JPH0439657A - Silver halide color photographic sensitive material - Google Patents

Abstract

PURPOSE:To improve color developability and color reproducibility and to lessen the change in photographic performance at the time of continuous processing by forming the above photosensitive material in such a manner that specific cyan couplers are dispersed in copresence with a water insoluble- and org. solvent-soluble solvent alone or at least one kind of copolymers into silver halide emulsion layers. CONSTITUTION:At least one kind of the cyan couplers expressed by formulas I to III, etc., and the water insoluble- and org. solvent- soluble solvent alone or at least one kind of the copolymers are dispersed so as to exist in the silver halide emulsion layers. In the formulas, R1 and R3 denote a hydrogen atom or substituent; R2 denotes a substituent; X denotes a hydrogen atom or the substituent which is eliminated by reaction with the oxidant of a color developing agent; (n) denotes an integer from 0 to 4. The silver halide photographic sensitive material which has the excellent color developability and the good color reproducibility and lessens the change in the photographic performance at the time of continuous processing 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 that has excellent color reproducibility, high color development, and little change in photographic properties during continuous processing.

[Background of the Invention] After a silver halide photographic material is exposed to light and subjected to color development processing, an oxidized aromatic primary amine color developing agent and a dye-forming coupler react to form a dye. A color image is formed.

Generally, this photographic method uses a subtractive color reproduction method to form yellow, magenta and cyan color images.

Phenols or naphthols have been widely used as cyan image forming couplers.

However, cyan images obtained from conventionally used phenols and naphthols have serious problems in color reproduction. This is because the absorption is not sharp on the short wavelength side, and there is also unnecessary absorption, that is, asymmetric absorption, in the edge region. As a result, in the case of negatives, it is necessary to correct the asymmetric absorption by masking or the like, and in the case of vapors, there is no means of correction, and the current situation is that color reproducibility is considerably deteriorated.

Furthermore, dye images obtained from conventionally used phenols and naphthols have some problems in their storage stability. For example, U.S. Patent Nos. 2 and 3
67.531, 2,369,929 and 2.423.730, the dye images obtained from the 2-acylaminophenol cyan couplers described in each specification are as follows:
Generally poor heat fastness, U.S. Patent No. 2.772,162
The dye images obtained from the 2,5-diacylaminophenol cyan coupler described in the specification generally have poor light fastness, and the dye images obtained from the 1-hydroxy-2-natutamido cyan coupler generally have poor light and heat fastness. It is inadequate in both gender aspects.

Also, U.S. Pat.
2,5-diacylaminophenol cyan couplers described in Japanese Patent No. 3,880,66, etc.
The 2,5-diacylaminophenol cyan coupler described in Specification No. 1, which has a hydroxyl group in the ballast part, must also have fastness to light and heat and the occurrence of yellow stain in order to preserve the dye image for a long time. In this respect, a fully satisfactory level has not yet been achieved.

In order to solve this problem, Japanese Patent Application No. 62-203450, No. 62-203451, No. 63-7204, No. 63-
No. 32094, No. 63-38086, No. 63-379
No. 98, No. 63-237681, etc., various pyrazolopyrimidone and pyrazoloquinazolone type cyan couplers,
Proposed.

It is true that the cyan images obtained from these cyan couplers have very advantageous characteristics in terms of color reproducibility, such as low secondary absorption and a small half-width on the spectral absorption curve.
,ing.

However, these couplers have the problem of low color development and large changes in photographic properties due to changes in concentration of processing liquid components during continuous processing.

[Object of the Invention] The present invention has been made in view of the above-mentioned circumstances, and provides a silver halide color that has sufficient color development, good color reproducibility, and little deterioration of photographic properties during continuous processing. Our objective is to provide photographic materials.

[Structure of the Invention] The above-mentioned object of the present invention is to provide a silver halide color photographic light-sensitive material having at least one silver halide emulsion layer on a support, in which the silver halide emulsion layer contains the following general formula [A1 - A silver halide color photograph characterized in that at least one cyan coupler represented by [I'l is co-dispersed with at least one water-insoluble and organic solvent-soluble homopolymer or copolymer. This was achieved using photosensitive materials.

Below are the blanks General formula [A] General formula [D] General formula [E] υ General formula [C General formula [G] General formula [H] General formula [1] [In the formula, R1 and R5 are hydrogen atoms or substitution represents a group, and R2 represents a substituent. X represents a hydrogen atom or a substituent which is eliminated by reaction with an oxidized product of a color developing agent, n represents an integer of 0 to 4, and Z represents a group of nonmetallic atoms necessary to form a heterocycle. ] [Specific Structure of the Invention] Cyan couplers represented by general formulas [A] to [N] of the present invention will be explained.

The cyan coupler of the present invention is fused with a pyrazole ring,
It has a 6-membered hetero ring structure, and the substituents represented by R, R, and R1 are not particularly limited, and typically include alkyl, aryl, anilino, acylamino, sulfonamide, alkylthio, and arylthio. , alkenyl, cycloalkyl, etc. In addition, halogen atoms and cycloalkenyl, alkynyl,
heterocycle, sulfonyl, sulfinyl, phosphonyl, acyl, carbamoyl, sulfamoyl, cyano, alkoxy, sulfonyloxy, acyloxy, heterocycleoxy,
acyloxy, acyloxy, carbamoyloxy, amino, alkylamino, imide, ureido, sulfamoylamino, alkoxycarbonylamino, aryloxycarbonylamino, alkoxycarbonyl, aryloxycarbonyl, heterocyclic thio, thioureido, carboxyl, hydroxy, mercapto, nitro , polygroups such as sulfonic acid, spiro compound residues, bridged hydrocarbon compound residues, and the like.

