JP2532841B2 - Silver halide photographic light-sensitive material hardened with a polymer hardener - Google Patents

Description

The present invention relates to a silver halide photographic light-sensitive material, and more particularly to a photographic light-sensitive material in which a specific layer is hardened with a polymer hardener.

(Background of the Invention) Generally, many photographic light-sensitive materials contain a hydrophilic colloid such as gelatin as a binder component, and the binder component is a silver halide emulsion layer, a protective layer, a filter layer, an intermediate layer, an antihalation layer. , A backing layer, a film base undercoat layer, a baryter layer, and the like.
Then, for example, a light-sensitive material containing gelatin is processed with various aqueous solutions having different pH or temperature, but a layer containing gelatin not treated with a curing agent has poor water resistance and swells excessively in the aqueous solution. The gelatin layer may be dissolved and even flow out in extreme cases, especially in a processing solution at a temperature of 30 ° C or higher.

In particular, the protective layer is required to have durability because it is susceptible to environmental changes and contact with devices and the like. Numerous compounds are known to date for hardening gelatin to increase the water and scratch resistance of protective layers. These are well known as "hardeners" used in the production of photographic light-sensitive materials. For example, inorganic compounds such as chromium alum, aldehyde compounds such as formaldehyde and glutaraldehyde, compounds having active halogen described in U.S. Pat.No. 3,288,775, etc., reactions described in U.S. Pat. Compounds having a polar ethylenically unsaturated group, aziridine compounds described in US Pat. No. 3,017,280, epoxy compounds described in US Pat. No. 3,091,537, halogenocarboxaldehydes such as mucochloric acid, etc. Organic compounds are known as hardeners.

However, such hardeners adversely affect the properties of the light-sensitive material (for example, increase in fog,
Sensitivity deterioration, gradation change, etc.), causing a long-term change in the hardening action called "post-hardening", or causing inhomogeneity in the photosensitive material due to insufficient solubility in water during use. Curing, loss of curing effect due to other common photographic additives (color couplers for color light-sensitive materials, for example), the hardener itself being unstable and poor storage stability, and the hardener itself being synthesized. All have some drawbacks such as difficulty and difficulty in mass production.

In addition, since the low molecular weight hardeners that have been often used to harden gelatin migrate in the gelatin layer by diffusion, the degree of hardening of each gelatin layer can be adjusted in a gelatin coating product in which a number of different layers are stacked and applied. It couldn't be adjusted freely according to the purpose. On the other hand, high molecular weight diffusion resistant gelatin hardeners such as dialdehyde starch or polyacrolein, which are well known at present, adversely affect photographic properties such as increased fog and decreased sensitivity, and therefore, are not suitable for photographic materials. Was not happy to use. Further, the polymeric hardeners having a vinylsulfone group as an active group described in U.S. Pat.No. 4,161,407 and JP-A-56-142524 have a slow hardening reaction and a post-hardening that the degree of swelling changes with time. I had a problem that

Therefore, it has been desired to develop a hardener that can harden a specific layer and does not adversely affect photographic properties, and that has no posthardening.

(Object of the Invention) Accordingly, the first object of the present invention is to harden a film with a polymer hardener having diffusion resistance which does not adversely affect photographic characteristics such as increased fog and decreased sensitivity. To provide photographic light-sensitive materials.

Secondly, there is no post-hardening in which the degree of swelling changes with time, it has excellent solubility, and it is hardened with a polymer hardener capable of selectively hardening only a specific layer. To provide the material.

(Structure of the Invention) The above object of the present invention is to provide a silver halide photographic light-sensitive material having at least one non-photosensitive layer and at least one silver halide emulsion layer on a support. This is achieved by a silver halide photographic light-sensitive material in which at least one of the silver halide emulsion layers is hardened with a polymer hardener having a repeating unit represented by the following general formula [I].

[In the formula, A represents a monomer unit copolymerizable with a copolymerizable ethylenically unsaturated monomer. R ₁ is a hydrogen atom, a lower alkyl group having 1 to 6 carbon atoms, a halogen atom or
It represents a CO-L-SO ₂ X.

J is a lower alkylene group having 1 to 6 carbon atoms, or-
O-, Represents (However, R ₂ represents an aryl group having 6 to 12 carbon atoms, Z ₁ and Z ₂ each represent an atom necessary for forming a ring containing at least one nitrogen atom.) L represents —CO ₂ -and 2 with 3 to 15 carbon atoms having at least one of the bonds
A valent linking group or -O-, -CO -, - SO -, - SO 2 -, - SO 3 -, 2 having 1 to 12 carbon atoms having at least one bond
Represents a valent linking group. (However, R ₃ is hydrogen atom, carbon number 1
It represents an alkyl group having from 6 to 6 or an aryl group having from 6 to 12 carbon atoms. Z ₃ represents an atomic group necessary for forming a ring containing at least one nitrogen atom. ) X represents a -CH = CH ₂ or -CH ₂ CH ₂ -Q. (However,
Q represents a group which can be replaced by a nucleophilic group or a group which can be eliminated in the form of HQ by a base. ) X and y represent mole percentages, x is 0 to 99,
And y is 1 to 100.

