JP2852699B2 - Silver halide photographic material - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to a halogenated dye having excellent spectral absorption characteristics of a dye formed, excellent color reproducibility, excellent image storability, and high maximum density. It relates to a silver photographic light-sensitive material.

BACKGROUND OF THE INVENTION In a silver halide photographic light-sensitive material used for direct viewing, for example, a color printing paper, a combination of a yellow coupler, a magenta coupler and a cyan coupler is usually used as a color forming agent for forming a dye image. Used. For these couplers, the color reproducibility in the resulting dye image,
Although basic performance such as color developability and image storability is required, in particular, in recent years, there has been an increasing demand from users for color reproducibility in order to faithfully reproduce the original color of an object.

For example, in the case of a yellow coupler, since unnecessary absorption on the long wavelength side of 500 nm or more is not sharply reduced with respect to the formed colorant, the color reproduction in yellow and green hues was insufficient. .

On the other hand, with the progress of silver halide photographic light-sensitive materials, improvement in color developability has been demanded in recent years. For such purposes, various studies have been made on the design of coupler molecules for yellow couplers. It has been proposed to improve the color developability by introducing a hydrophilic group such as an alkoxycarbonyl group, a sulfonyl group, an N-substituted or unsubstituted alkylsulfonamide group or an arylsulfonamide group into the component.

However, when such a hydrophilic group is introduced into the ballast component of the yellow coupler, the color developability generally improves, but the unnecessary absorption on the long wavelength side of the coloring dye further increases, thereby causing deterioration in color reproducibility. In other words, the light resistance tends to deteriorate.

Therefore, a silver halide photographic light-sensitive material excellent in color development, color reproducibility and light fastness has not been found yet.

[Object of the Invention] A first object of the present invention is to provide a silver halide photographic material having improved color reproducibility for forming a yellow dye image having an excellent hue in which absorption on the long wavelength side is sharply reduced. It is in.

A second object of the present invention is to provide a silver halide photographic light-sensitive material having excellent storage stability of a yellow dye image.

A third object of the present invention is to provide a silver halide photographic material having a high color density and a sufficient maximum density.

[Constitution of the Invention] The object of the present invention is to provide a silver halide photographic material having at least one silver halide emulsion layer on a support, wherein the silver halide emulsion layer contains the following general formula [Y
-I] (wherein at least one of the yellow couplers represented by the following formula [Y] is not present) and coexists with at least one water-insoluble and organic solvent-soluble homo- or copolymer. This is achieved by a silver halide photographic light-sensitive material characterized by containing a dispersion present in lipophilic fine particles in a hydrated state.

[Wherein, R _A represents an alkyl group or a cycloalkyl group;
R _B represents an alkyl group, R _C represents a group that can be substituted on a benzene ring, R _D represents an unsubstituted alkyl group, and J represents ( _RE represents a hydrogen atom, an alkyl group, an aryl group, or a heterocyclic group.), And X ₁ can be released upon coupling with an oxidized developing agent. (Wherein, Z ₁ represents a group of non-metallic atoms necessary for forming a 5- or 6-membered ring together with a nitrogen atom), and n represents 0 or 1. Formula [Y] [Specific Configuration of the Present Invention] The yellow coupler represented by the general formula [Y-I] will be described.

In the general formula [Y-I], examples of the alkyl group represented by _RA include a methyl group, an ethyl group, an isopropyl group, a t-butyl group, and a dodecyl group. This R _A
The alkyl group represented by also includes those having a substituent. Examples of the substituent include a halogen atom, an aryl group, an alkoxy group, an aryloxy group, an alkylsulfonyl group, an arylsulfonyl group, an acylamino group, and a hydroxy group. And the like.

Examples of the cycloalkyl group represented by _RA include a cyclopropyl group, a cyclohexyl group, an adamantyl group, and the like.

Particularly preferred as R _A is a branched alkyl group.

In the general formula [Y-1], the alkyl group represented by R _B include the same groups as the alkyl group represented by R _A.