The above alkyl group preferably has 1 to 32 carbon atoms, and may be linear or branched.

As the aryl group, a phenyl group is preferred.

Examples of the acylamino group include an alkylcarbonylamino group and an arylcarbonylamino group.

Examples of the sulfonamide group include an alkylsulfonylamino group and an arylsulfonylamino group.

Examples of the alkyl component and aryl component in the alkylthio group and arylthio group include the above-mentioned alkyl groups and aryl groups.

The alkenyl group preferably has 2 to 32 carbon atoms, and the cycloalkyl group preferably has 3 to I2 carbon atoms, particularly 5 to 7 carbon atoms, and the alkenyl group may be linear or branched.

The cycloalkenyl group has 3 to 12 carbon atoms, especially 5
-7 is preferred.

Sulfonyl groups include alkylsulfonyl groups, arylsulfonyl groups, etc.; sulfinyl groups include alkylsulfinyl groups, arylsulfinyl groups, etc.; phosphonyl groups include alkylphosphonyl groups, alkoxyphosphonyl groups, aryloxyphosphonyl groups, and arylphosphonyl groups. etc.; Acyl groups include alkylcarbonyl groups, arylcarbonyl groups, etc.; carbamoyl groups include alkylcarbamoyl groups, arylcarbamoyl groups, etc.

As the sulfamoyl group, an alkylsulfamoyl group,
Arylsulfamoyl groups, etc.; examples of acyloxy groups include alkylcarbonyloxy groups, arylcarbonyloxy groups, etc.

Carbamoyloxy groups include alkylcarbamoyloxy groups, arylcarbamoyloxy groups, etc.; ureido groups include alkylureido groups, arylureido groups, etc.; sulfamoylamino groups include alkylsulfamoylamino groups, arylsulfamoylamino groups, etc. The heterocyclic group is preferably a 5- to 7-membered one, specifically a 2-furyl group, 2-thienyl group, 2-pyrimidinyl group, 2-benzothiazolyl group, 1-pyrrolyl group, 1-tetrazolyl group, etc.; The heterocyclic oxy group preferably has a 5- to 7-membered heterocycle, such as 3,4.5.6-tetrahydropyranyl-2-oxy group, 1-phenyltetrazole-5-
Oxy group, etc.; The heterocyclic thio group is preferably a 5- to 7-membered heterocyclic thio group, such as 2-pyridylthio group, 2-benzothiazolylthio group, 2,4-diphenoxy1.3.5-triazole-6 monothio group, etc.; siloxy group includes trimethylsiloxy group, triethylsiloxy group, dimethylbutylsiloxy group, etc.; imide group includes succinimide group, 3-heptadecylsuccinimide group, phthalimide group, glutarimide group, etc.; The compound residue is spiro[3,3cohebutane-
1-yl, etc.; As a bridged hydrocarbon compound residue, bicyclo[2°2.1
] heptan-1-yl, tricyclo[3゜3.1.13
・7]Decan-1-yl, 7,7-dimethyl-bicyclo[2,2゜1cohebutan-1-yl and the like.

The above group may further have a substituent such as a long-chain hydrocarbon group or a diffusion-resistant group such as a polymer residue.

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 atom, bromine atom, fluorine atom, etc.), alkoxy, aryloxy, heterocyclic oxy, acyloxy, sulfonyloxy, alkoxy Carbonyloxy, aryloxycarbonyl, alkyloxalyloxy, alkoxyoxalyloxy, alkylthio, arylthio, heterocyclic thio, alkyloxythiocarbonylthio, acylamino, sulfonamide, nitrogen-containing heterocycle bonded via N atom, alkyloxycarbonylamino , aryloxycarboniamino, carboxyl, Next, general formulas [A] to [! ], but the present invention is not limited thereto.

(R' has the same meaning as R3 above, Z' represents a nonmetallic atom group necessary to form a nitrogen-containing 6-membered heterocyclic ring by condensation with the pyrazole ring, and Ra and Rb represent a hydrogen atom, an aryl group, alkyl group, or heterocyclic group), preferably a halogen atom. Among these, particularly preferred ones represented by X are hydrogen atoms and chlorine atoms.

R8 X CISH31- -H C+JbsO- -OCH3(2) -CI (CH3)2CH -OC12825 (3) ■-CI A-6 CH3S- -NH3OzCtJ2s (4) C.I. C12FI25 Margin below R8 R5 Margin below CssTo+- H C.I. CxaFIt70+NH- H -B+ ClJzsO- H -C! Hi- 0oC12H25 H R3 Cl282% ISH31 D-1 CIJzsNH- 6HI3 C12H2SO- R1 IJ31 (CH3)2CH Cut H H C1 H C.I. -NHCOC+J2t C.I. Margin below t CI6F! 33- -NHCOCIJe7 OCH3 Margin below CCH3)3C- -NHCOCaHn (1) (2) H (1) CsH.