n is an integer of 0 or 1. (Specific Structure of the Invention) In the polymer hardener of the present invention, A in the general formula [I] represents a monomer unit, and the monomer forming such a monomer unit is, for example, ethylenically unsaturated. A typical example is a monomer. Examples of preferred ethylenically unsaturated monomers are ethylene, propylene, 1-butene, isobutene, styrene, chloromethylstyrene, hydroxymethylstyrene, sodium vinylbenzene sulfonate, sodium vinylbenzyl sulfonate, N, N, N-trimethyl. -N-vinylbenzylammonium chloride, N, N-dimethyl-N-benzyl-N-
Vinylbenzylammonium chloride, α-methylstyrene, vinyltoluene, 4-vinylpyridine, 2-vinylpyridine, benzylvinylpyridinium chloride, N-vinylacetamide, N-vinylpyrrolidone,
1-vinyl-2-methylimidazole, vinyl sulfonic acid, monoethylenically unsaturated ester of aliphatic acid (eg vinyl acetate, allyl acetate), ethylenically unsaturated onocarboxylic acid or dicarboxylic acid and salts thereof (eg acrylic acid, Methacrylic acid, itaconic acid, maleic acid, sodium acrylate, potassium acrylate, sodium methacrylic acid), maleic anhydride, ethylenically unsaturated monocarboxylic acid or dicarboxylic acid esters (for example, n-butyl acrylate, n-hexyl acrylate) , Hydroxyethyl acrylate, cyanoethyl acrylate,
N, N-diethylaminoethyl acrylate, methyl methacrylate, n-butyl methacrylate, benzyl methacrylate, hydroxyethyl methacrylate, chloroethyl methacrylate, methoxyethyl methacrylate, N, N-diethylaminoethyl methacrylate, N, N, N
-Triethyl-N-methacryloyloxyethylammonium p-toluenesulfonate, N, N-diethyl-N
-Methyl-N-methacryloyloxyethylammonium p-toluenesulfonate, dimethyl itaconic acid, maleic acid monobenzyl ester, 3-sulfopropylacrylate, 2-ethylsulfomethacrylate), ethylenically unsaturated monocarboxylic acid or dicarboxylic acid Amides [eg acrylamide, N, N-dimethylacrylamide, N-methylolacrylamide, N- (N, N
-Dimethylaminopropyropyl) acrylamide, N, N,
N-trimethyl-N- (N-acryloylpropyl) ammonium p-toluenesulfonate, sodium 2-acrylamido-2-methylpropanesulfonate, acryloylmorpholine, methacrylamide, N, N-dimethyl-
N'-acryloyl propane diamine propionate betaine, N, N-dimethyl-N'-methacryloyl propane diamine acetate betaine] and the like.

The monomer represented by A in the general formula [I] is used in a light-sensitive material hardened with the polymer hardener of the present invention (for example, light-sensitive material for X-ray, light-sensitive material for plate making, color negative film, etc.). Properties of other additives and the polymeric hardener of the present invention (eg, solubility, glass transition point, ionicity, etc.)
It is arbitrarily selected according to. The monomer represented by A may contain two or more kinds of monomer units in order to exhibit a composite function as a polymer.

As a selection example of the monomer of A, for example, when the polymer of the present invention has a function as an antistatic agent, A is preferably a cation monomer or an anion monomer, and when it has a function as a mordant, A is a cation. Monomers are preferred.

Further, in order to increase the solubility in water, A is preferably an ionic monomer, acrylamide, N-vinylpyrrolidone, or vinyl acetate.

As the ionic monomer, an anionic monomer is particularly preferable.

When the polymer of the present invention is used as a crosslinked latex, in addition to the above ethylenically unsaturated monomer as A, a monomer having at least two copolymerizable ethylenically unsaturated groups (for example, Divinylbenzene, methylenebisacrylamide, ethylene glycol diacrylate, trimethylene glycol diacrylate, ethylene glycol dimethacrylate, trimethylene glycol dimethacrylate, neopentyl glycol dimethacrylate, etc.) are used.

In the above general formula [I] of the present invention, R ₁ is a hydrogen atom,
It represents a lower alkyl group having 1 to 6 carbon atoms, a halogen atom or -COLS0 ₂ X, among which a hydrogen atom, a methyl group, a chlorine atom, a fluorine atom and -COLS0 ₂ X are preferable.

J is a lower alkylene group having 1 to 6 carbon atoms, or
-O-, Wherein R ₂ represents an aryl group having 6 to 12 carbon atoms, Z ₁ and Z ₂ represent an atomic group necessary for forming a ring containing at least one nitrogen atom.

 Examples of J include the following.

However, R ₄ represents an alkyl group having 1 to 6 carbon atoms or an aryl group having 6 to 12 carbon atoms.

L is -CO ₂ - and A divalent linking group having 3 to 15 carbon atoms having at least one bond, or -O-, -CO -, - SO -, - SO 2 -, - SO 3 -, 2 having 1 to 12 carbon atoms having at least one of the bonds
Represents a valent linking group, in which R ₃ represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or an aryl group having 6 to 12 carbon atoms. n is 0 or 1, and when J is an arylene group having 6 to 10 carbon atoms, n is 0.

Examples of the divalent linking group represented by L include the following.

(1) -NH- (2) -O- (3) -CH ₂ CO ₂ CH _2- (4) -CH ₂ CO ₂ CH ₂ CH _2- (5) -CH ₂ CH ₂ CO ₂ CH ₂ CH _{2 - (6) CH 2 5 CO} 2 CH 2 CH 2 - (7) CH 2 10 CO 2 CH 2 CH 2 - (8) -CH 2 NHCOCH 2 - (9) -CH 2 NHCOCH 2 CH 2 - (10) CH _{2 3} NHCOCH ₂ CH ₂ − (11) CH _{2 5} NHCOCH ₂ CH ₂ − (12) −SO ₃ CH ₂ CH ₂ CH ₂ − (13) −SO ₃ CH ₂ CO ₂ CH ₂ CH ₂ − (14) −SO ₃ CH ₂ CH ₂ CO ₂ CH ₂ CH ₂ − (15) −SO ₂ NHCH ₂ CO ₂ CH ₂ CH ₂ − (16) −SO ₂ NHCH ₂ CH ₂ CO ₂ CH ₂ CH ₂ − (17) − NHCONHCH ₂ CH ₂ − (18) −NHCOCH ₂ CH ₂ − (19) −CH ₂ NHCONHCH ₂ CH ₂ − (20) −NHCO ₂ CH ₂ CH ₂ − (21) −CH ₂ NHCO ₂ CH ₂ CH ₂ − The divalent linking group represented by L is the object of the present invention, the properties of the polymeric hardener of the present invention (eg, cationic, anionic, nonionic, soluble, hydrophilic, hydrophobic, glass transition point) or It is arbitrarily selected depending on the form (for example, a water-soluble polymer or polymer dispersion (latex)).

