

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

P-1; poly-N-acryloyl-N-ethyl-1
-Amino-1-deoxy-D-galactitol, P-2; Poly-N-acryloyl-N-propyl-1-amino-1-
Deoxy-D-galactitol, P-3; Poly-N-acryloyl-N-butyl-1-amino-1-deoxy-D-galactitol, P-4; Poly-N-acryloyl-N-hexyl-1- Amino-1-
Deoxy-D-galactitol, P-5; Poly-N-acryloyl-N-octyl-1-amino-1-
Deoxy-D-galactitol, P-6; Poly-N-acryloyl-N-phenylethyl-1-amino-1-deoxy-D-galactitol, P-7; Poly-N-acryloyl-N- (2- (Hydroxyethyl)
-1-amino-1-deoxy-D-glucitol, P-8; poly-N-acryloyl-N- (2-hydroxyethyl)
Amino-1-deoxy-D-galactitol, P-9; Poly-N-acryloyl-N, N-bis (1-deoxy-D
-Galactitol), P-10; poly-N-acryloyl-N, N-bis (1-deoxy-D
-Glucitol), Tg (glass transition temperature) of the polymer forming the hydrophobic polymer particles used in the present invention is preferably higher than the development temperature, and particularly preferably higher than the development temperature by 5 ° C or more.

The Tg's of many polymers of ethylenic monomers used in the present invention are described in "Polymer Handbook" by Brand Wrap et al., Pages III-139 to III-179 (1966) (Wiley & Sun Corporation edition). 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 monomer in the copolymer, and Tg ₁ , Tg ₂ ... Tg _W represents the Tg (° K) of the homopolymer of each monomer in the copolymer.

The Tg calculated according to the above equation is ± 5 ° C.
There is a precision of.

Regarding the method for synthesizing the hydrophobic polymer particles used in the present invention, US Pat. Nos. 2,852,386 and 2,853,457 are cited.
No. 3,41,911, 3,411,912, 4,197,127,
Pergie Patents 688,882, 691,360, 712,823,
JP-B-45-5331, JP-A-60-18540, 51-130217
No. 58-137831, No. 55-50240, etc.

The average particle size of the hydrophobic polymer particles used in the present invention is particularly preferably 0.01 to 0.8 μm, and 0.005 to 2.
Any one having a thickness of 0 μm can be preferably used.

The hydrophobic polymer particles used in the present invention can be contained in the photographic constituent layer 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 used in 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 a method for producing hydrophobic polymer particles will be described.

(Production Method of Hydrophobic Polymer Particles) Production Example 1 (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 ml 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, the mixture is cooled and adjusted to pH 6 with aqueous ammonia to obtain hydrophobic polymer particles. Tg was 105 ° C.

Production Example 2 (Synthesis of Lx-2) A 500 ml three-necked flask was charged with 200 ml of dioxane and deoxidized with nitrogen gas. Then, 40 g of N-acryloyl-N-butyl-1-amino-1-deoxy-D-galactitol and 80 g of methyl methacrylate according to the present invention were added, and 1.2 g of dimethyl azobisisobutyrate as an initiator was further added, and the mixture was added at 60 ° C.
And continue the reaction for 6 hours. After completion of the reaction, the reaction solution is added to 3 liters 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 and added to 500 ml of distilled water containing 2 g of dispersant (SF-1) with vigorous stirring, and then ethyl acetate was removed to remove hydrophobicity. Obtain polymer particles. Tg is 62
It was ℃.

[0073] The structure of (SF-1) is, pC ₉ H ₁₉ - is _{(C 6 H 4) -O- (} CH 2 CH 2 O) 6 (CH 2) 3 SO 3 Na.

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

[0075]

[Chemical 2]

[0076]

[Chemical 3]

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 No.42-2
It is described in No. 6845.

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

The silver halide grain may be one having a uniform silver halide composition distribution within the grain, or may be a core / shell grain having a different silver halide composition between the inside and the surface layer of the grain, 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.

Further, 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 high-sensitivity / low-sensitivity two-layer structure.

When embodied in a typical multicolor color light-sensitive material, this 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 one Magenta dye-forming coupler having at least one green-sensitive silver halide emulsion layer, and a yellow dye image having at least one blue-sensitive silver halide emulsion layer having at least one yellow dye-forming coupler. The constitutional unit is formed by coating the support together with the non-photosensitive layer.

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

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, naphthol type couplers and phenol couplers 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.

[0096]

【Example】

Example 1 A backing layer (coating gelatin amount: 2.0 g / m ² ) using the following coating solution for a backing layer, and a backing protective layer using a coating solution for a backing layer protective film layer on a subbed polyethylene rephthalate support. (Coating gelatin amount of 1.5 g / m ² ) is placed on the undercoat layer on the opposite side of the support, and an emulsion layer (coating gelatin amount of 2.
0 g / m ² ) and emulsion protective layer (coating gelatin amount 1.0 g / m ² ),
Light-sensitive material samples 1 to 24 were prepared by coating four layers simultaneously and drying.