G-4 υ Below margin H3NN The above coupler according to the present invention is disclosed in Japanese Patent Application No. 63-3214.
No. 88, No. 64-3699fi, No. 84-41183
No. 64-52293, No. 64-97598, No. 64-9884, and No. 64-125052, and the synthesis methods described and the cited literature. It can be synthesized according to the proposed synthesis method.

The cyan coupler of the present invention usually contains IX 10-' mol-1 mol per mol of silver halide, preferably IX 1
It can be used in the range of 0-2 mol-8X 10-' mol.

Moreover, the coupler of the present invention can also be used in combination with other types of cyan couplers.

Next, the water-insoluble and organic solvent-soluble homopolymer or copolymer according to the present invention will be explained.

Various types of water-insoluble and organic solvent-soluble homopolymers or copolymers can be used, and for example, those shown below can be preferably used.

(1) Vinyl polymers and copolymers The monomers forming the vinyl polymers and copolymers of the present invention will be described in more detail.

Acrylic esters: for example, methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-puracrylate, tert
-butyl acrylate, isobutyl acrylate, 5e
e-butyl acrylate, amyl acrylate, hexyl acrylate, 2-ethylhexyl acrylate, octyl acrylate, tert-octyl acrylate, 2-chloroethyl acrylate, 2-bromoethyl acrylate, 4-chlorobutyl acrylate, cyanethyl acrylate, 2- Acetoxyethyl acrylate, dimethylaminoethyl acrylate, benzyl acrylate, methoxybenzyl acrylate 2-chlorocyclohexyl acrylate, cyclohexyl acrylate, furfuryl acrylate, tetrahydrofurfuryl acrylate, phenyl acrylate, 5-hydroxypentyl acrylate ), 2,2-dimethyl-3-hydroxypropyl acrylate, 2-methoxyethyl acrylate, 3-methoxybutyl acrylate, 2-ethoxyethyl acrylate, 2-1s.

-Propoxyethyl acrylate, 2-butoxyethyl acrylate, 2-(2-methoxyethoxy)ethyl acrylate, 2-(2-butoxyethoxy)ethyl acrylate, ω-methoxypolyethylene glycol acrylate (number of moles added n-9), 1- Bromo-2-methoxyethyl acrylate, 1,1-dichloro-2-ethoxyethyl acrylate; Methacrylic acid esters: For example, methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, tert-butyl methacrylate, Isobutyl methacrylate, 5ee-butyl methacrylate, amyl methacrylate, hexyl methacrylate, cyclohexyl methacrylate, benzyl methacrylate, chloropenzyl methacrylate, octyl 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 mono methacrylate, 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 (number of moles added n-6); Two examples of vinyl esters include vinyl acetate, vinyl propionate, vinyl butyrate, vinyl isobutyrate, vinyl caproate, vinyl chloroacetate,
Vinyl methoxy acetate, vinyl phenylacetate, vinyl benzoate, vinyl salicylate; Acrylamide: for example, acrylamide, methyl acrylamide, ethyl acrylamide, propylacrylamide, butylacrylamide, tert-butylacrylamide, cyclohexylacrylamide, benzyl acrylamide, hydroxymethyl acrylamide, methoxyethyl Acrylamide, dimethylaminoethyl acrylamide, phenylacrylamide, dimethylacrylamide, diethylacrylamide, β-cyanoethyl acrylamide, N-(2-acetoacetoxyethyl)acrylamide, diacetone acrylamide; two examples of methacrylamide: methacrylamide, methylmethacrylamide, ethyl methacrylamide, propyl methacrylamide, butyl methacrylamide, ter
t-butylmethacrylamide, cyclohexylmethacrylamide, benzylmethacrylamide, hydroxymethylmethacrylamide, methoxyethylmethacrylamide, dimethylaminoethylmethacrylamide, phenylmethacrylamide, dimethylmethacrylamide, diethylmethacrylamide, β-cyanoethylmethacrylamide, N-(2-acetoacetoxyethyl)methacrylamide; Two examples of olefins include dicyclopentadiene, ethylene, propylene, 1-butene, 1-pentene, vinyl chloride, vinylidene chloride, isoprene, chlorobrene, butadiene, 2,3- Dimethylbutadiene; Styrenes: For example, styrene, methylstyrene, dimethylstyrene, trimethylstyrene, ethylstyrene,
Isopropylstyrene, chloromethylstyrene, methoxystyrene, chlorostyrene, dichlorostyrene, bromostyrene, vinylbenzoic acid methyl ester; Crotonate esters: e.g. butyl crotonate, hexyl crotonate; Itaconate diesters: e.g. dimethyl itaconate, Diethyl itaconate, dibutyl itaconate; diesters of maleate; for example, diethyl maleate, dimethyl maleate, dibutyl maleate; diesters of fumarate: for example, diethyl fumarate, dimethyl fumarate, dibutyl fumarate and the like.

Examples of other comonomers include:

Allyl compounds: For example, allyl acetate, allyl caproate, allyl laurate, allyl benzoate; Vinyl ethers: For example, methyl vinyl dimonyl, butyl vinyl ether, hexyl vinyl ether, methoxyethyl vinyl ether, dimethylaminoethyl vinyl ether; Vinyl ketones: For example, , methyl vinyl ketone, phenyl vinyl ketone, methoxyethyl vinyl ketone; vinyl heterocyclic compounds: for example, vinylpyridine, N-vinylimidazole, N-vinyloxazolidone, N-vinyltriazole, N-vinylpyrrolidone; glycidyl esters: for example , glycidyl acrylate, glycidyl methacrylate; unsaturated nitriles: for example, acrylonitrile, methacrylatrile; and the like.