In the general formula [I], X- is -CH = CH ₂ or, -CH ₂
Represents CH ₂ Q, wherein Q represents a group which can be displaced by a nucleophilic group or a group which can be eliminated by a base in the form of HQ.

The Preferred as X, for _{example, -CH = CH 2, -CH 2} CH 2 Cl, -CH 2 CH 2 Br, -CH 2 CH 2 O 3 SCH 3, --CH ₂ CH ₂ OH, --CH ₂ CH ₂ O ₂ CCH ₃ --CH ₂ CH ₂ O ₂ CCF ₃ , --CH ₂ CH ₂ O ₂ CCHCl _2, etc., among which --CH = CH
₂ , -CH ₂ CH ₂ Br, -CH ₂ CH ₂ Cl, Is particularly preferable.

x and y represent mole percentages, x has a value of 0 to 99, and y has a value of 1 to 100.

x and y are arbitrarily selected according to the purpose of the present invention, and for example, when used as a polymer hardener for selectively hardening only a specific layer with increased diffusion resistance, x is 50 to 99, y takes a value of 1 to 50, x is 0 to 75 and y is 25 to 25 when used as a polymer hardener having no post-hardening, little increase in fog and little decrease in sensitivity. It can take a value of 100.

In the polymer hardener of the present invention, among the polymer hardeners having the repeating unit represented by the general formula [I],
Those in which X is —CH ₂ CH ₂ Q are generally obtained by polymerizing the ethylenically unsaturated monomer of A and the ethylenically unsaturated monomer represented by the following general formula (II). Further those wherein X is -CH = CH ₂ may, X is -CH ₂ CH
It can be easily obtained by treating the ₂ Q polymer with a base such as triethylamine or pyridine.

(However, R ₁ , J, L, X and n have the same meanings as described in the general formula [I].) Next, among the ethylenically unsaturated monomers represented by the general formula [II], preferable ones are as follows. Are the following:

Next, specific examples of the polymer hardener of the present invention will be given.

The method for synthesizing the polymer of the polymer hardener of the present invention is shown below.

Synthesis Example 1 Synthesis of HM-3 1400 ml of distilled water and sodium sulfite were placed in the reaction vessel of 2.
224 g and 220 g of sodium hydrogencarbonate were added, dissolved with stirring, cooled to 5 ° C., and 260 g of chloroethanesulfonyl chloride was added dropwise over about 1 hour and 30 minutes. 49% after dropping
Add 160 g of sulfuric acid, filter the precipitated crystals, and
It was washed with 400 ml distilled water. This liquid and washing water were placed in the reaction vessel of 3 and 182 g of methacrylic acid allyl ester was added.
What was dissolved in 480 ml of distilled water and 1500 ml of ethanol was added dropwise at 5 ° C. for about 30 minutes. 5 reaction samples in the refrigerator
After leaving it for a day to complete the reaction, it was extracted with ether. After extraction, the ether was distilled off to obtain 200 g of white crystals.

Synthesis Example 2 Synthesis of HP-5 3.7 g of monomer of Synthesis Example 1, 9.3 g of potassium salt of 3-sulfopropyl acrylate, 50% of 80 ml in a 200 ml reaction vessel.
Add an aqueous ethanol solution, stir to dissolve it, raise the temperature to 80 ° C while passing nitrogen gas, add 0.6 g of 2,2'-azobis (2,4-dimethylvaleronitrile), and the same after 30 minutes. The same amount was added, and heating and stirring were continued for 8 hours. Then cool to 10 ° C and add 2.5 g of triethylamine.
A mixture of 80 ml of ethanol was added, stirring was continued for 1 hour, the reaction sample was added to 2 of acetone, and the resulting precipitate was collected by filtration and vacuum dried to obtain 10.6 g of a white polymer.

The intrinsic viscosity [η] of this polymer was 0.230 centipoise and the vinyl sulfone content was 0.88 × 10 ⁻³ equivalent / g polymer. Other polymers can be easily synthesized according to these synthetic methods.

As described above, the polymer of the present invention has a highly reactive vinyl sulfone group, and therefore, in the silver halide photographic light-sensitive material to be added, for example, a polymer hardener effective as follows. Also used as.

i) as a hardener for the gelatin layer, ii) as a diffusion-resistant polymer mordant, antistatic agent, neutralizing agent, thickener, sensitizer, etc. iii) other photographic additives used in combination As the polymer for immobilization or diffusion resistance, the amount and place of use of the polymer of the present invention in the applications i) to iii) are the same as the conventional ones.

The amount of the polymer hardener of the present invention used is 0.5 × 10 ⁻³ equivalent to 5 of vinylsulfone group per 100 g of dry gelatin.
It is preferred to use an amount corresponding to a range of up to × 10 ^-2 equivalents. Particularly preferably, it is in the range of 5 × 10 ⁻³ equivalent to 5 × 10 ⁻² equivalent.

The polymeric hardener of the present invention may be used alone or in combination with another low molecular hardener or a polymeric hardener. As a hardening agent that can be used in combination, a compound having a reactive halogen atom such as 2-hydroxy-4,6-dichloro-1,3,5-triazine, a compound having a reactive olefin such as divinyl sulfone. , Isocyanates, aziridine compounds, epoxy compounds, mucochloric acid, chrome alum, and aldehydes.

In the polymer hardener of the present invention, a reactive polymer having a vinyl sulfone group as a pendant is used. Since the gelatin hardens quickly due to the high reactivity of the vinyl sulfone group, the polymeric hardener of the present invention shows almost no defects in post-hardening. In addition, the polymer hardener of the present invention can be arbitrarily adjusted in solubility with a copolymerization monomer and the like, and has a diffusion resistance, so that a specific layer added, that is, a large number of gelatin layers are stacked. It has excellent properties such that the individual gelatin layers in the coated laminated gelatin coating material can be independently adjusted to the degree of hardening depending on the purpose. Further, the polymer hardener of the present invention has almost no adverse effect on the photographic performance of the photographic light-sensitive material used, such as increased fog and decreased sensitivity.

