JPH0443346A - Silver halide color photographic sensitive material - Google Patents

Abstract

PURPOSE:To improve color reproducibility by providing at least one layer of silver halide photographic emulsion layers on a base. CONSTITUTION:At least one layer of the silver halide photographic emulsion layers contg. the emulsified dispersion of lipophilic fine particles obtd. by dispersing a liquid mixture contg. at least one kind of the cyan dye forming couplers expressed by formula I and at least one kind of water-insoluble and org. solvent- soluble independent or copolymers are provided on the base. In the formula I, A denotes an aryl group or heterocyclic group; Z denotes a constituting element forming a nitrogenous heterocycle together with a nitrogen atom; X denotes a hydrogen atom or a group which can be eliminated by reaction with the oxidant of a color developing agent. The silver halide color photographic sensitive material which has cyan dye images of good light absorption characteristics and forms the color images fast under dark preservation and photoirradiation is obtd. in this way.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a silver halide color photographic light-sensitive material, and more particularly to a /X silver halide photographic light-sensitive material with improved color reproducibility.

[Background of the invention]

Silver halide color photographic light-sensitive materials are selectively sensitized to have sensitivity to blue light, green light, and red light.
A photosensitive layer consisting of a seed silver halide emulsion layer is coated on a support in a multilayer configuration.

In order to form a color photographic image, photographic couplers of yellow magenta and 7,773 colors are contained in the photosensitive layer, and the exposed photosensitive material is subjected to color development using a color developing agent such as an aromatic primary amine. do. The oxidized product of the aromatic primary amine undergoes a camping reaction with the coupler to give a coloring dye. In this case, the coupling rate is as high as possible, and the coloring is done in such a way as to give a high coloring density within a limited development time. Those with good properties are preferred. Furthermore, the color-developing dyes are all required to be bright yellow, magenta, and yellow dyes with little side absorption, and to provide color photographic images with good color reproducibility.

In order to meet the above-mentioned requirements for color sensitive materials, couplers play a major role as color image forming agents, and many improvements have been made by changing the structure of couplers.

Conventionally, phenol derivatives have been mainly used as cyan couplers, but the color image formed from this has unnecessary absorption not only in the target red light region but also in the green and blue light regions, making it difficult to achieve sufficient performance. I cannot say that I have it.

An imidazole coupler was published in JP-A-63-2266 as a cyan coupler with excellent light absorption properties for color images.
It is disclosed in No. 53. However, when imidazole-based cyan couplers are used, the fastness under high temperature, high humidity, and even light irradiation is insufficient, and further improvements have been desired.

On the other hand, an imidazole coupler with improved fastness is disclosed in European Patent No. 0,320,778.

It is true that the fastness is improved by using the coupler described in this patent, but it was found that the light absorption characteristics were deteriorated.

[Purpose of the invention]

Therefore, a first object of the present invention is to provide a color photographic material with excellent color reproducibility due to a cyan image having good light absorption characteristics.

The second purpose is to provide a color photographic material that has a robust color image both under dark storage and under light irradiation.

[Structure of the invention]

As a result of various studies, the present inventors have discovered that the above object can be achieved by the following silver halide color photographic light-sensitive material. That is, a liquid mixture containing at least one cyan dye-forming coupler represented by the following (I) and at least one water-insoluble and organic solvent-soluble homopolymer or copolymer is dispersed on a support. 1. A silver halide color photographic light-sensitive material, comprising at least one silver halide photographic emulsion layer containing an emulsified dispersion of lipophilic fine particles obtained by the process.

General Formula (I) In the formula, A represents an aryl group or a heterocyclic group. 2 represents a component that forms a nitrogen-containing heterocycle together with a nitrogen atom. X represents a hydrogen atom or a group that can be separated by reaction with an oxidized product of a color developing agent.

The present invention will be explained in more detail below.

- The compound represented by installation (1) may be a monomer or a multimer. Multimer means one having two or more groups represented by the general formula [I] in one molecule, and includes bis forms and polymer couplers. Here, the polymer coupler may be a homopolymer consisting only of a monomer having a moiety represented by general formula (1) (preferably one having a vinyl group, hereinafter referred to as vinyl monomer), or A copolymer may be prepared with a non-color-forming ethylene-like monomer that does not couple with the oxidized product of the grade amine developing agent.

Among the compounds represented by the general formula [I], representative examples include the following in which A is a phenyl group: General formula (II) In the general formula (II), R represents a substituent, m is 0~
represents an integer of 5, and X and Z have the same meanings as in the above-mentioned (1).

Next, the compound represented by the general formula (It) will be explained in more detail.

The substituent represented by R is not particularly limited, but for example, the halogen atom and the alkyl group represented by cyano, nitro, carpokyl, alkyl, alkoxy, carbamoyl, sulfamoyl, acyl, afluoxy, and alkyl R include a carbon atom. A linear or branched alkyl group having numbers 1 to 22 is preferable, such as methyl, ethyl, butyl, dodecyl, and the like. These alkyl groups also include cycloalkyl groups such as cyclohexyl groups, and may be substituted. Preferred substituents include halogen atoms, hydroxyl groups, carboxyl groups, cyano groups, sulfo groups, and alkoxy groups having 1 to 22 carbon atoms.