The polymer used in the present invention may be a homopolymer of the above monomers, or, if necessary, a copolymer of two or more monomers. Further, the polymer used in the present invention may contain a monomer having an acid group to an extent that it does not become water-soluble (preferably 20% or less), but it is preferable that it contains no monomer at all.

Monomers having the above acid groups include acrylic acid; methacrylic acid; itaconic acid; maleic acid; monoalkyl itaconate (e.g., monomethyl itaconate); monoalkyl maleate (e.g., monomethyl maleate); citraconic acid; styrene sulfone Acids; vinylbenzyl sulfonic acid; acryloyloxyalkylsulfonic acid (e.g., acryloyloxymethylsulfonic acid); methacryloyloxyalkylsulfonic acid (e.g., methacryloyloxymethylsulfonic acid, methacryloyloxyethylsulfonic acid, methacryloyloxypropylsulfonic acid); acrylamide Alkylsulfonic acids (e.g. 2
-acrylamido-2-methylethanesulfonic acid, 2-acrylamido-2-methylpropanesulfonic acid, 2-acrylamido-2-methylbutanesulfonic acid): methacrylamide alkylsulfonic acid (e.g. 2-methacrylamido-2-methylethanesulfonic acid) acids, 2-methacrylamido-2-methylpropanesulfonic acid, 2-methacrylamido-2-methylbutanesulfonic acid); acryloyloxyalkyl phosphates (e.g., acryloyloxyethyl phosphate, 3-acryloyloxypropyl-2-phosphate); Examples include methacryloyloxyalkyl phosphates (eg, methacryloyloxyethyl phosphate, 3-methacryloyloxypropyl-2-phosphate), and the like.

These acid group-containing monomers may be salts of alkali metals (eg, Na% K, etc.) or ammonium ions.

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

Polymers formed from the above monomers can be obtained by solution polymerization, bulk polymerization, suspension polymerization, and latex polymerization. As the initiator used in these polymerizations, a water-soluble polymerization initiator and a lipophilic polymerization initiator are used.

Examples of water-soluble polymerization initiators include potassium persulfate,
Persulfates such as ammonium persulfate and sodium persulfate, sodium 4.4'-azobis-4cyanovalerate,
Water-soluble azo compounds such as 2.2'-azobis(2-amidinopropane) hydrochloride and hydrogen peroxide can be used.

Examples of lipophilic polymerization initiators include azobisisobutyronitrile, 2,2'-azobis(24-dimethylvaleronitrile), 2,2'-azobis(4-methoxy-
24-dimethylvaleronitrile), 1.1'-azobis(cyclohexanone-1-carbonide lyl), 2.2
Examples include lipophilic azo compounds such as dimethyl '-azobisisobutyrate and diethyl 2.2'-azobisisobutyrate, benzoyl peroxide, lauryl peroxide, diisopropyl peroxide dicarbonate, and di-tert-butyl peroxide.

(2) Polyester resin obtained by condensing polyhydric alcohol and polybasic acid Polyhydric alcohols include HO-R, -0H (Rs is a hydrocarbon having 2 to about 12 carbon atoms, especially an aliphatic hydrocarbon) )
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 having 1 to 12 carbon atoms) are effective.

Specific examples of polyhydric alcohols include ethylene glycol, diethylene glycol, triethylene glycol,
, 2-propylene glycol, 1°3-propylene glycol, trimethylolpropane, 1,4-butanediol, isobutylene diol, 1,5-bentanediol, neopentyl glycol, 1,6-hexanediol, 1°7- Butanediol, 1,8-octanediol, 1,9-nonanediol, 1. IO-Decanediol, 1.11-Undecanediol, 1. ■2 Dodecanediol, 1.13-1 Lysocandiol, 1.14
-tetradecanediol, glycerin, diglycerin,
Examples include triglycerin, 1-methylchrycerin, erythritol, mannitol, sorbitol, and the like.

Specific examples of polybasic acids include oxalic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, corkic acid, azelaic acid, sebacic acid, nonanedicarboxylic acid, decanedicarboxylic acid, undecanedicarboxylic acid, dodecanedicarboxylic acid, and fumaric acid. Acid, maleic acid, itaconic acid, citraconic acid, phthalic acid, isophthalic acid, terephthalic acid, tetrachlorophthalic acid, methaconic acid, isohimelic acid, cyclopentadiene-maleic anhydride adduct, rosin-maleic anhydride adduct. It will be done.

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

(4) Other polycarbonate resins obtained by polycondensation of glycols or dihydric phenols with carbonic esters or phosgene, polyurethane resins obtained by polyaddition of polyhydric alcohols and polyvalent isocyanates, or polyvalent amines and polybasic acids. Examples include polyamide resins obtained from.

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 or more and 10,000 or less.