[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 63 mg of compound (C-8) was further added. A methanol solution was added.

To this solution, 800 g of a styrene-maleic acid copolymer water-soluble polymer was added as a thickener to adjust the viscosity, and the pH was adjusted to 5.4 with 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 ml.

[Preparation of Coating Solution for Protective Layer of Backing Layer] 50 g of gelatin was swollen in water and dissolved by heating, and then 340 mg of 2-sulfonate-succinic acid bis (2-ethylhexyl) 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 size of 4 μm was added as a matting agent in an amount 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) was added. In addition, 5 ml of a 20% saponin aqueous solution, 180 mg of sodium dodecylbenzene sulfonate, and 8-methylbenzotriazole were added per mol of silver halide.
0 mg, 43 ml of the following latex (L) for emulsion addition, 60 mg of compound (M), 280 mg of styrene-maleic acid copolymer water-soluble polymer as a thickening agent, and compounds of the present invention (described in Table 1) were sequentially added. To 475 ml with water to prepare a silver halide emulsion coating solution.

[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 at 40 ° C. for 25 minutes, 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 mixed liquid 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 ammonium persulfate was added at 0.005 kg was added, and the mixture was further stirred for 1.5 hours, cooled, and the pH was adjusted to 0.6 with aqueous ammonia.

The latex solution thus obtained 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 μm.

[Preparation of Coating Liquid for Emulsion Protective Film] Water was added to gelatin to swell, and then dissolved 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 with a particle size of 4.0 μm) was added, and Table 1 was added.
The compound of the present invention was added to prepare a coating solution for emulsion protective film as shown in.

[0108]

[Chemical 4]

[0109]

[Chemical 5]

[0110]

[Chemical 6]

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 Potassium sulfite (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 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 using the developer, the above composition A and composition in 500 ml of water are used. Object B
Were dissolved in this order, and water was added to make 1 liter.

[Fixing solution 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 (Al ₂ O ₃ equivalent content is 8.1% w / w aqueous solution) 26.5 g Water when using fixer The above composition A and composition B were dissolved in 500 ml 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 24 were evaluated by the evaluation methods shown below.

[Evaluation Method] [Haze] The unexposed sample treated in the above treatment step was measured by 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] The unexposed sample was developed, fixed, and washed in the above-mentioned processing steps, and then, while still immersed in the developing solution at the specified developing temperature, the film surface was scratched and scratched by a heavy metal needle. Minimum sticking metal needle weight (scratch strength)
I asked.

The results are shown in Table 1.

[0121]

[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, 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 ,
It was dried at 80 ° C for 5 minutes.

Alumina sol AS-100 (manufactured by Nissan Chemical Industries, Ltd.) 40 g Acetone 500 ml Methanol 400 ml Dimethylformamide 100 ml Back layer 2nd layer On top of the back layer 1st layer, the following back layer 2nd layer coating liquid is 20ml / It was coated so as to have a surface area of m ² and dried at 80 ° C. for 5 minutes.

Diacetyl cellulose 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 On the above back layer 2nd layer, the following back layer 3rd layer coating liquid is applied.
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, on the surface side (emulsion layer side) of the support provided with a back layer, each layer having the composition shown below was sequentially formed 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 4th layer; High-sensitivity red-sensitive emulsion layer (RH) Silver iodobromide emulsion (Average particle size 0.7 μm, average iodine content 7.5 mol%) 0.9 Sensitizing dye (S-1) 1.7 × 10 ^-4 (mol / silver 1 mol) 〃 (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 Additive (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 7th layer; high-sensitivity green-sensitive emulsion layer (GH) Silver iodobromide emulsion (average grain 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 8th 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 9th layer; Low sensitivity blue sensitive emulsion layer (BL) Silver iodobromide emulsion (average grain size 0.3 μm, average iodide content of 2.0 mol%) 0.25 silver iodobromide emulsion (average particle size 0.4 .mu.m, the average iodide content of 8.0 mol%) 0.25 sensitizing dye (S-9) 5.8 × 10 -4 ( mol / mole of silver) yellow Puller (Y-1) 0.60 〃 (Y-2) 0.32 DIR 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) Odor Silver halide (average particle size 0.08 μm, average iodine content 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 point 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: Copolymer of methacrylic acid = 3: 3: 4 (weight ratio) (average particle size 3 μm) 0.13 gelatin 0.5 The silver iodobromide emulsion used in the 10th layer was prepared by the following method.

A silver iodobromide emulsion was prepared by a double jet method using monodispersed silver iodobromide grains (silver iodide content 2 mol%) having an average grain size of 0.33 μm as seed crystals.

The solution <G-1%> was heated at a temperature of 70 ° C., pAg7.8 and pH.
The seed emulsion corresponding to 0.34 mol was added while maintaining the ratio at 7.0 while stirring well.

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

(Formation of External Low Iodity Phase-Shell Phase) Next, <H-2> and <S- while maintaining pAg10.1 and pH 6.0.
2> was added at a flow rate accelerated by a flow rate ratio of 1: 1 (the flow rate at the end was 5.2 times the initial flow rate) over 65 minutes.