The alkoxy group is preferably a straight chain or branched alkoxy group having 1 to 22 carbon atoms, such as methoxy, ethoxy,
Examples include i-propyloxy, octyloxy, and dodecyloxy groups.

Examples of the carbamoyl group include unsubstituted alkylcarbamoyl groups such as ethylcarbamoyl and dodecylcarbamoyl groups, and substituted alkylcarbamoyl groups such as diethylcarbamoyl, butyloxypropylcarbamoyl and dodecyloxypropylcarbamoyl groups.

Similarly, regarding sulfamoyl groups, unsubstituted alkylsulfamoyl groups such as ethylsulfamoyl, diethylsulfamoyl, and dodecylsulfamoyl groups, substituted alkylsulfamoyl groups such as dodecyloxypropylsulfamoyl groups, etc. Can be mentioned.

Examples of the arylcarbamoyl group include a phenylcarbamoyl group and a substituted phenylcarbamoyl group, and examples of the arylsulfamoyl group include a phenylsulfamoyl group and various substituted phenylsulfamoyl groups.

Also, acyl groups such as acetyl, benzoyl, butanesulfonyl, benzenesulfonyl groups, acyloxy groups such as acetoxy, lauroyloxy, butanesulfonyloxy Me, alkoxy groups such as ethoxycarbonyl, i-propyloxycarbonyl, 2-ethylhexyloxycarbonyl groups, etc. Examples include carbonyl groups.

The -NHCOR, group represents an alkylamide group having 1 to 22 carbon atoms, and representative examples of the unsubstituted alkylamide group include acetamide, butanamide, laurylamide, stearylamide groups, and the like. In addition, an alicyclic amide group such as a cyclohexanecarbonamide group may be used, and 2
- It may have a branched structure such as an ethylhexanamide group, or it may contain an unsaturated bond.

Examples of the substituted alkylamide group include halogen-substituted alkylamide groups such as monochloroacetamide, trichloroacetamide, perfluorobutanamide, m-pentadecylphenoxyacetamide, σ-(2,4-di-t-
amylphenoxy)pentanamide, ff-(2,4-
Examples include phenoxy-substituted alkylamide groups such as di-t-amylphenoxy)acetamide and 0-chlorophenoxymyristic acidamide groups.

In addition, -NHCOR, group represents an arylamide group, typically an unsubstituted arylamide group such as benzamide or naphthamide group, and a substituted arylamide group such as p
-L-butylbenzamide, alkyl-substituted benzamide groups such as p-methylbenzamide groups, alkoxy-substituted benzamide groups such as p-methoxybenzamide and 0-dodecyloxybenzamide groups, p-acetamidobenzamide, m- lauroylamitohenzamide, m, -(2+
Representative examples include amide-substituted benzamide groups such as 4-di-t-amylphenoquinacetamide) benzamide groups, sulfonamide-substituted benzamide groups such as 0-hexadecanesulfonamide benzamide groups, and p-butanesulfonamide benzamide groups. It is mentioned in

The NHCOOR+ group represents a substituted or unsubstituted alkoxycarbonylamino group having 1 to 22 carbon atoms, and representative examples include ethoxycarbonylamino, 1-propoxycarbonylamino, octyloxycarbonylamino, decyloxycarbonylamino, and methoxycarbonylamino. Examples include amino groups.

The -NHCOOR, group also represents an aryloki7carponylamino group, and a typical example thereof is a phenoxycarbonylamino group.

represents a group, typically dimethyl, rubamoylamino,
Examples include diethylcarbamoylamino group.

NH30! The Rr group represents an alkylsulfonamide group or an arylsulfonamide group.

Examples of the alkylsulfonamide group include substituted alkylsulfonamide groups such as unsubstituted alkylsulfonamide groups having 1 to 22 carbon atoms, such as methanesulfonamide, butanesulfonamide, and dodecanesulfonamide groups.

Further, the arylsulfonamide group includes unsubstituted arylsulfonamide groups such as benzenesulfonamide and naphthalenesulfonamide groups, and alkyl-substituted benzenesulfonamide groups such as haptoluenesulfonamide benzenesulfonamide group and zoyldecylbenzenesulfonamide group. , p-dodecyloxybenzenesulfonamide, p-butoxybenzenesulfonamide, and other alkoxy-substituted benzenesulfonamide groups.

Typical examples include dimethylsulfamoylamino,
Dialkylsulfamoylamino groups such as dibutylsulfamoylamino groups are preferred.

Groups that can be separated by reaction with the oxidized product of the color developing agent represented by X include, for example, halogen atoms (chlorine, bromine, fluorine, etc.), hydroxyl, alkoxy, aryloxy,
Heterocyclicoxy, acyloxy, sulfonyloxy, alkoxycarbonyloxy, aryloxycarbonyl,
Alkyloxalyloxy, alkoxyoxalyloxy, alkylthio, mercapto, arylthio, heterocyclicthio, alkoxythiocarbonylthio, acylamino,
Various groups such as substituted amino, nitrogen-containing heterocycle bonded with NJ atom, sulfonamide, alkoxycarbonylamino, aryloxycarbonylamino, and carpoquinyl are mentioned, and preferably a halogen atom, particularly a fluorine atom or a chlorine atom.

Among the compounds represented by (n), compounds represented by the general formula (I[[) are more preferred.