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.) P-1) Poly(N-see-butylacrylamide)
P-2) Poly(N-tert-butylacrylamide) P-3) Diacetone acrylamide-methyl methacrylate copolymer (25Nia 5) P-4) Polycyclohexyl methacrylate P-5) N-tert
-Butylacrylamide-methyl methacrylate copolymer (80:40) P -6) P-8) P -9) P -10) P -11) P -12) P-13) P -14) P -15) P-16) P-17) P-18) P-19) P-20) Poly(N,N-dimethylacrylamide) Poly(tert-butyl methacrylate) Polyvinyl acetate Polyvinyl probionate Polymethyl methacrylate Polyethyl methacrylate poly Ethyl acrylate vinyl acetate-vinyl alcohol copolymer (90:10) Poly n-butyl acrylate poly n-butyl methacrylate polyisobutyl methacrylate polyisopropyl methacrylate polyoctyl acrylate n-butyl acrylate-acrylamide copolymer (95:5) Stearyl methacrylate - Acrylic acid copolymer (90/10) P -21) P -22) P -23) P -24) P -25) P -26) P -28) P -29) Methyl methacrylate-vinyl chloride copolymer Combined (70:30) Methyl methacrylate-styrene copolymer (90:10) Methyl methacrylate-ethyl acrylate copolymer (50:50) n-Butyl methacrylate-methyl methacrylate-styrene copolymer (50:20:30) Vinyl acetate-acrylamide copolymer (85:15) Vinyl chloride-vinyl acetate copolymer (85:35) Methyl methacrylate-acrylonitrile copolymer (85:35) n-Butyl methacrylate-pentyl methacrylate-N-vinyl- 2-pyrrolidone copolymer (38: 3g: 24) Methyl methacrylate-〇-butyl methacrylate-isobutyl-meta P-30) P-32) P-33) P-34) P-35) P-36) P- 37) Acrylate-acrylic acid copolymer C37: 29: 25: 9) n-butyl methacrylate-acrylic acid (95+5) Methyl methacrylate-acrylic acid copolymer (95:5) Benzyl methacrylate-acrylic acid copolymer (93 n-butyl methacrylate to methyl methacrylate-benzyl methacrylate-acrylic acid copolymer (35: 35:25:5) n-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-〇-butyl P -38) P -40) P-41) P -42) P -43 ) Acrylate copolymer (70:30) Diacetone acrylamide-n-butyl acrylate copolymer (60+40) Methyl methacrylate-stearyl methacrylate-diacetone acrylamide copolymer (40:40:20) n-butyl acrylate-stearyl methacrylate -Diacetone acrylamide copolymer (70:20:10) Stearyl methacrylate-methyl methacrylate-acrylic acid copolymer (50:40:10) Methyl methacrylate-styrene-vinyl sulfonamide copolymer (70:20:10) Methyl methacrylate-phenyl vinyl ketone copolymer (70:30) n-butyl acrylate-methyl methacrylate-n-butyl methacrylate copolymer (35: 35: 30) P-45) P-46) P-47) P -48) P-49) P -50) P-51) P -52) P -53) n-Butyl methacrylate-N-vinyl-2-pyrrolidone copolymer (90:10) Polypentyl acrylate cyclohexyl methacrylate -Methyl methacrylate-n-propyl methacrylate copolymer (37:29: polypentyl methacrylate-methyl methacrylate-〇-butyl methacrylate copolymer (65.35)) vinyl acetate-vinyl propionate copolymer (75:25) n -Butyl methacrylate-3-acryno is xybutane-sodium 1-sulfonate copolymer (97:3) n-butyl methacrylate-methyl methacrylate-acrylamide copolymer (35: 35: 30) n-butyl methacrylate- Methyl P-54) P-55) P-56) P-57) P-58) P-59) P-80) P-61) P-62) Methacrylate-vinyl chloride copolymer (87: 36: 27) ) n-butyl methacrylate-styrene copolymer (82:18) tert-butyl methacrylate-methyl methacrylate copolymer (70:30) poly(N-tert-butyl methacrylamide) N-tert-butylacrylamide-methylphenyl methacrylate Copolymer (60:40) Methyl methacrylate-acrylonitrile copolymer (70:30) Methyl methacrylate-methyl vinyl ketone copolymer (38Nia 2) Methyl methacrylate-styrene copolymer (75:25) Methyl methacrylate- Hexyl methacrylate copolymer (70:30) Butyl methacrylate-acrylic acid P -63) P -64) P-65) P-66) P-67) P-88) P -69) P-70) P - 71) P-72) P-73) Copolymer (85:15) Methyl methacrylate-acrylic acid copolymer (80:20) Methyl methacrylate-acrylic acid copolymer (90:10) Methyl methacrylate-acrylic acid copolymer Polymer (98:2) Methyl methacrylate-N-vinyl-2-pyrrolidone copolymer (90:to) n-butyl methacrylate-vinyl chloride copolymer (90:10) n-butyl methacrylate-styrene copolymer ( 70:30) 1.4-Butanediol-adipic acid polyester ethylene glycol-sebacic acid polyester polycaprolactam polypropiolactam polydimethylpropiolactone P-74) N-tert-butylacrylamide-dimethylaminoethyl acrylamide copolymer (85:15) P-75) N-tert-butylmethacryamide-
Vinylpyridine copolymer (95:5) P-78) Diethyl maleate--butyl acrylate copolymer (65:85) P-77) N-tert-butylacrylamide 2
-Methoxyethyl acrylate copolymer (55:45) In the present invention, the above general formula [I
A dispersion in which at least one cyan coupler represented by It can be obtained by dissolving the above-mentioned coupler and at least one of the above-mentioned single or copolymers in a substantially water-insoluble high-boiling organic solvent and emulsifying and dispersing the solution in a hydrophilic protective colloid.