The alkyl group represented by R _B includes those having the same substituent as R _A.

In the general formula [Y-I], the group that can be substituted on the benzene ring represented by R _C includes a halogen atom (for example, a chlorine atom), an alkyl group, an alkoxy group (for example, a methoxy group), an aryloxy group, and an acyloxy group. , An acylamino group, a carbamoyl group, an alkylsulfonamide group, an arylsulfonamide group, a sulfamoyl group, and an imide group.

 n is 0 or 1.

In the general formula [Y-I], examples of the unsubstituted alkyl group represented by R _D include linear and branched alkyl groups having 1 to 30 carbon atoms, such as methyl, ethyl, n-propyl, and isopropyl. Group, t-butyl group, n-pentyl group,
n-hexyl group, 2-ethylhexyl group, n-octyl group, n-decyl group, linear and branched dodecyl group, tridecyl group, tetradecyl group, pentadecyl group, hexadecyl group, heptadecyl group, octadecyl group, nonadecyl group, eicosyl Group, docosyl group, tetracosyl group and hexacosyl group. Particularly preferred among these alkyl groups are those having 8 to 20 carbon atoms.

In the general formula [Y-I], J is The stands, R _E represents a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group.

_Examples of the alkyl group represented by RE include a methyl group, an ethyl group, an isopropyl group, a t-butyl group, and a dodecyl group.

The aryl group represented by R _E include such as a phenyl group or a naphthyl group.

Alkyl group or aryl group represented by these R _E include those having a substituent.

Although this substituent is not particularly limited, typical examples include a halogen atom, an alkyl group, and an aryl group (for example, a phenyl group, a p-methoxyphenyl group,
Naphthyl group), an alkoxy group, an aryloxy group, an alkylthio group, an arylthio group, an alkylsulfonyl group, an arylsulfonyl group, an acylamino group, and the like. Further, a carbamoyl group, an acyl group, which may have a substituent, Examples thereof include a sulfonamide group, a sulfamoyl group which may have a substituent, a hydroxy group, and a nitrile group.

In the general formula [Y-I], X ₁ can be released at the time of coupling with the oxidized form of the developing agent. (Wherein, Z ₁ represents a group of non-metallic atoms necessary for forming a 5- or 6-membered ring together with a nitrogen atom).

Here, the atomic groups required to form the non-metallic atomic group include, for example, methylene, methine, substituted methine, C =
O, -NH -, - N = , - O -, - S -, - SO 2 - , and the like.

Among the groups capable of leaving upon coupling with the oxidized form of the developing agent, particularly preferred groups are those represented by the following general formula [Y-
V] to [Y-IX].

In the general formulas [YV], [Y-VI] and [Y-VII], R _J and R _K are each a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, an aryl group, a heterocyclic group, a carboxylic acid ester Group, amino group, acylamino group, alkylsulfonyl group, arylsulfonyl group, alkylsulfinyl group, arylsulfinyl group, alkylsulfonamide group, arylsulfonamide group, and carboxylic acid group. May be.

R _J and R _K may form a ring.

Wherein Z ₂ is a heteroatom (eg, —NH—, —O—, —S
- etc.) represents, R _L has the same meaning as R _J. R _M represents an alkyl group, an aryl group, an alkylcarbonyl group, an arylcarbonyl group, an alkylsulfonyl group, or an arylsulfonyl group.

Wherein W is a heteroatom (eg, -NH-, -N =, -O
-, -S-, etc.), sulfonyl, carbonyl group or It represents a group represented in, Z ₃ is Represents a group of nonmetallic atoms necessary for forming a 5- or 6-membered ring in cooperation with R _N , R _O and R _P represent the same groups as R _J and R _K described above.

Further, R _N , R _O , and R _P may form a ring together with a part of Z ₃ .

The yellow coupler of the present invention preferably has a ballast group. A ballast group is an organic group that imparts anti-diffusion properties to a coupler, and includes an alkyl group having 6 or more carbon atoms, an aryl group having 10 or more carbon atoms, and a linear or branched alkyl group having a total of 10 or more carbon atoms. The aryl group substituted by is mentioned as an example. Each of these
It is a group included in the above description as R _B , R _C , R _D or a partial structure thereof in the general formula [Y-I].