-Installation (Ill) In the formula, R, Z and X have the same meanings as in -Installation CI [), and n represents an integer of O to 4. R,
is an alkyl group, an aryl group, -COR. , - SO.
R. .

. . As the alkyl group and aryl group represented by N<R·COOR + or R, the alkyl group and aryl group explained in -Installation [■] can be specifically mentioned.

Also, - NHR. is -NHCOR+, -NHCOO
R+.

In the case, R and R2 are those in the general formula [1[),
- In the introduction [I], any one of A, X, and Z groups may form a dimer or more multimeric coupler independently or together. When dimerized, these groups can be used as simple bonds or as divalent linking groups (e.g., divalent groups such as alkylene groups, arylene groups, ether groups, ester groups, amide groups, and divalent groups that are combinations of these groups). etc.), and when forming an oligomer or polymer, those groups are preferably in the polymer backbone chain or bonded to the polymer backbone through a divalent group as described for dimers.

When forming the polymer, even if it is a homopolymer of the coupler derivative, other non-chromogenic ethylene-like monomers (e.g. acrylic acid, methacrylic acid, methyl acrylate, n-
butylacrylamide, β-hydroquine methacrylate, vinyl acetate, acrylonitrile, styrene, crotonic acid, maleic anhydride, N-vinylpyrrolidone, etc.) each has the same meaning.

Compound X 2Hs c, n, (i) Compound Compound Compound Compound X Compound Compound Compound Compound X A Compound X Compound
-sche Berichte), volume 34, 639-
642 pages (1901), Franz Kunke l.
or according to the method reported by EP 32
It can be synthesized by the method described in 0778.

Next, the water-insoluble and organic solvent-soluble polymer according to the present invention will be specifically explained.

(1) Vinyl polymers and copolymers To be more specific about the monomers forming the vinyl polymers and copolymers, examples of acrylic esters include methyl acrylate, ethyl acrylate, isopropyl acrylate, butyl acrylate, and t-butyl acrylate. Acrylate, amyl acrylate, hexyl acrylate,
2-Ethylhexyl acrylate, [-octyl acrylate, 2-chloroethyl acrylate, 4-chlorobutyl acrylate, cyanethyl acrylate, 2-acetoquinoethyl acrylate, dimethylamine ethyl acrylate, methquinbenzyl acrylate, chlorohexyl acrylate, tetrahydro Furfuryl acrylate, phenyl acrylate, 2.2 dimethyl-3-hydroquinopropyl acrylate, 2methoxy/ethyl acrylate, 2-ethkynoethyl acrylate, 2-i-
Prophoqui/acrylate, 2-(2-methocinoethquine)ethyl acrylate, ω-methocinopolyethylene glycol acrylate (number of moles added n-9), l-bromo-
Examples include 2-methoxyethyl acrylate.

Examples of methacrylic esters include methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, inbutyl methacrylate,
amyl methacrylate, cyclohexyl methacrylate, benzyl methacrylate, octyl methacrylate,
Sulfopropyl methacrylate, N-ethyl-N-phenylaminoethyl methacrylate, dimethylaminophenoxyethyl methacrylate, furfuryl methacrylate, phenyl methacrylate, talesyl methacrylate, naphthyl methacrylate, 2-hydroxyethyl methacrylate, triethylene glycol monomethacrylate, 2-methoxy Examples include ethyl methacrylate, 2-acetoxyethyl methacrylate, 2-ethoxyethyl methacrylate, 2-(2-methoxyethoxy)ethyl methacrylate, and ω-methquine polyethylene glycol methacrylate (number of moles added n-6).

Examples of vinyl esters include vinyl acetate, vinyl propionate, vinyl butyrate, vinyl isobutyrate, vinyl caproate, vinyl chloroacetate, vinyl methoxy acetate, vinyl phenylacetate), vinyl abflu, and vinyl salicylate. Examples include.

Examples of acrylamide include acrylamide, ethylacrylamide, propylacrylamide, butylacrylamide, t-butylacrylamide, cyclohexylacrylamide, benzylacrylamide, hydroxymethylacrylamide, methoxyethylacrylamide, dimethylaminoethyl acrylamide, phenyl acrylamide, dimethyl acrylamide, β-cyanoethyl Acrylamide, N-(2-acetoacetoxyethyl)acrylamide, diacetone acrylamide, etc.;
Examples of methacrylamide include methacrylamide, methylmethacrylamide, ethylmethacrylamide, propylmethacrylamide, butylmethacrylamide, t~
Butylmethacrylamide, cyclohexylmethacrylamide, benzylmethacrylamide, hydroxymethylmethacrylamide, methoxyethylmethacrylamide,
Examples include dimethylaminoethylmethacrylamide, phenylmethacrylamide, dimethylmethacrylamide, β-cyanoethylmethacrylamide, and N-(2-acetoacetoxyethyl)methacrylamide.

Examples of olefins include dicyclopentadiene, ethylene, phlopyrene, l-phthene, l-pentene, vinyl chloride, vinylidene chloride, isoprene, chloroprene, butadiene, 2.3-, methylbutadiene, and the like. I can do it.

Examples of the styrenes include styrene, methylstyrene, trimethylstyrene, ethylstyrene, chloromethylstyrene, metkynestyrene, chlorostyrene, dichlorostyrene, and vinylbenzoic acid methyl ester.