The pAg and pH during grain formation were controlled using an aqueous potassium bromide solution and a 56% aqueous acetic acid solution. After the particles are formed, they are washed with water by a conventional flocculation method, and then gelatin is added to redisperse the resulting mixture.
The pAg was adjusted to 5.8 and 8.06, respectively.

The obtained emulsion was a monodisperse emulsion containing octahedral silver iodobromide grains having an average grain size of 0.80 μm, a broad distribution of 12.4% and a silver iodide content of 8.0 mol%.

<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 Finish with water 3776.8ml <S-2> Silver nitrate 1130.0g 28% aqueous ammonia solution Equivalent Finish with water 3776.8ml Average grain size of seed crystal, temperature, pAg, pH, flow rate, addition in the same manner The above emulsions having different average grain sizes and different silver iodide contents were prepared by changing the time and the 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-1-phenyl-5-mercaptotetrazole was added.

The above-mentioned light-sensitive material sample was further prepared by adding 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 contained.

[0138]

[Chemical 7]

[0139]

[Chemical 8]

[0140]

[Chemical 9]

[0141]

[Chemical 10]

[0142]

[Chemical 11]

[0143]

[Chemical 12]

[0144]

[Chemical 13]

[0145]

[Chemical 14]

[0146]

[Chemical 15]

[0147]

[Chemical 16]

Next, as shown in Table 2, the second, third, fifth,
Sample Nos. 26 to No. 26 to No. 26 to No. 6 except that the compound having the repeating structural unit represented by the general formula (I) used in the present invention was added to the sixth, ninth and twelfth layers. 39
Was 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) The sample is 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.

Then, 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 and the non-fogged portion on the sample front side were measured with a microdensitometer, and the density difference ΔD was obtained and evaluated according to the following criteria.

○: 0 to 0.06 △: 0.07 to 0.12 ×: 0.12 to 0.19
XX: 0.20 or more (Evaluation of photographic performance) Each sample 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 780ml Bleach 45 seconds 38 ° C 150ml Settling 1 minute 30 seconds 38 ° C 830ml Stabilization 60 seconds 38 ° C 830ml 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 water 800 ml potassium carbonate 35 g sodium hydrogen carbonate 3 g potassium sulfite 5 g sodium bromide 0.4 g hydroxylamine sulfate 3.1 g 4-amino-3-methyl-N-ethyl-N- (β-hydroxylethyl) Aniline sulfate 6.3g Potassium hydroxide 2g Diethylenetriaminepentaacetic acid 3g 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-Diaminopropanetetraferric ammonium ammonium 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.

Water for replenishing bleaching 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 to 4.0 using ammonia water or glacial acetic acid After the adjustment, add water to make 1 liter.

Fixing solution Water 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 aqueous ammonia, add water to make 1 liter.

Fixing replenisher water 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 with acetic acid and aqueous ammonia, add water to make 1 liter.

Stabilizer and stable replenisher Paraoctylphenol ethylene oxide 10 mol adduct 2.0 g Dimethylolurea 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-mentioned 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.

[0165]

[Table 2]

[0166]

[Chemical 17]

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

[0168]

According to the present invention, there is provided a silver halide photographic light-sensitive material in which the physical properties of the film are improved without adversely affecting the photographic characteristics and the coating failure does not occur.

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

Claims (7)

[Claims] 1. A silver halide photographic light-sensitive material characterized in that at least one layer on a support contains at least one compound having a repeating structural unit represented by the following general formula (I). [Chemical 1] [In the formula, R ₁ represents a hydrogen atom or-(CHOH) _m -CH ₂ OH,
R ₂ represents a hydrogen atom, a monohydroxyalkyl group, a polyhydroxyalkyl group or a hydrocarbon group having 1 to 30 carbon atoms. R ₃ represents a hydrogen atom or a methyl group, and L is 2
Represents a valent linking group. m represents 0, 1 or 2, and n is 1 to
Represents an integer of 4. ] 2. A silver halide photographic light-sensitive material, wherein the compound according to claim 1 is a polymer particle. 3. A silver halide photographic light-sensitive material, wherein the polymer particles according to claim 2 are hydrophobic polymer particles. 4. At least one hydrophobic polymer particle produced in the presence of a compound having a repeating structural unit represented by the general formula (I) is contained in at least one layer on a support. Item 1. A silver halide photographic light-sensitive material according to Item 1. 5. The at least one layer on the support contains at least one compound having a repeating structural unit represented by the general formula (I) and hydrophobic polymer particles. Silver halide photographic light-sensitive material. 6. The hydrophobic polymer particle according to claim 5,
The silver halide photographic light-sensitive material according to claim 5, which is a hydrophobic polymer particle polymerized in the presence of a compound having a repeating structural unit represented by the general formula (I). 7. The hydrophobic polymer particle according to claim 5,
The silver halide photographic light-sensitive material according to claim 5, which is a hydrophobic polymer particle having a repeating structural unit represented by the general formula (I).