The most preferable ones of the general formulas [YV] to [Y-IX] are those represented by the general formula [Y-IX].

The yellow coupler represented by the general formula [Y-I] according to the present invention can be synthesized by a conventionally known method.

The yellow coupler represented by the general formula [Y-I] according to the present invention can be used alone or in combination of two or more, and can be used in combination with another type of yellow coupler.

The yellow coupler according to the present invention may be used in an amount of usually about 1 × 10 ^-3 mol to about 1 mol, preferably 1 × 10 ^-2 mol to 8 × 10 ^-1 mol, per mol of silver halide. it can.

Next, typical specific examples of the 2-equivalent yellow coupler represented by the general formula [Y-I] used in the present invention will be shown, but the present invention is not limited thereto.

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

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

(1) Vinyl Polymer and Copolymer The monomers forming the vinyl polymer and the copolymer of the present invention will be more specifically described.

Acrylate: for example, methyl acrylate,
Ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-bull acrylate, tert-
Butyl acrylate, isobutyl acrylate, sec-
Butyl acrylate, amyl acrylate, hexyl acrylate, 2-ethylhexyl acrylate, octyl acrylate, tert-octyl acrylate, 2-chloroethyl acrylate, 2-bromoethyl acrylate, 4-chlorobutyl acrylate, cyanoethyl acrylate, 2-acetoxyethyl acrylate, dimethyl Aminoethyl 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-iso-propoxyethyl acrylate, 2-butoxyethyl acrylate, 2- (2-methoxyethoxy) ethyl acrylate, 2- (2-butoxyethoxy) ethyl acrylate, ω-methoxy Polyethylene glycol acrylate (additional mole number n = 9),
1-bromo-2-methoxyethyl acrylate, 1,1-
Dichloro-2-ethoxyethyl acrylate; methacrylate: For example, methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, tert-butyl methacrylate, isobutyl methacrylate, sec-butyl methacrylate, amyl methacrylate, hexyl Methacrylate, cyclohexyl methacrylate, benzyl methacrylate, chlorobenzyl methacrylate, octyl methacrylate, sulfopropyl methacrylate, N-ethyl-N-phenylaminoethyl methacrylate, 2- (3-phenylpropyloxy) ethyl methacrylate, dimethylaminophenoxyethyl methacrylate, furfuryl Methacrylate, tetrahydrofurfurylme Acrylate, phenyl methacrylate, cresyl methacrylate, naphthyl methacrylate, 2-hydroxyethyl methacrylate,
4-hydroxybutyl methacrylate, triethylene glycol monomethacrylate, dipropylene glycol monomethacrylate, 2-methoxyethyl methacrylate, 3-methoxybutyl methacrylate, 2-acetoxyethyl methacrylate, 2-acetoacetoxyethyl methacrylate, 2-ethoxyethyl methacrylate,
2-iso-propoxyethyl methacrylate, 2-butoxyethyl methacrylate, 2- (2-methoxyethoxy) ethyl methacrylate, 2- (2-ethoxyethoxy) ethyl methacrylate, 2- (2-butoxyethoxy) ethyl methacrylate, ω-methoxy Polyethylene glycol methacrylate (number of moles added: n = 6); Vinyl esters: for example, vinyl acetate, vinyl propionate, vinyl butyrate, vinyl isobutyrate, vinyl caproate, vinyl chloroacetate, vinyl methoxy acetate, vinyl phenyl Acetate, vinyl benzoate, vinyl salicylate; acrylamide: for example, acrylamide, methylacrylamide, ethylacrylamide, propylacrylamide, butylacrylamide, tert- Chill acrylamide, cyclohexyl acrylamide, benzyl acrylamide, hydroxymethyl acrylamide, methoxyethyl acrylamide, dimethylaminoethyl acrylamide, phenyl acrylamide, dimethyl acrylamide, diethyl acrylamide, beta-cyanoethyl acrylamide, N-(2-acetoacetoxyethyl)
Acrylamide, diacetone acrylamide; methacrylamides: for example, methacrylamide, methyl methacrylamide, ethyl methacrylamide, propyl methacrylamide, butyl methacrylamide, tert
-Butyl methacrylamide, cyclohexyl methacrylamide, benzyl methacrylamide, hydroxymethyl methacrylamide, methoxyethyl methacrylamide,
Dimethylaminoethyl methacrylamide, phenyl methacrylamide, dimethyl methacrylamide, diethyl methacrylamide, β-cyanoethyl methacrylamide,
N- (2-acetoacetoxyethyl) methacrylamide; olefins: dicyclopentadiene, ethylene, propylene, 1-butene, 1-pentene, vinyl chloride, vinylidene chloride, isoprene, chloroprene, butadiene, 2,3-dimethyl Butadiene; styrenes: for example, styrene, methylstyrene, dimethylstyrene, trimethylstyrene, ethylstyrene, isopropylstyrene, chloromethylstyrene, methoxystyrene, chlorostyrene, dichlorostyrene,
Bromostyrene, methyl vinyl benzoate; Crotonic acid esters: for example, butyl crotonate, hexyl crotonate; diesters of itaconic acid: for example, dimethyl itaconate, diethyl itaconate, dibutyl itaconate; diesters of maleic acid: for example, maleic Diethyl fumarate, dimethyl maleate, dibutyl maleate; fumaric acid diesters: for example, diethyl fumarate,
Dimethyl fumarate, dibutyl fumarate; and the like.