Examples of crotonate esters include butyl crotonate,
Examples include hequinyl crotonic acid.

Examples of itaconic diesters 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 the fumaric acid diesters include diethyl fumarate, dimethyl fumarate, and dibutyl hexamalate.

Examples of other monomers include:

Allyl compounds, such as allyl acetate, allyl caproate, allyl laurate, allyl benzoate! And so on.

Vinyl ethers, such as methyl vinyl ether, butyl vinyl ether, methoxyethyl vinyl ether,
Dimethylaminoethyl vinyl ether; vinyl ketones such as methyl vinyl ketone, phenyl vinyl ketone, metquin ethyl vinyl ketone, etc.

Vinyl heterocyclic compounds, such as vinylpyridine, N-vinylimidazole, N-vinyloxazolidone, N-vinyltriazole, N-vinylpyrrolidone, etc. Nigrindyl esters, such as glycidyl acrylate, glycidyl methacrylate, etc.: unsaturated nitriles, For example, acrylonitrile, methacrylate trile, etc. can be mentioned.

The polymer used in the present invention may be a homopolymer of the above-mentioned heptamers, or if necessary, two or more heptamers.
A copolymer consisting of the following may also be used. Furthermore, the polymer used in the present invention may contain a monomer having an acid group shown below to the extent that it does not become water-soluble, but preferably 2 monomers have an acid group.
The content is 0% or less, more preferably not at all.

Acrylic acid, methacrylic acid, itafonic acid, maleic acid,
Monoalkyl itaconate, monoalkyl maleate, citraconic acid, styrene sulfonic acid, vinylbenzyl sulfonic acid, acryloyloxyalkylsulfonic acid, acryloyloxyalkylsulfonic acid, methacryloyloxyalkylsulfonic acid, acrylamide alkyl sulfonic acid, methacrylamide alkyl sulfonic acid , acryloyloxyalkyl phosphate, methacryloyloxyalkyl phosphate, and the like.

These acids may be salts of alkali metals (such as Na1) or ammonium ions.

As the seven polymers forming the polymer used in the present invention, acrylate-based, methacrylate-based, acrylamide-based and methacrylate-based are preferred.

The polymer formed from the above seven polymers can be obtained by a solution polymerization method, a bulk polymerization method, a suspension polymerization method, and a latex polymerization method. As the initiators used in these polymerizations, water-soluble polymerization initiators and lipophilic polymerization initiators are used.

Examples of water-soluble polymerization initiators include potassium persulfate,
Persulfates such as ammonium persulfate and sodium persulfate, sodium 4,4'-azobis-4-cyanovalerate,
2. Water-soluble azo compounds such as 2'-azobis(2-amidinopron(one) hydrochloride) and hydrogen peroxide can be used.As the lipophilic polymerization initiator, for example, azobisisobutyronitrile, 2. 2'-azobis-2,4-dimethylvaleronitrile), l,1''-azobis(cyclohexanone-1-carbonitrile), dimethyl 2,2'-azobisisobutyrate, diethyl 2,2'-azobisisobutyrate, etc. Mention may be made of lipophilic azo compounds, benzoyl peroxide, lauryl peroxide, diisopropyl peroxide, and di-t-butyl peroxide.

(2) Polyester resin obtained by condensation of polyhydric alcohol and polybasic acid Polyhydric alcohols include HO-R, -OH (R is a hydrocarbon chain having from 2 to about 12 carbon atoms, especially aliphatic carbon hydrogen chain)
Glycols or polyalkylene glycols having the structure are effective, and as polybasic acids, HOOC-
Those having R, -COOH (R2 represents a simple bond or a hydrocarbon chain having 1 to 12 carbon atoms) are effective.

Specific examples of polyhydric alcohols include ethylene glyfur, diethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, trimethylolpropane, 1,4-butanediol, isobutylene diol, 1,5-bentanediol, Neopentyl glycol, l, 6-hexanediol, l.

8-octanediol, 1.9-7nanediol, 1.
10 Decanediol, glycerin, diglycerin, triglycerin, ■-methylglycerin, erythrinite,
Examples include mannitol, sorbi nodo, etc.

Specific examples of polybasic acids include phosphoric acid, cono-phosphoric acid, glutaric acid, adipic acid, pimelic acid, corric acid, azelaic acid, sebacic acid, decanedicarboxylic acid, dodecanedicarboxylic acid, fumaric acid, maleic acid, Itaconic acid, Nthraconic acid, Phthalic acid, Isophthalic acid, Terephthalic acid, Tetrachlorophthalic acid, Methaconic acid, Isohimelic acid, /
Examples include clopentadiene-maleic anhydride adduct, rosin-maleic anhydride adduct, and the like.

(3) Polyesters Obtained by Ring-Opening Polymerization These polyesters are obtained from β-propiolactone, ε-caprolactone, dimethylpropiolactone, and the like.

(4) Other polymers Polycarbonate resin obtained by polycondensation of glycol or dihydric phenol with carbonate ester or phosgene, polyurethane resin obtained by polyaddition of polyhydric alcohol and polyhydric incyanate, or polyhydric amine and polyamide resins obtained from polybasic acids.

The number average molecular weight of the polymer used in the present invention is not particularly limited, but is preferably 200,000 or less, more preferably 5,000 to 10,000.