Hydrophilic absorption of colloids such as silver halides, chemical sensitizers, silver halide solvents, spectral sensitizing dyes, antifoggants and gelatin used in the silver halide emulsion layer or other layers of the photographic light-sensitive material of the present invention. Agent, polymer latex brightener, color coupler anti-fading agent, dye, matting agent,
There is no particular limitation on the surfactant, and for example, Research Disclosure 1
Reference can be made to the description in Volume 76, pages 22 to 31 (December 1978).

Further, with respect to the support of the photographic light-sensitive material, the development processing method, the constituent layers of the light-sensitive material, etc., the description in the above Research Disclosure Magazine can be referred to.

For example, the photographic emulsion used in the present invention is [P. Grafkid; Chemie Physique Photography] Paul Montel (P. Glafkides Chimie et Physique Phot
ographique) (Paul Montel, 1967), [Gee
F Duffin; Photographic Emulsion Chemistry] The Focal Press (G-F-Duffin
By Photographic Emulsion Chemistry) (The Focal Pre
ss, 1966), [Buoy El Gerikman Eto
Earl; Making and Coating Photographic Emulsion] The Focal Press (by VL-Zelikman et al Making and Coating Photo
graphic Emulsion) (published by The Focal Press, 1964) and the like. That is, any of an acidic method, a neutral method, an ammonia method and the like may be used, and as a form of reacting a soluble silver salt and a soluble halogen salt, a one-sided mixing method, a simultaneous mixing method, a combination thereof,
Etc. may be used. A sulfur compound, a gold compound, etc. can be used as a chemical sensitizer. As antifoggants or stabilizers, azoles such as benzothiazolium salts, nitroindazoles, nitrobenzimidazoles, chlorobenzimidazoles, bromobenzimidazoles, mercaptathiazoles, mercaptobenzothiazoles, mercaptobenzimidazoles , Mercaptothiadiazoles, aminotriazoles, benzotriazoles, nitrobenzotriazoles, mercaptotetrazoles (especially 1-phenyl-5
-Mercaptotetrazole); mercaptopyrimidines; mercaptotriazines; thioketo compounds such as oxazolinethione; azaindenes, such as triazaindenes, tetraazaindenes (especially 4-hydroxy-substituted (1,3,3a, 7 ) Tetrazaindenes), pentaazaindenes and the like; many compounds known as antifoggants or stabilizers such as benzenethiosulfonic acid, benzenesulfinic acid, benzenesulfonic acid amide, etc. can be added. For example, those described in US Pat. Nos. 3,954,474, 3,982,947 and JP-B-52-28660 can be used.

Gelatin is advantageously used as a binder or protective colloid of the photographic emulsion, but other hydrophilic colloids can also be used.

For example, gelatin derivatives, graft polymers of gelatin and other polymers, proteins such as albumin and casein;
Cellulose derivatives such as hydroxyethyl cellulose, carboxymethyl cellulose, cellulose sulfates and the like, sugar derivatives such as sodium alginate and starch derivatives;
Polyvinyl alcohol, polyvinyl alcohol partial acetal, poly-N-vinylpyrrolidone, polyacrylic acid, polymethacrylic acid, polyacrylamide, polyvinylimidazole, polyvinylpyrazole, etc. Can be used.

As gelatin, lime-treated gelatin, acid-treated gelatin and Bull.Soc.Sci.Phot.Japan, No.16, p.30 (1966)
You may use the enzyme-treated gelatin as described in,
Also, a hydrolyzate or an enzymatic hydrolyzate of gelatin can be used. Examples of the surfactant include saponin (steroidal), alkylene oxide derivative (eg, polyethylene glycol, polyethylene glycol / polypropylene glycol condensate, polyethylene glycol alkyl or alkylaryl ether, polyethylene glycol ester, polyethylene glycol sorbitan ester, polyalkylene). Glycol alkylamines or amides, polyethylene oxide adducts of silicones), glycidol derivatives (eg alkenyl succinic acid polyglycerides, alkylphenol polyglycerides), fatty acid esters of polyhydric alcohols, alkyl esters of sugars, also urethanes or ethers. Nonionic surfactants such as triterpenoid saponin, alkyl carbo Acid salts, alkyl sulfonates, alkyl benzene sulfonates, alkyl naphthalene sulfonates, alkyl sulfates, alkyl phosphates, N-acyl-N-alkyl taurines, sulfosuccinates, sulfoalkyl polyoxyethylenes Anionic surfactants containing an acidic group such as a carboxy group, a sulfo group, a phospho group, a sulfuric acid ester group, a phosphoric acid ester group such as alkylphenyl ethers and polyoxyethylene alkyl phosphates; amino acids, aminoalkyl Amphoteric surfactants such as sulfonic acids, aminoalkyl sulfuric acid or phosphoric acid esters, alkyl betaines, amine imides, amine oxides; alkyl amine salts, aliphatic or aromatic quaternary ammonium salts, pyridinium, imidazo Can be used cationic surfactants such as phosphonium or sulfonium salts containing heterocyclic quaternary ammonium salts such as um, and aliphatic or heterocyclic.

Examples of the dye include oxonol dye, hemioxonol dye, styryl dye, merocyanine dye, cyanine dye and azo dye. Of these, oxonol dyes; hemioxonol dyes and merocyanine dyes are useful. Specific examples of dyes that can be used are described in British Patent 584,609.
No. 1,177,429, JP-A-48-85130, and JP-A-49-99620.
No. 49-114420, No. 52-108115, U.S. Pat.
782, 2,533,472, 2,956,879, 3,148,187
No. 3,177,078, 3,247,127, 3,540,887,
3,575,704, 3,653,905, 3,718,472, 4,0
71,312 and 4,070,352.