Examples of other monomers include the following.

Allyl compounds: for example, allyl acetate, allyl caproate, allyl laurate, allyl benzoate; vinyl ethers: for example, methyl vinyl ether,
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, methacrylonitrile;

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

Examples of the monomer having an acid group include acrylic acid; methacrylic acid; itaconic acid; maleic acid; monoalkyl itaconate (eg, monomethyl itaconate); monoalkyl maleate (eg, monomethyl maleate); citraconic acid; Acid; vinylbenzylsulfonic acid; acryloyloxyalkylsulfonic acid (eg, acryloyloxymethylsulfonic acid); methacryloyloxyalkylsulfonic acid (eg, methacryloyloxymethylsulfonic acid, methacryloyloxyethylsulfonic acid, methacryloyloxypropylsulfonic acid); acrylamide Alkyl sulfonic acids (eg,
2-acrylamide-2-methylethanesulfonic acid, 2
-Acrylamide-2-methylpropanesulfonic acid, 2
-Acrylamido-2-methylbutanesulfonic acid); methacrylamidoalkylsulfonic acid (for example, 2-methacrylamido-2-methylethanesulfonic acid, 2-methacrylamido-2-methylpropanesulfonic acid, 2-methacrylamido-2-) Acryloyloxyalkyl phosphate (e.g., acryloyloxyethyl phosphate, 3-acryloyloxypropyl-2-phosphate); methacryloyloxyalkyl phosphate (e.g., methacryloyloxyethyl phosphate, 3-methacryloyloxypropyl-2-phosphate) ).

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

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

The polymer formed from the above monomers is a solution polymerization method,
It can be obtained by bulk polymerization, suspension polymerization and latex polymerization. Initiators used in these polymerizations include:
A water-soluble polymerization initiator and a lipophilic polymerization initiator are used.

As the water-soluble polymerization initiator, for example, potassium persulfate, ammonium persulfate, persulfates such as sodium persulfate, sodium 4,4′-azobis-4cyanovalerate,
A water-soluble azo compound such as 2,2'-azobis (2-amidinopropane) hydrochloride and hydrogen peroxide can be used.