The ratio (weight ratio) of the polymer of the present invention to the coupler is:
l:20-20:l is preferable, more preferably 1:
10-10:l.

Specific examples of the polymer used in the present invention are shown below, but the invention is not limited thereto. (The composition of the copolymer is
Shown in weight ratio. ) A-1 Poly(N-5ec-butylacrylamide) A-
2 Poly(N-t-butylacrylamide) A-3 Diacetone acrylamide-methyl methacrylate copolymer (
25 Near 5) A-4 Polycyclohexyl methacrylate A-5N-t
-Butylacrylamide-methyl methacrylate copolymer (60:40) -1O Pol(N,N-dimethylacrylamide)poly([-butyl methacrylate) Polyvinyl acetate Polyvinyl glopionate Polymethyl methacrylate Polyethyl methacrylate Polyethyl acrylate Vinyl acetate- Vinyl alcohol copolymer (90:10) Polybutyl acrylate polybutyl methacrylate polyisobutyl methacrylate polyisopropyl methacrylate polyoctyl acrylate butyl acrylate-acrylamide copolymer (95:
5) Stearyl methacrylate-acrylic acid copolymer (90
:10) Methyl methacrylate-vinyl chloride copolymer (70:3
0) 8-22 Methyl methacrylate-styrene copolymer (
90:10) A-23 Methyl methacrylate-ethyl acrylate copolymer (50:50) A-24 Butyl methacrylate-methyl methacrylate-styrene copolymer (50:20:30) A-2
5 Vinyl acetate-acrylamide copolymer (85:
15) A-26 Vinyl chloride-vinyl acetate copolymer (65:3
5) A-27 Methyl methacrylate-acrylonitrile copolymer (65:35) A-28 Butyl methacrylate-pentyl methacrylate-N-vinyl-2-pyrrolidone copolymer (38:
38:24) A-29 Methyl methacrylate-butyl methacrylate-inbutyl methacrylate-acrylic acid copolymer (
37:29:25co9) A-30 Butyl methacrylate-acrylic acid copolymer (95: 5') A-31 Methyl methacrylate-acrylic acid copolymer (95: 5) Benzyl methacrylate-acrylic acid Copolymer (9
3) Butyl methacrylate-methyl methacrylate-benzyl methacrylate-acrylic acid copolymer (35:35:
25+5) Butyl methacrylate-methyl methacrylate-benzyl methacrylate copolymer (40:30
:30) Diacetone acrylamide-methyl methacrylate copolymer (50:50) Methyl vinyl ketone-isobutyl methacrylate copolymer (55:45) Ethyl methacrylate-butyl acrylate copolymer (
70:30) Diacentacrylamide doptyl acrylate copolymer (60:40) Methyl methacrylate-styrene methacrylate-diacetone acrylamide copolymer (40:40:20) A-40 A-43 Butyl acrylate-styrene methacrylate -Diacetone acrylamide copolymer (70: 20: 10
) Stearyl methacrylate-methyl methacrylate-acrylic acid copolymer (50:40:1O) Methyl methacrylate-styrene-vinyl sulfonamide copolymer (70:20:10) Methyl methacrylate-phenyl vinyl ketone copolymer (70:10) 30) Butyl acrylate-methyl methacrylate-butyl methacrylate copolymer (35: 35: 30) Butyl methacrylate = vinyl-2-pyrrolidone copolymer (90: 10) Polypentyl acrylate cyclohexyl methacrylate-methyl methacrylate-propyl methacrylate Copolymer (37:29:34
) Polypentyl methacrylate Methyl methacrylate-butyl methacrylate copolymer (65: 35) Vinyl acetate vinyl propionate copolymer (75:
:25) Butyl methacrylate-3-acryloxybutane-1
-sodium sulfonate copolymer (97:3) butyl methacrylate-methyl methacrylate-acrylamide copolymer (35:35:30) butyl methacrylate-methyl methacrylate-vinyl chloride copolymer (37:36:27) butyl methacrylate Tate-styrene copolymer (82:12) t-butyl methacrylate-methyl methacrylate copolymer (70:30) Poly(N-t-butyl methacrylamide) N-t-butylacrylamide-methylphenyl methacrylate copolymer ( 60:40) Methyl methacrylate-acrylonitrile copolymer (70:30) Methyl methacrylate-methyl vinyl ketone copolymer (
38 Near 2) Methyl methacrylate-styrene copolymer (75:25
) Methyl methacrylate-hexyl methacrylate copolymer (70:30) Butyl methacrylate-acrylic acid copolymer (85:1
5) Methyl methacrylate-acrylic acid copolymer (80:2
0) Methyl methacrylate-acrylic acid copolymer (90:1
0) Methyl methacrylate-acrylic acid copolymer (98:2
) Methyl methacrylate N-vinyl-2-pyrrolidone copolymer (90:10) Butyl methacrylate-vinyl chloride copolymer (90:10)
10) Butyl methacrylate-styrene copolymer (70:30
) 1.4-butanediol ster ethylene glycol ster polycaprolactam polygropiolactam polydimethylpropiolactone N-L-butylacrylamide-dimethylaminoethylacrylamide copolymer adipic acid polyesebacic acid polyester (85:15) N-t- Butyl methacrylamide-vinyl pyridine copolymer (95:5) Diethyl maleate-butyl acrylate copolymer (6:5)
5: 35) Nt-butylacrylamide-2-methquine ethyl acrylate copolymer (55:45) ω-methquine polyethylene glycol methacrylate (number of moles added n = 6)
-Methyl methacrylate (40:60) A-79 A-80 ω-methoxypolyethylene glycol acrylate (number of moles added n-9) -Nt-butylacrylamide (2
5 Near 5) Poly(2-methoxyethyl acrylate) Poly(2-methoxyethyl methacrylate) Poly(2-(2-methoxyethoxy)ethyl acrylate) 2-(2-Butoxyethoxy)ethyl acrylate-methyl methacrylate (58: 42 ) Poly(oxycarbonyloxy-1,4-phenyleneisobutylidene-1)
,4-)unishin)poly(oxyethyleneoxycarbonyliminohexamethyleneiminocarbonyl)N-(4
-(4'-Hydroxyphenylsulfonyl)phenylcoacrylamide-butyl acrylate copolymer (65:
35) N-(4-hydroxyphenyl)methacrylamide-N
-t-Butylacrylamide copolymer (50:50) (4-(4'-hydroxyphenylsulfonyl)phenoxymethyl]styrene (m, p mixture) -Nt-butylacrylamide copolymer (15-:85) The dispersion containing lipophilic fine particles obtained by emulsification and dispersion of the present invention is prepared by dispersing the cyan coupler of the present invention and a water-insoluble and organic solvent-soluble polymer compound in a low boiling point and/or water-soluble organic solvent as necessary. After emulsifying and dispersing in a hydrophilic binder such as an aqueous gelatin solution using a dispersion means such as a stirrer, homogenizer, colloid mill, flow jet mixer, or ultrasonic device, using a surfactant as necessary, It may be added to the desired hydrophilic colloid layer.Low boiling point and/or water-soluble organic solvents may be removed from the prepared dispersion by distillation, noodle washing, or ultrafiltration.