Here, the substantially water-insoluble high-boiling organic solvent is a compound that is immiscible with water and has a melting point of 100°C or lower and a boiling point of 140°C or higher, such as phenol derivatives, esters such as phthalate esters and phosphate esters. etc., organic acid amides, carbamates, Kents, etc. These are U.S. Patent Nos. 2,322,027, 2,353,262, 2,533,514, and 2,801.170.
No. 2.801,171, No. 2.835,57
No. 9, No. 2,852,383, No. 2,870,0
No. 12, No. 2,991.171, No. 3.287,
No. 134, No. 3.554.755, No. 3,678
, No. 137, No. 3.676.142, No. 3,70
0.454, 3,748,141, 3,7
No. 79,765 and No. 3,837,883.

Furthermore, to aid the dissolution, a low-boiling organic solvent or an organic solvent miscible with water can be used.

Examples of low-boiling organic solvents include ethyl acetate, butyl acetate, cyclohexanone, isobutyl alcohol, methyl ethyl ketone, methyl cellosolve, and the like.

Examples of organic solvents miscible with water include methyl alcohol, ethyl alcohol, acetone, phenoxyethanol, tetrahydrofuran, and dimethylformamide.

These low boiling point organic solvents and water-miscible organic solvents can be removed by washing with water or by coating and drying.

Moreover, the organic solvents mentioned above can also be used in combination of two or more types.

To emulsify and disperse into hydrophilic protective colloid to form lipophilic fine particles, use a dispersion aid such as a surfactant, a stirrer,
Homogenizer: Disperse using a colloid mill, flow jet mixer, ultrasonic device, etc. A step of removing the low boiling point organic solvent may be included simultaneously with the dispersion.

As the hydrophilic protective colloid, an aqueous gelatin solution is preferably used.

The average particle size of lipophilic particles is 0.04μ to 2μ
is preferred, more preferably 0.06μ to 0.4
μ. The particle size can be measured using Coulter Model N4 manufactured by Coulter Co., Ltd., UK.

In the present invention, the mixing ratio of the coupler, a single or copolymer, a high boiling point solvent, a low boiling point solvent, or an auxiliary solvent such as a water-miscible organic solvent is such that the coupler alone or a copolymer, the high boiling point solvent is added to the auxiliary solvent. The viscosity may be selected so that the resulting solution can be easily dispersed in the hydrophilic colloid. The value at this time varies depending on the solubility of the coupler used, the type of polymer, and the degree of polymerization.
Weight ratio) is 1:lO to 5:1, preferably 1:3 to 2:
It is 1.

The ratio (weight ratio) of the high boiling point solvent to the coupler used is 1:20 to 5:1, preferably 1:10 to 2:
It is 1. Ratio of low boiling point solvent to polymer (weight ratio)
is 1:1O to 1O:1, preferably 1:4 to 5:1.

In the present invention, at least one cyan coupler represented by the general formula [1] is present in the lipophilic fine particles in coexistence with one of the water-insoluble and organic solvent-soluble homopolymers or copolymers. Preferably, the dispersion is added to the red-sensitive silver halide emulsion layer.

The dispersion also contains compounds that do not need to be adsorbed onto the silver halide crystal surface, such as image stabilizers, color antifoggants, ultraviolet absorbers, fluorescent whitening agents, sensitizing dyes, and oil-soluble dyes. They can also be distributed at the same time.

JP-A-59-125732, JP-A No. 62-96944
It is preferable to simultaneously disperse the image stabilizer described in the above publication.

When the silver halide color photographic light-sensitive material of the present invention is used as a full-color light-sensitive material, a magenta coupler and a yellow coupler are used in addition to the cyan coupler of the present invention. As the magenta coupler and yellow coupler at this time, there are no particular restrictions and any known ones can be used.

As the magenta coupler, for example, a 5-pyrazolone coupler, a pyrazolopenzimidazole coupler, or an open-chain acylacetonitrile coupler can be used.

As the yellow coupler, for example, acylacetanilide couplers can be used, including benzoylacetanilide and pivaloylacetanilide compounds.

The silver halide color photographic light-sensitive material of the present invention may contain a water-soluble dye in the hydrophilic colloid layer as a filter dye or for various purposes such as preventing irradiation.

The silver halide color photographic material of the present invention may contain various other photographic additives. For example, antifoggants, development accelerators, development retarders, bleach accelerators, stabilizers, ultraviolet absorbers, color stain inhibitors, fluorescent whitening agents, color image fading inhibitors, antistatic agents, hardeners, interfaces. Activators, plasticizers, wetting agents, etc. can be used. (Refer to Research Disclosure No. 17643.) Furthermore, by coupling with competing couplers and oxidized forms of developing agents, development accelerators, bleach accelerators, developing agents, silver halide solvents, toning agents, hardeners, fogging agents, etc. Compounds that release photographically useful fragments such as agents, antifoggants, chemical sensitizers, spectral sensitizers, and desensitizers can be used.

The support for the silver halide color photographic light-sensitive material of the present invention is
Examples include baryta paper, polyethylene-coated paper, polypropylene synthetic paper, glass plates, polyester films such as cellulose acetate, cellulose nitrate, and polyethylene terephthalate, polyamide films, polycarbonate films, and polystyrene films. In the case of transparent supports, reflective layers are used. May be used together.

These supports are appropriately selected depending on the intended use of the photosensitive material.