Examples of the spectral sensitizing dye include cyanine dyes, merocyanine dyes, complex cyanine dyes, complex merocyanine dyes, holopolar cyanine dyes, hemicyanine dyes, styryl dyes, and hemioxonol dyes. Particularly useful dyes are those belonging to the cyanine dyes, merocyanine dyes and complex merocyanine dyes. Any of the nuclei normally used for cyanine dyes as a basic heterocyclic nucleus can be applied to these dyes. That is,
Pyrroline nuclei, oxazoline nuclei, thiazoline nuclei, pyrrole nuclei, oxazole nuclei, thiazole nuclei, selenazoles, imidazole nuclei, tetrazole nuclei, pyridine nuclei, etc. Nuclei fused with aromatic hydrocarbon rings, namely indolenine nucleus, benzindolenine nucleus, indole nucleus, benzoxazole nucleus, naphthoxazole nucleus, benzothiazole nucleus, naphthothiazole nucleus, benzoselenazole nucleus, benzimidazole nucleus, quinoline Nuclear etc. can be applied. These nuclei may be substituted on carbon atoms.

In the merocyanine dye or the complex merocyanine dye, as a nucleus having a ketomethylene structure, a pyrazolin-5-one nucleus, a thiohydantoin nucleus, 2-thiooxazolidine-
A 5- or 6-membered heterocyclic nucleus such as 2,4-dione nucleus, thiazolidine-2,4-dione nucleus, rhodanine nucleus, or thiobarbituric acid nucleus can be applied.

As the yellow color coupler, a known open-chain ketomethylene coupler can be used. Among these, benzoylacetanilide compounds and pivaloylacetanilide compounds are advantageous.

As a magenta color coupler, a pyrazolone compound,
Indazolone compounds and cyanoacetyl compounds can be used, and pyrazolone compounds are particularly advantageous.

As the cyan color coupler, a phenol compound, a naphthol compound or the like can be used.

Examples of the polymer latex include alkyl (meth) acrylate, acryloxyalkyl (meth) acrylate, glycidyl (meth) acrylate, (meth) acrylamide, vinyl ester (for example, vinyl acetate), acrylonitrile, olefin, styrene, etc., alone or in combination, or A polymer having a monomer component of a combination of these with acrylic acid, methacrylic acid, α, β-unsaturated dicarboxylic acid, hydroxyalkyl (meth) acrylate, sulfoalkyl (meth) acrylate, styrenesulfonic acid, etc. is used. You can

The color antifoggant may include, for example, a hydroquinone derivative, an aminophenol derivative, a gallic acid derivative, an ascorbic acid derivative and the like, and specific examples thereof are U.S. Patents 2,360,290, 2,336,327 and 2,403,721,
2,418,613, 2,675,314, 2,701,197, 2,7
04,713, 2,728,659, 2,732,300, 2,735,76
5, JP-A-50-92988, 50-92989, 50-93928
No. 50-110337, No. 52-146235, and Japanese Patent Publication No. 50-2381
It is described in No. 3 etc.

Examples of the ultraviolet absorber include benzotriazole compounds substituted with an aryl group (see, for example, US Pat.
533,794), 4-thiazolidone compounds (for example, those described in U.S. Pat. Nos. 3,314,794 and 3,352,681), benzophenone compounds (for example, JP-A No.
No. 2784), cinnamic acid ester compounds (for example, those described in US Pat. Nos. 3,705,805 and 3,707,375), butadiene compounds (for example, US Pat. No. 4,045,229).
Or those described in U.S. Pat. No. 3,700,455). Further, those described in US Pat. No. 3,499,762 and JP-A-54-48535 can also be used. Ultraviolet absorbing couplers (for example, α-naphthol type cyan dye forming couplers) and ultraviolet absorbing polymers may be used.

As the anti-fading agent, for example, U.S. Patent No. 2,360,290,
2,418,613, 2,675,314, 2,701,197, 2,7
04,713, 2,728,659, 2,732,300, 2,735,76
5, 2,710,801, 2,816,028, British Patent 1,363,9
No. 21, etc., hydroquinone derivatives, US patents
Gallic acid derivatives described in 3,457,079, 3,069,262, etc., U.S. Patents 2,735,765, 3,698,909, Japanese Patent Publication
P-alkoxyphenols described in 49-20977 and 52-6623, U.S. Pat. Nos. 3,432,300 and 3,573,050
No. 3,574,627, No. 3,764,337, JP-A-52-35633
Nos. 52-147434 and 52-152225.
Oxyphenol derivatives, bisphenols described in US Pat. No. 3,700,455 and the like can be used.

As the support of the silver halide photographic light-sensitive material of the present invention, a film-shaped or sheet-shaped support is usually used.
The material of the support is cellulose nitrate, cellulose ester (these may be partially acetylated) polyvinyl acetal, polyethylene, polyethylene terephthalate, polycarbonate, a film or sheet of plastic such as polyimide, glass,
Examples thereof include films and sheets of paper, metals such as aluminum. Also, baryta paper, resin coated paper and water resistant paper can be used. As the paper support, clay-treated paper such as art paper and coated paper is most suitable, and paper sized with polysaccharide or the like may be used.

Hereinafter, the present invention will be further described with reference to Examples, but the present invention is not limited thereto.

Example 1-1 The polymeric hardeners shown in Table 1-1 were added to a 7% by weight gelatin solution and uniformly coated on a subbed polyethylene terephthalate support to a dry film thickness of about 7μ. A sample I was prepared by coating and drying. 25 of these samples
A part of each sample was taken out 1 day, 7 days and 14 days after application while keeping the humidity at ℃ and 50% RH and swelled in water at 30 ℃ for 5 minutes and the swelling degree V expressed by the following formula was measured. did.

Also, immerse the sample in water at 30 ° C for 5 minutes to get a radius of 0.3mm.
Sapphire needle is pressed onto the sample surface, and the sapphire needle pressing load is continuously changed within the range of 0 to 200 g while moving parallel on the film surface at a speed of 2 mm per second, and the sample film surface is damaged. The load of the needle (scratch resistance) at the time of occurrence of was measured. The results are shown in Table 1-1.