Examples of the lipophilic polymerization initiator include, for example, azobisisobutyronitrile, 2,2'-azobis (2,4-dimethylvaleronitrile), 2,2'-azobis (4-methoxy-2,4-dimethyl Valeronitrile), lipophilic azo compounds such as 1,1'-azobis (cyclohexanone-1-carbonitrile), dimethyl 2,2'-azobisisobutyrate, diethyl 2,2'-azobisisobutyrate, benzoyl peroxide, lauryl peroxide , Diisopropyl peroxydicarbonate and di-tert-butyl peroxide.

(2) Polyester Resin Obtained by Condensing Polyhydric Alcohol and Polybasic Acid As the polyhydric alcohol, HO—R ₁ —OH (R ₁ has 2 carbon atoms)
Hydrocarbons and about 12, especially glycols having an aliphatic hydrocarbon) comprising structure or polyalkylene glycols are effective, as the polybasic acid, HOOC-R ₂ -COOH
Those having (R ₂ 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,
1,2-propylene glycol, 1,3-propylene glycol, trimethylolpropane, 1,4-butanediol,
Isobutylene diol, 1,5-pentanediol, neopentyl glycol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1 , 11-undecanediol, 1,12-dodecanediol, 1,13-tridecanediol, 1,14-tetradecanediol, glycerin, diglycerin, triglycerin, 1-methylglycerin,
Erythritol, mannit, sorbit 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, dedocanedicarboxylic acid, Fumaric acid, maleic acid, itaconic acid, citraconic acid, phthalic acid, isophthalic acid, terephthalic acid, tetrachlorophthalic acid, metaconic acid, isohimeric acid, cyclopentadiene-maleic anhydride adduct, rosin-maleic anhydride adduct Can be

(3) Polyesters obtained by ring-opening polymerization These polyesters are β-propiolactone, ε
-It is obtained from caprolactone, dimethylpropiolactone and the like.

(4) Others Polycarbonate resin obtained by polycondensation of glycol or dihydric phenol with carbonate or phosgene, polyurethane resin obtained by polyaddition of polyhydric alcohol and polyvalent isocyanate, or polyamine and polybasic acid And the like.

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
It is between 5,000 and 100,000.