For coating the emulsion layer and other constituent layers used in the present invention, a number of coating methods can be used, such as dipping coating, air doctor coating, curtain coating, and hopper coating. Also, U.S. Patent No. 2.781,791;
It is also possible to use a simultaneous coating method of two or more layers by the method described in No. 941.898.

In the present invention, the coating position of each emulsion layer can be arbitrarily determined. It is preferable to do so.

In the photosensitive material of the present invention, it is optional to provide an intermediate layer with an appropriate thickness depending on the purpose, and a filter layer,
Various layers such as an anti-curl layer, a protective layer, and an antihalation layer can be used in appropriate combinations as constituent layers. Hydrophilic colloids can be used as binders in these constituent layers, and gelatin is preferably used. Further, the layer may contain various photographic additives mentioned in the explanation of the emulsion layer.

There are no particular limitations on the method of processing photographic materials using the silver halide emulsion of the present invention, and any commonly known processing method can be applied. For example, typical methods include a method in which bleach-fixing is performed after color development, followed by further washing and/or stabilization treatment if necessary, and a method in which bleaching and fixing are performed separately after color development, and then bleach-fixing is performed as necessary. The silver halide color photographic light-sensitive material of the present invention may be further processed by any method of washing with water and/or stabilizing. suitable for rapid processing.

[Example] Specific examples of the present invention will be described below, but the present invention is not limited thereto.

Example 1 On a paper support laminated with polyethylene (titanium oxide content: 2.7 g/nr), the following layers were sequentially coated from the support side, and a silver halide color photographic material (No.
, 1) was created.

Layer 1: 3.5g / Seratin, 2.3g
/d (in terms of silver) red-sensitive silver chlorobromide emulsion (silver chloride content 70 mol%), dissolved in 0.20 g/rrr of dioctyl phthalate (hereinafter referred to as DOP).
, 4 g/rd of cyan coupler (A-2).

Layer 2 - = 2.2g/rrr gelatin, 0
．． 63g/rrIl'notricresyl phosphate (
Hereinafter referred to as TCP. ) A layer containing 0.75 g/rd of ultraviolet absorber (UV-1) and 0.25 g/rd of ultraviolet absorber (UV-2) dissolved in.

In addition, as a hardening agent, 2,4-dichloro-6-hydroxy-5-) riazine sodium was added in layer 2, and gelatin 1 was added as a hardening agent.
It was added in an amount of 0.017g/g.

Further, the types and amounts of the cyan coupler, high boiling point solvent, and water-insoluble and organic solvent-soluble single or copolymer in layer 1 were prepared as shown in Table 1, and silver 10ogenide color photosensitive materials (No. 2 to 20) was created.

Below margin (UV-1) Ultraviolet absorber Table 1 (UV-2) Ultraviolet absorber Below margin Each of the above photosensitive material samples Nos. 1 to 20 was exposed through an optical wedge and then processed in the following steps.

Processing steps (38°C) Color development 3 minutes 30 seconds Bleach-fixing 1 minute 30 seconds Washing with water 1 minute Drying 60-80°C 2 minutes The composition of each processing solution is as follows.

<Color developer> Pure water 8
00mρ benzyl alcohol 15m9
Hydroxyamine sulfate 2.0g Potassium bromide 1.0g Sodium chloride 1.0g Potassium sulfite
2.0g triethanolamine
2.0g N-ethyl-N-β-methanesulfonamidoethyl-3-methyl-4-aminoaniline sulfate 4.5g 1-hydroxyethylidene-1,l-diphosphonic acid (60% aqueous solution)
1.5 mρ potassium carbonate
32gWhitex BB (50% aqueous solution)
2mfl (fluorescent brightener, manufactured by Sumitomo Chemical Co., Ltd.) Add pure water to make Ifl 20% potassium hydroxide or 10%
% dilute sulfuric acid p) Adjust to I-10.1.

<Bleach-fix solution> Pure water
550ml Iron ethylenediaminetetraacetate (m) Ammonium 65g Ammonium thiosulfate 85g Sodium bisulfite lOg Sodium metabisulfite
2g ethylenediaminetetraacetic acid-disodium 20g sodium bromide 1
Add 0g of pure water to bring the concentration to 1ρ, and adjust to pn-7.0 with aqueous ammonia or dilute sulfuric acid.

The cyan density of each sample obtained through the development process was measured, and the sensitivity and maximum density (Dmax) were determined. The sensitivity was determined from the reciprocal of the exposure amount corresponding to a density of 0.5.

The results are shown in Table 2.

Note that the sensitivity is expressed relative to the sensitivity of Sample Soil 1 as 100.

Margin Table 2 Below: As is clear from the results in Table 2, it can be seen that the present invention has excellent coloring properties.

Example 2 On a paper support laminated with polyethylene (titanium oxide content: 2.7 g/rrr), the following layers were sequentially coated from the support side, and a silver halide color photographic material (Nα
21) was prepared.

Layer 1... 1.2g lrd gelatin, 0.
Blue-sensitive silver chlorobromide emulsion (silver chloride content: 99.3 mol%), 0.50
A layer containing 0.80 g/rrr of yellow coupler (Y-1) dissolved in a DOP of g/g.

Layer 2: Middle layer consisting of 0.7glrd gelatin.

Layer 3: 1.25 g/rrr of gelatin, 0.
22 g/rrr green-sensitive silver chlorobromide emulsion (silver chloride content 9
9.5 mol %), o, sog /- of DOP containing 0.62 g/sesame magenta coupler (M-1).