From Table 1-1, in the gelatin layer to which the polymer hardener of the present invention is added, a preferable degree of hardening as a photographic light-sensitive material is obtained in a short period of time, and the phenomenon of post-hardening is not recognized from the result of the swelling degree V. .

The scratch resistance is also sufficient. On the other hand, in Sample 5, sufficient hardness cannot be obtained in a short period of time, and post-hardening continues. In addition, it can be seen that the sample 6 (comparative) has not yet obtained a sufficient degree of hardening and the scratch resistance is insufficient.

Example 1-2 The following polymer hardeners HP-21 and HP-22 were synthesized using the monomer HM-14.

Using HP-21 and HP-22, the degree of swelling and scratch resistance were determined in the same manner as in Example 1-1. The results are shown in Table 1-2.

In Table 1-2, Comparative * 1 and Comparative * 2 are shown in Example 1-1.
The same as the comparison * 1 and the comparison * 2.

From Table 1-2, the same results as in Example 1-1 were obtained for the gelatin layer containing the polymer hardener of the present invention.

Example 2 In the following examples, the addition amount in the silver halide photographic light-sensitive material is per 1 m ² unless otherwise specified.
Also, silver halide and colloidal silver are shown in terms of silver.

Multilayer color photographic elements were prepared by sequentially forming on the triacetylcellulose film support each layer having the composition shown below from the support side.

Multi-Layer Color Photographic Element First Layer; Antihalation Layer (HC-1) Gelatin layer containing black colloidal silver.

Gelatin 2.2 g / m ² Second layer; Intermediate layer (IL) A gelatin layer containing an emulsified dispersion of 2,5-di-t-octylhydroquinone.

Gelatin 1.2 g / m ² 3rd layer; low-sensitivity red-sensitive silver halide emulsion layer (RL-1) Average grain size () 0.30 μm, consisting of AgBrI containing 6 mol% AgI Monodisperse emulsion (Emulsion I) ... Silver coating Amount of 1.8 g / m ² Sensitizing dye I ... 6 × 10 ^-5 mol per mol of silver Sensitizing dye II ... 1.0 × 10 ^-5 mol per mol of silver Cyan coupler (C-1) ... ... 0.06 moles per 1 mole silver Colored cyan coupler (CC-1) ... per 1 mole silver
0.003 mol DIR compound (D-1) ... 0.0015 mol per 1 mol of silver DIR compound (D-2) ... 0.002 mol per 1 mol of silver Gelatin 1.4 g / m ² 4th layer; high sensitivity red sensitivity Silver halide emulsion layer (RH-1) Monodisperse emulsion consisting of AgBrI containing average grain size () 0.5 μm and AgI 7.0 mol% (Emulsion H) ... Silver coating amount 1.3 g / m ² Sensitizing dye I .... 3 × 10 ⁻⁵ mol Sensitizing Dye II per 1 mol of silver 1.0 × 10 ⁻⁵ mol per 1 mol of silver Cyan coupler (C-1) …… 0.02 mol per 1 mol of silver Colored cyan coupler (CC-1) ... for 1 mole of silver
0.0015 mol DIR compound (D-2): 0.001 mol per mol of silver Gelatin 1.0 g / m ² 5th layer; Intermediate (IL) The same gelatin layer as the 2nd layer.

Gelatin 1.0 g / m ² 6th layer; low-sensitivity green-sensitive silver halide emulsion layer (GL-1) Emulsion-I ... Coating silver amount 1.5 g / m ² Sensitizing dye III ... 2.5 per 1 mol of silver × 10 ^-5 1.2 × 10 ^-5 mol magenta color moles sensitizing dye IV ...... silver mole (M-1) ...... silver mole relative to 0.05 mole colored magenta coupler (CM-1) ... silver 0.009 mol to 1 mol DIR compound (D-1) ... 0.0010 mol to 1 mol silver DIR compound (D-3) ... 0.0030 mol to 1 mol silver Gelatin 2.0 g / m ² 7th layer High-sensitivity green-sensitive silver halide emulsion layer (GH-1) Emulsion-II: coating amount of silver 1.4 g / m ² sensitizing dye III: 1.5 × 10 ^-5 mol sensitizing dye per 1 mol of silver IV …… 1.0 × 10 ^-5 mol for 1 mol of silver Magenta coupler (M-1) …… 0.02 for 1 mol of silver
0 mol Colored magenta coupler (CM-1) ... 0.002 mol per mol of silver DIR compound (D-3) ... 0.0010 mol per mol of silver Gelatin 1.8 g / m ² Eighth layer; Yellow filter layer ( YC-1) A gelatin layer containing yellow colloidal silver and an emulsified dispersion of 2,5-di-t-octylhydroquinone.

Gelatin 1.5 g / m ² Ninth layer; low-sensitivity blue-sensitive silver halide emulsion layer (BL-1) consisting of AgBrI containing 0.48 μm in average particle size and 6 mol% of AgI.

Monodisperse emulsion (Emulsion III): Silver coating amount 0.9 g / m ² Sensitizing dye V: 1.3 × 10 ⁻⁵ mol per 1 mol of silver Yellow coupler (Y-1): 0.29 per 1 mol of silver
Molar gelatin 1.9 g / m ² 10th layer; high-sensitivity blue-sensitive emulsion layer (BH-1) Monodisperse emulsion (Emulsion IV) consisting of AgBrI with average grain size 0.8 μm and AgI 15 mol% ... Silver coating amount 0.5 g / m ² Sensitizing dye V: 1.0 × 10 ⁻⁵ mol per mol of silver Yellow coupler (Y-1): 0.08 per mol of silver
Molar DIR compound (D-2) ... 0.0015 mol per mol of silver Gelatin 1.6 g / m ² 11th layer; 1st protective layer (Pro-1) Silver iodobromide (AgI mol% average particle size 0.07 μm) ) Silver coating amount 0.5g /
m ² A gelatin layer containing UV absorbers UV-1 and UV-2.