Examples of the low-boiling organic solvent include ethyl acetate, butyl acetate, ethyl propionate, secondary butyl alcohol, methyl ethyl ketone, methyl isobutyl ketone, β-ethoxyethyl acetate, methyl cellosolve acetate, and cyclohexanone.

Examples of water-soluble organic solvents include methyl alcohol, ethyl alcohol, acetone, and tetrahydrofuran. These organic solvents can be used in combination of two or more types, if necessary.

Alternatively, in JP-A-60-107642, monomer components of the above-mentioned single or copolymer are dispersed in a hydrophilic binder by suspension polymerization, solution polymerization or bulk polymerization in the presence of a coupler. The method described in the issue may also be used.

The dispersion may contain a high boiling point organic solvent,
Examples of high boiling point organic solvents that can be used include phenol derivatives, phthalates, phosphates, citric esters, benzoates, alkylamides, fatty butyric esters, trimenoic esters, etc., which do not react with the oxidized form of the developing agent, and have a boiling point of 150°C. The above organic solvents are used.

The silver halide used in the present invention includes any silver halide such as silver chloride, silver bromide, silver iodide, silver chlorobromide, silver iodobromide, and silver chloroiodide.

When rapid processing is desired, such as for color paper, the silver halide grains preferably used in the present invention have a silver chloride content of 90 mol% or more, and a silver bromide content of 1.
The silver iodide content is preferably 0 mol% or less, and the silver iodide content is preferably 0.5 mol% or less. More preferably, the silver bromide content is 0.
．． 1 to 2 mol% silver chlorobromide.

The silver halide grains may be used alone or in combination with other silver halide grains having different compositions.

Further, it may be used in combination with silver halide grains having a silver chloride content of 90 mol % or less.

Further, in a silver halide emulsion layer containing silver halide grains having a silver chloride content of 90 mol % or more, the silver chloride content in the total silver halide grains contained in the emulsion layer is 90 mol %. The proportion of silver halide grains above is 60
It is at least 80% by weight, preferably at least 80% by weight.

In the present invention, it is advantageous to use gelatin as the binder, but gelatin derivatives, graft polymers of gelatin and other polymers, other proteins, sugar derivatives,
Hydrophilic colloids such as synthetic hydrophilic polymeric materials such as cellulose derivatives, monopolymers or copolymers can also be used.

The dye-forming coupler used in the silver halide photographic light-sensitive material of the present invention is usually selected in such a way that a dye is formed in each emulsion layer that absorbs light in the sensitivity spectrum of the emulsion layer. A yellow dye-forming coupler is used in the sensitive emulsion layer, a magenta dye-forming coupler is used in the green-sensitive emulsion layer, and a cyan dye-forming coupler is used in the red-sensitive emulsion layer. However, depending on the purpose, silver halide color photographic materials may be produced using different combinations from the above combinations.

In the present invention, the yellow dye-forming coupler is
Acylacetanilide couplers can be preferably used. Among these, benzoylacetanilide and pivaloylacetanilide compounds are advantageous.

In addition to the above-mentioned compounds, various photographic additives can be added to the silver halide photographic material of the present invention.

Examples include ultraviolet absorbers, development accelerators, surfactants, hardeners, film property improvers, color turbidity inhibitors, dye image stabilizers, background color regulators, and the like.