Specific examples of the polymer used in the present invention are shown below,
It is not limited to these. (The composition of the copolymer is indicated by weight ratio.) P-1) Poly (N-sec-butylacrylamide) P-2) Poly (N-tert-butylacrylamide) P-3) Diacetone acrylamide-methyl methacrylate copolymer Polymer (25:75) P-4) Polycyclohexyl methacrylate P-5) N-tert-butylacrylamide-methyl methacrylate copolymer (60:40) P-6) Poly (N, N-dimethylacrylamide) P- 7) Poly (tert-butyl methacrylate) P-8) Polyvinyl acetate P-9) Polyvinyl propionate P-10) Polymethyl methacrylate P-11) Polyethyl methacrylate P-12) Polyethyl acrylate P-13) Vinyl acetate -Vinyl alcohol copolymer (9
0:10) P-14) Poly n-butyl acrylate P-15) Poly n-butyl methacrylate P-16) Polyisobutyl methacrylate P-17) Polyisopropyl methacrylate P-18) Polyoctyl acrylate P-19) N-butyl Acrylate-acrylamide copolymer (95: 5) P-20) Stearyl methacrylate-acrylic acid copolymer (90:10) P-21) Methyl methacrylate-vinyl chloride copolymer (70:30) P-22) Methyl Methacrylate-styrene copolymer (90:10) P-23) Methyl methacrylate-ethyl acrylate copolymer (50:50) P-24) n-butyl methacrylate-methyl methacrylate-styrene copolymer (50:20:30) ) P-25) Vinyl acetate-acrylamide copolymer (85: 1
5) P-26) Vinyl chloride-vinyl acetate copolymer (65:35) P-27) Methyl methacrylate-acrylonitrile copolymer (65:35) P-28) n-butyl methacrylate-pentyl methacrylate-N- Vinyl-2-pyrrolidone copolymer (38: 3
8:24) P-29) Methyl methacrylate-n-butyl methacrylate-isobutyl-methacrylate-acrylic acid copolymer (37: 29: 25: 9) P-30) n-butyl methacrylate-acrylic acid (9
5: 5) P-31) Methyl methacrylate-acrylic acid copolymer (95: 5) P-32) Benzyl methacrylate-acrylic acid copolymer (93: 7) P-33) n-butyl methacrylate-methyl methacrylate Benzyl methacrylate-acrylic acid copolymer (35: 35: 25: 5) P-34) n-butyl methacrylate-methyl methacrylate-benzyl methacrylate copolymer (40:30:30) P-35) diacetone acrylamide-methyl Methacrylate copolymer (50:50) P-36) Methyl vinyl ketone-isobutyl methacrylate copolymer (55:45) P-37) Ethyl methacrylate-n-butyl acrylate copolymer (70:30) P-38) Diacetone acrylamide-n-butyl acrylate copolymer (60:40) P-39) Methyl methacrylate-stearyl methacrylate-diacetone Acrylamide copolymer (40: 40: 2
0) P-40) n-butyl acrylate-stearyl methacrylate-diacetone acrylamide copolymer (70:20:
10) P-41) Stearyl methacrylate-methyl methacrylate-acrylic acid copolymer (50:40:10) P-42) Methyl methacrylate-styrene-vinyl sulfonamide copolymer (70:20:10) P-43) Methyl methacrylate-phenyl vinyl ketone copolymer (70:30) P-44) n-butyl acrylate-methyl methacrylate-n-butyl methacrylate copolymer (35:35:30) P-45) n-butyl methacrylate-N -Vinyl-2
-Pyrrolidone copolymer (90:10) P-46) Polypentyl acrylate P-47) Cyclohexyl methacrylate-methyl methacrylate-n-propyl methacrylate copolymer (3
7:29:34) P-48) Polypentyl methacrylate P-49) Methyl methacrylate-n-butyl methacrylate copolymer (65:35) P-50) Vinyl acetate-vinyl propionate copolymer (75:25) ) P-51) n-butyl methacrylate-3-acryloxybutane-1-sodium sulfonate copolymer (97:
3) P-52) n-butyl methacrylate-methyl methacrylate-acrylamide copolymer (35:35:30) P-53) n-butyl methacrylate-methyl methacrylate-vinyl chloride copolymer (37:36:27) P -54) n-butyl methacrylate-styrene copolymer (82:18) P-55) tert-butyl methacrylate-methyl methacrylate copolymer (70:30) P-56) poly (N-tert-butyl methacrylamide) P-57) N-tert-butylacrylamide-methylphenyl methacrylate copolymer (60:40) P-58) Methyl methacrylate-acrylonitrile copolymer (70:30) P-59) Methyl methacrylate-methyl vinyl ketone Polymer (38:72) P-60) Methyl methacrylate-styrene copolymer (75:25) P-61) Methyl methacrylate-hexyl methacrylate Polymer (70:30) P-62) Butyl methacrylate-acrylic acid copolymer (85:15) P-63) Methyl methacrylate-acrylic acid copolymer (80:20) P-64) Methyl methacrylate-acrylic acid Copolymer (90:10) P-65) Methyl methacrylate-acrylic acid copolymer (98: 2) P-66) Methyl methacrylate-N-vinyl-2-pyrrolidone copolymer (90:10) P-67 ) N-butyl methacrylate-vinyl chloride copolymer (90:10) P-68) n-butyl methacrylate-styrene copolymer (70:30) P-69) 1,4-butanediol-adipate polyester P- 70) Ethylene glycol-sebacic acid polyester P-71) Polycaprolactam P-72) Polypropiolactam P-73) Polydimethylpropiolactone P-74) N-tert-butylacrylamide-dimethyl L-aminoethylacrylamide copolymer (85:15) P-75) N-tert-butyl methacrylamide-vinylpyridine copolymer (95: 5) P-76) diethyl maleate-n-butyl acrylate copolymer ( 65:35) P-77) N-tert-butylacrylamide-2-methoxyethyl acrylate copolymer (55:45) In the present invention, coupling with an oxidized aromatic primary amine developing agent, At least one of the yellow couplers represented by the general formula [Y-I] which forms a dye;
The dispersion in which the species are present in the lipophilic fine particles in the state of being co-existed with at least one of a water-insoluble and organic solvent-soluble homo- or copolymer is the coupler and at least one of the homo- or copolymers. Is dissolved in a substantially water-insoluble high-boiling organic solvent and emulsified and dispersed in a hydrophilic protective colloid.