Gelatin 1.2 g / m ² 12th layer; 2nd protective layer (Pro-2) Polymethyl methacrylate particles (diameter 1.5 μm) Ethyl methacrylate: methyl methacrylate: methacrylic acid copolymer particles (average particle size 2.5 μm) And a gelatin layer containing formalin scavenger (HS-1) 1.2 g / m ^{2 of} gelatin In addition to the above composition, each layer contains a gelatin hardener (H-
1) and the polymer hardener of the present invention (shown in Table 2) were added.

The compounds contained in each layer of the photographic element are as follows.

Sensitizing dye I; anhydro 5,5'-dichloro-9-ethyl-
3,3'-di- (3-sulfopropyl) thiacarbocyanine hydroxide sensitizing dye II; anhydro 9-ethyl-3,3'-di- (3-
Sulfopropyl) -4,5,4 ', 5'-dibenzothiacarbocyanine hydroxide Sensitizing dye III; anhydro 5,5'-diphenyl-9-ethyl-3,3'-di- (3-sulfopropyl) Oxacarbocyanine hydroxide sensitizing dye IV; anhydro 9-ethyl-3,3'-di- (3-
Sulfopropyl) -5,6,5 ', 6'-dibenzoxacarbocyanine hydroxide Sensitizing dye V; anhydro 3,3'-di- (3-sulfopropyl) -4,5-benzo-5'-methoxy Thiacyanine Each of the samples thus prepared was subjected to wedge exposure with white light and then subjected to the following development treatment, and the scratch resistance and the degree of swelling were measured in the same manner as in Example 1. Sensitivity is the reciprocal of the exposure amount that gives a density of fog +0.5, and the sensitivity of the blank is 100.

The blank did not contain the polymer hardener of the present invention.

 The results are shown in Table-2.

Treatment process (38 ℃) Color development 3 minutes 15 seconds Bleach 6 minutes 30 seconds Washing 3 minutes 15 seconds Fixing 6 minutes 30 seconds Washing 3 minutes 15 seconds Stabilization 1 minute 30 seconds Drying The composition of the treatment solution used in each processing step is as follows. Is the street.

[Color developer] 4-amino-3-methyl-N-ethyl-N- (β-hydroxyethyl) -aniline ・ sulfate 4.75g anhydrous sodium sulfite 4.25g hydroxylamine ・ 1/2 sulfate 2.0g anhydrous potassium carbonate 37.5g Sodium bromide 1.3g Nitrilotriacetic acid.3 sodium salt (monohydrate) 2.5g Potassium hydroxide 1.0g Add water to make 1.

[Bleach] Ethylenediaminetetraacetic acid iron ammonium salt 100.g Ethylenediaminetetraacetic acid diammonium salt 10.0g Ammonium bromide 150.0g Glacial acetic acid 10.0ml Add water to make 1 and pH = 6.0 using ammonia water.
Adjust to.

[Fixing solution] Ammonium thiosulfate 175.0 g Anhydrous sodium sulfite 8.5 g Sodium metasulfite 2.3 g Add water to make 1 and adjust the pH to 6.0 with acetic acid.

[Stabilizing solution] Formalin (37% aqueous solution) 1.5 ml Conidax (manufactured by Konishi Roku Kogyo Co., Ltd.) 7.5 ml Make up to 1 by adding water.

From Table 2, in the light-sensitive material to which the polymer hardener of the present invention is added, the sensitivity is not decreased, the fog is less generated, and the fog is less increased even under the forced condition.

Furthermore, the degree of swelling is extremely small, and the scratch resistance is greatly improved.

On the other hand, in the comparative example, the deterioration of the sensitivity and the increase of the fog are not so much observed, but the scratch resistance is not sufficiently obtained as compared with the sample of the present invention, and the problem of post-duraion remains at all. There is.

Example 3 An X-ray photosensitive material sample was obtained by sequentially forming layers having the compositions shown below on both sides of a polyethylene terephthalate support which had been subjected to subbing, from the support side.

Additives other than silver halide are shown in amounts per mol of silver halide unless otherwise specified.

1st layer Crossover layer Dye (I) 3 mg / m ² Gelatin 0.2 g / m ² 2nd layer Emulsion layer Emulsion consisting of AgBrI containing 1.2 μm average grain size and 1.5 mol% AgI Silver coating amount …… 4 g / m ² 4-Hydroxy-6-methyl-1,3,3a, 7-tetrazaindene …… 1.2g Diethylene glycol …… 11.0g Paranitrophenyl triphenylphosphide chloride …… 0.2g Gelatin …… 2.0g / m ² Polyethyl acrylate latex …… 1.0g / m ² Third layer Protective layer Diethylhexyl succinate sodium sulfonate …… .0.
015g / m ² glyoxal …… 0.02g / m ² mucochloric acid …… 0.015g / m ² Polymethylmethacrylate particles (average particle size 3-4μ)
...... 50 mg / m ² Sodium polyoxyethylene-di-nonylphenyl ether sulfate …… 50 mg / m ² Gelatin …… 1.0 g / m ² Polyethyl acrylate latex …… 0.5 g / m ² C ₈ F ₁₇ SO ₃ K… ... 3 mg / m ² Polymeric hardener of the present invention (described in Table 3) Each sample was exposed in the same manner as in Example 2 and then subjected to the following processing to measure the same photographic characteristics and film strength as in Example 2. The results are shown in Table-3.

[Processing step] Development 30 ℃ 45 seconds Fixing 25 ℃ 35 seconds Washing with water 15 ℃ 35 seconds Drying 45 ℃ 20 seconds [Developer] Phenidone 0.4g Methol 5g Hydroquinone 1g Anhydrous sodium sulfite 60g Sodium hydrocarbonate 54g 5-Nitroimidazole 100mg Bromide Add 2.5 g of potassium water to make 1000 ml and adjust the pH to 10.20.