Among dye-forming couplers, colored couplers, DIR couplers, DIR compounds, image stabilizers, color antifoggants, ultraviolet absorbers, etc. other than the phenolic cyan coupler according to the present invention, which do not need to be adsorbed on the silver halide crystal surface, The hydrophobic compound can be dispersed using various methods such as solid dispersion method, latex dispersion method, oil-in-ice emulsion dispersion method, etc., and this is appropriately selected depending on the chemical structure of the hydrophobic compound such as the coupler. be able to. Various methods for dispersing hydrophobic additives such as couplers can be applied to the oil-in-water emulsion dispersion method, and usually a high boiling point organic solvent with a boiling point of about 150'O or higher is mixed with a low boiling point and/or Dissolved using a water-soluble organic solvent and emulsified and dispersed in a hydrophilic binder such as an aqueous gelatin solution using a surfactant using a dispersion means such as a stirrer, homogenizer, colloid mill, flow jet mixer, or ultrasonic device. After that, it may be added to the desired hydrophilic colloid layer. The dispersion may include a step of removing the low-boiling organic solvent simultaneously with dispersion.

The ratio of high boiling point organic solvent to low boiling point organic solvent is 1:0.1~
1:50, more preferably i:l-1:20.

Examples of high boiling point solvents include organic compounds with a boiling point of 150°C or higher, such as phenol derivatives, phthalate alkyl esters, phosphate esters, citric acid esters, benzoate esters, alkylamides, fatty acid esters, and trimenoate esters, which do not react with the oxidized form of the developing agent. A solvent is used.

Images can be formed on the photographic material of the present invention by subjecting it to a color development treatment known in the art.

The color developing agent used in the color developing solution in the present invention includes known color developing agents that are widely used in various color photographic processes.

These developers include aminophenol and p-phenylenediamine derivatives. These compounds are generally used in the form of salts which are more stable than in the free state, such as hydrochlorides or sulfates. Additionally, these compounds are generally present in concentrations of about 0.1 g to about 30 g for Color Developer IQ, preferably about 1 g to about 15 g for Color Developer 1 (2).
Use at a concentration of g.

Examples of aminophenol-based developers include 0-aminophenol, p-aminephenol, 5-amino-2-hydroquinetoluene, 2-amino-3-hydroquinetoluene, and 2-hydroquine-3-amino-1°4- Contains dimethylbenzene.

Particularly useful primary aromatic amine color developers include N, N-
A dialkyl-p-)echolene diamine compound,
The alkyl group and phenyl group may be substituted with any substituent. Among them, examples of particularly useful compounds include:
N,N-diethyl-p-phenylenediamine hydrochloride,
N-methyl-p-phenylenediamine hydrochloride, N,N-
Dimethyl-p-phenylenediamine til[,2-amino-5-(N-ethyl-N-)'thenuramine)toluene, N-ethyl-N-β-methanesulfonamidoethyl-3-methyl-4-aminoaniline sulfate salt, N-ethyl-N-β-hydroxyethylaminoaniline, 4-amino-3-methyl-N,N-diethylaniline, 4-amino-N-(2-methoxyethyl)-N-ethyl-3-methyl Aniline-1)-toluenesulfonate and the like can be mentioned.

In addition to the above-mentioned primary aromatic amine color developer, known developer component compounds can be added to the color developer applied to the processing of the silver halide photographic material of the present invention. For example, alkaline agents such as sodium hydroxide, sodium carbonate, potassium carbonate, alkali metal sulfites,
Alkali metal bisulfites, alkali metal thiocyanates, alkali metal halides, benzyl alcohol, water softeners, thickeners, and the like may optionally be included.

The pl value of the color developer is usually greater than or equal to 7, most commonly between about 10 and 13.

The color development temperature is usually 15°C or higher, and -20°C for boat fishing.
~50°C. For rapid development, it is preferable to carry out the process at 30°C or higher.

Furthermore, the silver halide photographic material of the present invention is preferably processed with a color developing solution that does not contain benzyl alcohol.

After color development, the silver halide photographic material of the present invention is subjected to bleaching and fixing. Bleaching treatment may be carried out simultaneously with fixing treatment.

Many compounds are used as bleaching agents, but iron (
■), cobalt (■), copper (II), and other polyvalent metal compounds, especially complex salts of these polyvalent metal cations and organic acids, such as ethylenediaminetetraacetic acid, nitrilotriacetic acid,
Aminopolycarboxylic acids such as N-hydroxyethylethylenediaminediacetic acid, malonic acid, tartaric acid, malic acid,
Metal complex salts such as diglycolic acid and dithioglycolic acid,
Alternatively, ferricyanates, dichromates, etc. may be used alone or in appropriate combinations.

As the fixing agent, a soluble complexing agent that solubilizes silver halide as a complex salt is used. Examples of the soluble complexing agent include sodium thiosulfate, ammonium thiosulfate,
Examples include potassium thiocyanate, thiourea, and thioether.

After the fixing process, a washing process is usually performed.

Further, as an alternative treatment to the water washing treatment, a stabilization treatment may be performed, or both may be used in combination.

〔Example〕

EXAMPLES Hereinafter, the present invention will be specifically explained with reference to Examples, but the embodiments are not limited thereto.