Layer 4... 1.2g/rrr of gelatin and 1
2mg/rr? An intermediate layer consisting of (A1.C-1).

Layer 5... L4glrd gelatin, 0.20
g/a red-sensitive silver chlorobromide emulsion (silver chloride content 99.7 mol%), 0.20 g/rrr dibutyl phthalate (
Hereinafter referred to as DBP. layer containing 0.40 g/g of cyan coupler (A-2) dissolved in ).

Layer 6... L, gelatin of Og/rrr and 0.2
A layer containing 0.3 g/rd of ultraviolet absorber (UV-1) dissolved in g/rrf of DOP.

Layer 7: A layer containing 0.5 g/rrr of gelatin.

As a hardening agent, 2.4-di-chloro-6-hydroxy-5-) riazine sodium was added to layers 2.4 and 7 in an amount of 0.017 g per 1 g of seratin, respectively.

The following margins (AIC-1) (Y-1) O Furthermore, among the above layer configurations, the types and amounts of the cyan coupler, high boiling point solvent, and water-insoluble and organic solvent-soluble single or copolymer in layer 5 are shown in Table 3. Silver halide color photosensitive materials (Nos. 22 to 31) were prepared as shown in FIG.

The cyan coupler of each sample was added in an equimolar amount with the cyan coupler (A-2) of sample k21.

Table 3 (M-1) D After exposing each of the above photosensitive materials No. 21 to 31 through an optical wedge, use a paper processing machine to replenish twice the tank amount for color development in the following processing steps. Continuous processing was performed until

Processing process temperature Time Replenishment amount Tan') Capacitive color development
34.7±03℃ 45 seconds 160m1 tex bleach fixing 34.7±0.5℃ 45 seconds 215m1 1t
14 Stabilization ■ 30-34℃ 30 seconds 1
ofl■ 30~34℃ 30 seconds 10 sentences■ 30~34℃ 30 seconds 245m1 IOQ
Drying: 60-80℃ Stabilization for 60 seconds■
The replenisher was replenished in a countercurrent manner to -■.

The composition of each treatment liquid is as follows.

[Color developer] 1 ink solution Replenisher pure water 800 ml 8
00 ml triethanolamine sg
togN, N-diethylhydroxyamine 5g
7g potassium chloride 2.
1.1gN-Ethyl-N-β-methanesulfonamidoethyl-3-methyl-4-aminoaniline sulfate Sodium tetrapolyphosphate Potassium carbonate Potassium sulfite Fluorescent brightener (4,4'-diaminostilbendisulfonic acid derivative) Add pure water to bring the total volume to 1ρ.

[Bleach-fix solution] Pure water Ferric ethylenediaminetetraacetate ammonium dihydrate Ethylenediaminetetraacetic acid Ammonium thiosulfate (70% solution) Ammonium sulfite (40% solution) Add water to bring the total volume to 12 and carbonate power. Adjust the pH to 5.7 with hydroacetic acid.

[Stabilizing liquid] (Tank liquid and replenisher liquid) Ig 1
．． 2g Adjust to pH 10.2g g 0g 0.2g (tank liquid and replenisher) 7.4g 2.8g 0g 0.3g 800 ml 0g g 00ml 27.5ml Lithium or pure water 800 ml
5-Chloro-2-methyl-4-isothiazolin-3-one 1g 1-hydroxyethylidene-1,1-diphosphonic acid 2g Water was added to make lfl, and the pH was adjusted to 7.0 with sulfuric acid or potassium hydroxide.
Adjust to 0.

The photographic performance was compared between the case where the processing step was performed with a fresh liquid and the case where the process was performed with a running liquid that was continuously processed until twice the tank amount was refilled, and the change in photographic performance during continuous processing was evaluated.

The results are shown in Table 4.

Note that the sensitivity is expressed as a relative sensitivity, with the sensitivity when sample Nα21 was treated with a fresh solution being 100.

As is clear from the results in Table 4, the sample of the present invention has sensitivity D
It can be seen that the max is high and the change in photographic properties during continuous processing is small.

[Effect of the invention] In the silver halide color photographic light-sensitive material of the invention,
It has excellent color development and color reproducibility, and also has the effect of improving changes in photographic properties during continuous processing.

Applicant Konica Co., Ltd. Representative Yoshio IwamaTable 4

Claims (1)

[Scope of Claims] A silver halide color photographic light-sensitive material having at least one silver halide emulsion layer on a support, in which the silver halide emulsion layer contains compounds represented by the following general formulas [A] to [I]. 1. A silver halide color photographic light-sensitive material, characterized in that at least one of the cyan couplers shown above is co-dispersed with at least one water-insoluble and organic solvent-soluble homopolymer or copolymer. General formula [A] ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ General formula [B] ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ General formula [C] ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ General formula [D] ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ General formula [E] ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ General formula [F] ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ General formula [G] ▲ Mathematical formulas, chemical formulas, There are tables, etc. ▼ General formula [H] ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ General formula [I] ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [In the formula, R_1 and R_3 represent a hydrogen atom or a substituent. , R_2 represents a substituent. X represents a hydrogen atom or a substituent which is eliminated by reaction with an oxidized product of a color developing agent, n represents an integer of 0 to 4, and Z represents a group of nonmetallic atoms necessary to form a heterocycle. ]