[Fixer] (Part A) Ammonium thiosulfate 170g Sodium sulfite 15g Boric acid 6.5g Glacial acetic acid 12ml Sodium citrate (dihydrate) 2.5g Add water to make 275ml.

(Part B) Aluminum sulfate 15g 98% Sulfuric acid 2.5g Add water to make 40ml.

When using, add water to Part A: 275 ml, Part B: 40 ml to make 1.

From Table 3, in the X-ray light-sensitive material in which the polymer hardener of the present invention is added to the protective layer, the sensitivity of the photographic performance is slightly decreased, and fog is generated or fog is increased under the forced condition. Absent. In terms of film strength, the degree of swelling is small and the scratch resistance is extremely improved.

In the comparative example, although a decrease in sensitivity and a slight increase in fog were observed, it cannot be said that the scratch resistance is sufficient.

Example 4 Each layer having the composition shown below was sequentially formed on both surfaces of a polyethylene terephthalate support which had been subjected to subbing, from the support side to obtain a photosensitive material sample for plate making.

Additives other than silver halide are shown in amounts per mol of silver halide unless otherwise specified.

1st layer Emulsion layer Emulsion consisting of AgBrCl containing average grain size 0.2μ AgBr24 mol% Silver coating amount …… 4.0g / m ² 4-hydroxy-6-methyl-1,1,3a, 7-tetrazaindene …… 0.6g Polyoxyethylene nonyl phenyl ether ... 50mg / m
² Polyco (styrene-butyl acrylate) latex ...
… 1.5mg / m ² Gelatin …… 2.5g / m ² Second layer Protective layer Gelatin …… 1.0g / m ² Polyco (styrene-butyl acrylate) latex…
… 0.8g / m ² Polymethylmethacrylate particles (average particle size 3-4μ) …… 50
mg / m ² mucochloric acid ... 15 mg / m ² Polymeric hardener of the present invention (described in Table 4) Each sample was wedge-exposed and processed as described below, and sensitivity as in Example 2, Fog and film strength were examined.
The results are shown in Table-4.

[Processing conditions] Development 29 ℃ 30 seconds Fixing 28 ℃ 20 seconds Washing 20 ℃ 20 seconds Drying 45 ℃ 30 seconds [Developer (stock solution)] Potassium bromide 2.5g Ethylenediaminetetraacetic acid disodium 1g Potassium sulfite (55% aqueous solution) 90ml Potassium carbonate 25g Hydroquinone 10g 5-Methylbenzotriazole 100mg 5-Nitrobenzotriazole 100mg 1-Phenyl-5-mercaptotetrazole 30mg 5-Nitroimidazole 50mg 1-Phenyl-4-methyl-4-hydroxymethyl-3
-Pyrazolidone 0.5g Diethylene glycol 60g Sodium hydroxide Adjust the pH to 10.6 Add water to make 500 ml. (PH 10.6) When using, dilute the above stock solution with water to double volume.

[Fixer] (Part A) Ammonium thiosulfate 170g Sodium sulfite 15g Boric acid 6.5g Glacial acetic acid 12ml Sodium citrate (dihydrate) 2.5g Add water to make 275ml.

(Part B) Aluminum sulfate (18-hydrate) 15 g 98% sulfuric acid 2.5 g Add water to make 40 ml.

About 600 ml of water is added to 275 ml of Part A above.
Then add 40 ml of Part B, and then add water to add 1
Make up to 000 ml.

From Table 4, in the light-sensitive material for plate making in which the polymeric hardener of the present invention is added to the protective layer, the sensitivity of photographic performance is extremely low, and the deterioration of sensitivity and the increase of fog under forced conditions are very slight.

In the comparative example in which the film strength is also low in swelling degree and the scratch resistance is extremely improved, a decrease in sensitivity and a slight increase in fog under forced conditions are observed, and the scratch resistance is insufficient.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (56) Reference JP-A-56-142524 (JP, A) JP-A-60-61742 (JP, A) JP-A-61-97649 (JP, A) JP-A-57- 212427 (JP, A) JP 59-31944 (JP, A) JP 59-113074 (JP, A) JP 59-121327 (JP, A) JP 60-83936 (JP, A) JP 60-112034 (JP, A) JP 61-61146 (JP, A)

Claims (1)

(57) [Claims] 1. A silver halide photographic light-sensitive material having at least one non-photosensitive layer and at least one silver halide emulsion layer on a support, wherein at least the non-photosensitive layer and the silver halide emulsion layer are provided. A silver halide photographic light-sensitive material, wherein one layer is hardened with a polymer hardener having a repeating unit represented by the following general formula [I]. [In the formula, A represents a monomer unit copolymerizable with a copolymerizable ethylenically unsaturated monomer. R ₁ is a hydrogen atom, a lower alkyl group having 1 to 6 carbon atoms,
It represents a halogen atom or a CO-L-SO ₂ X. J is a lower alkylene group having 1 to 6 carbon atoms or Represents (However, R ₂ represents an aryl group having 6 to 12 carbon atoms, Z ₁ and Z ₂ each represent an atom necessary for forming a ring containing at least one nitrogen atom.) L represents —CO ₂ -and 2 with 3 to 15 carbon atoms having at least one of the bonds
A valent linking group or -O-, -CO -, - SO -, - SO 2 -, - SO 3 -, 2 having 1 to 12 carbon atoms having at least one bond
Represents a valent linking group. (However, R ₃ represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms or an aryl group having 6 to 12 carbon atoms. Z ₃ is necessary for forming a ring containing at least one nitrogen atom. represents an atomic group.) X represents a -CO = CH ₂ or -CH ₂ CH ₂ -Q. (However, Q
Represents a group which can be displaced by a nucleophilic group or a group which can be split off in the form of HQ by a base. ) X and y represent mole percentages, x is 0 to 99, and y is 1 to 100. n is an integer of 0 or 1. ]