Example 1 Each layer having the structure shown in Table 1 was coated on a support laminated with polyethylene on one side of a paper support and polyethylene containing titanium oxide on the first layer side of the other side. A silver oxide color photographic material was prepared. The coating solution was prepared as follows.

First layer coating solution: 26.7 g of yellow coupler (Yl), 0.67 g of stain inhibitor (HQ-1), 13.3 g of high boiling point organic solvent (D B P ), and 60 m< of ethyl acetate.
1 was added and dissolved, and this solution was emulsified and dispersed in 200 mQ of a lO% gelatin aqueous solution containing 10% sodium alkylnaphthalene sulfonate (i) using a homogenizer to prepare a yellow coupler dispersion.

This dispersion was mixed with a blue-sensitive silver chlorobromide emulsion (lO% silver chloride, 90% silver bromide, 10 g in terms of silver) and a gelatin solution for coating to prepare a first layer coating solution.

The second to seventh layer coating solutions were also prepared in the same manner as the first layer coating solution. However, the uncoupler dispersion liquid used for the fifth layer coating liquid was prepared as follows.

12 g of cyan coupler (n-4), high boiling point organic solvent (D
BP) 10 g and 18 g of the exemplary compound (A-2) of the present invention having an average molecular weight of about 60,000 was dissolved in 40 mQ of ethyl acetate, and this solution was mixed with 20 10% aqueous gelatin solution containing 10 mQ of 10% sodium alkylnaphthalene sulfonate.
An uncoupler dispersion liquid was prepared by emulsifying and dispersing the mixture at 0 mQ using a homogenizer.

In addition, the following compound (H-1) was used as a hardening agent for gelatin.
．． 08g/m” added.

UV 5T-1 LIH3CH3 Table = 1-2 UV-1 T-2 The obtained sample was wedge exposed using a photosensitive needle KS-7 (manufactured by Konica Corporation) and processed according to the following color development process. , perform the following evaluation.

[Processing process] Color development 3 minutes 30 seconds Temperature 33℃ Bleach fixing 1 minute 30 seconds Temperature 33℃ Water washing
3 minutes Temperature: 33°C Color developer recipe N-ethyl-N-β-methanesulfonamidoethyl-3-methyl-4-aminoaniline sulfate 4.9g Hydroquinylamine sulfate 2.0g Potassium carbonate 25.0g bromide sodium
0.6g anhydrous sodium sulfite
2.0g benzyl alcohol
13m12 polyethylene glycol (average degree of polymerization 400) 3.0m4 Add water to make 1Q, dilute with sodium hydroxide (p) (1O80
Adjust to.

Bleach-fix solution formulation Ethylenediaminetetraacetic acid iron (III) sodium salt 6.0g Ammonium thiosulfate 100g Sodium bisulfite 1Og Sodium metabisulfite 3g Add water to make 1Q, and adjust the pH to 7.0 with aqueous ammonia.

Lightfastness> The obtained sample was stored outdoors under sunlight (on an exposure stand) for one week, and evaluated by determining the residual rate (%) of the dye image at an initial density of 1.0.

Fade Resistance> The obtained sample was stored under conditions of 77° C. and 60% RH for 14 days, and evaluated by determining the residual rate (%) of the dye image at an initial density of 1.0.

Further, the reflection spectrum of the obtained dye image was measured by attaching an integrating sphere to a self-recording spectrophotometer (Model 321O, manufactured by Hitachi, Ltd.), and λ1Ilax was measured at a density of 1.0. (
The reference side is magnesium oxide) In addition, the wavelength (λ.2) on the short wave side at which the absorbance is 20% of the absorbance at λmaX was determined, and the cutoff of absorption on the short wave side was determined using the following definition.

ΔλS−λwax−λ. .

The smaller ΔλS is, the sharper the absorption on the short wavelength side is.

It can be seen that in Table 2 and Samples 5 to 1O using the polymer, the heat resistance and light resistance were improved, and the sharpness of absorption was also improved at the same time.

Sample 3 using comparative compound CC-2 has sharp absorption, but its heat resistance and light resistance are poor (l/~).

As is clear from Table 2, samples 1 and 2 using comparative compound CC-1 have good heat resistance and light resistance, but
Absorption sharpness is lacking.

Further, in Sample 4 in which the cyan coupler of the present invention was used alone, although the sharpness of absorption was improved, the heat resistance and light resistance were still insufficient.

Compared to these samples, the cyan coupler C-2 of the present invention [Effects of the invention] According to the present invention, it has a cyan color image with good light absorption characteristics, and the color image is robust under dark storage and under light irradiation. A silver halide color photographic material could be provided.

Claims (1)

[Scope of Claims] A mixture containing on a support at least one cyan dye-forming coupler represented by the following general formula [I] and at least one water-insoluble and organic solvent-soluble homopolymer or copolymer. A silver halide color photographic light-sensitive material comprising at least one silver halide photographic emulsion layer containing an emulsified dispersion of lipophilic fine particles obtained by dispersing a liquid. General formula [I] ▲There are mathematical formulas, chemical formulas, tables, etc.▼ [In the formula, A represents an aryl group or a heterocyclic group. Z represents a component that forms a nitrogen-containing heterocycle together with a nitrogen atom. X represents a hydrogen atom or a group that can be separated by reaction with an oxidized product of a color developing agent. ]