Here, a substantially water-insoluble high-boiling organic solvent is a compound having a melting point of 100 ° C. or lower and a boiling point of 140 ° C. or higher, which is immiscible with water, and is an ester such as a phenol derivative, a phthalate ester or a phosphate ester. , Organic acid amides, carbamates, kents and the like. These are U.S. Patent Nos.
No. 2,322,027, No. 2,353,262, No. 2,533,514, No. 2,801,170, No. 2,801,171, No. 2,835,579,
No. 2,852,383, No. 2,870,012, No. 2,991,171
No. 3,287,134, No. 3,554,755, No. 3,676,13
No. 7, No. 3,676,142, No. 3,700,454, No. 3,748,1
No. 41, 3,779,765 and 3,837,863.

In addition, a low-boiling organic solvent or an organic solvent miscible with water can be used to assist the dissolution.

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

Water-miscible organic solvents include methyl alcohol,
Ethyl alcohol, acetone, phenoxyethanol,
Examples include tetrahydrofuran and dimethylformamide.

These low-boiling organic solvents and water-miscible organic solvents are:
It can be removed by a method such as washing with water or by coating and drying.

Further, two or more kinds of the organic solvents described above can be used in combination.

In order to emulsify and disperse the lipophilic fine particles in the hydrophilic protective colloid, the dispersion is carried out using a dispersing aid such as a surfactant using a stirrer, a homogenizer, a colloid mill, a flow jet mixer, an ultrasonic device or the like. A step of removing the low-boiling organic solvent at the same time as the dispersion may be included.

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

The average particle diameter of the lipophilic fine particles is preferably from 0.04 μm to 2 μm, more preferably from 0.06 μm to 0.4 μm. The particle size can be measured using a Coulter model N4 manufactured by Coulter, UK.

In the present invention, the mixing ratio of the coupler, the homo- or copolymer, the auxiliary solvent such as a high-boiling solvent and a low-boiling solvent or an organic solvent miscible with water, the coupler, the homo- or copolymer, the high-boiling solvent is the auxiliary solvent. May be selected so as to have a viscosity suitable for easily dissolving a solution dissolved in a hydrophilic colloid. The value at this time depends on the solubility of the coupler used, the type and degree of polymerization of the polymer, and cannot be determined uniformly. For example, the ratio (weight ratio) of the polymer to the coupler (weight ratio) is 1:10 to 5: 1. , Preferably 1: 3 to 2: 1.

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

In the present invention, at least one kind of the yellow coupler represented by the general formula [Y-I] is present in the lipophilic fine particles in a state where it is present together with one kind of a water-insoluble and organic solvent-soluble homo- or copolymer. The dispersion is preferably added to a blue-sensitive silver halide emulsion layer.

Further, in the dispersion, compounds which do not need to be adsorbed on the silver halide crystal surface, for example, an image stabilizer, a color fogging inhibitor, an ultraviolet absorber, a fluorescent brightener, an oil-soluble dye, and the like are simultaneously dispersed. Can also.

It is preferable to simultaneously disperse the image stabilizers described in JP-A-59-125732 and JP-A-62-96944.

The silver halide photographic light-sensitive material of the present invention can be applied to, for example, color negative and positive films, color photographic paper, etc., and particularly when applied to color photographic paper for direct viewing. The effect is effectively exhibited.

The silver halide photographic light-sensitive material of the present invention including the color photographic paper may be of a single color or a multicolor. In the case of a silver halide photographic material for multicolor, in order to perform color-reduced color reproduction, a silver halide emulsion layer containing a yellow, magenta and cyan coupler as a photographic coupler and a non-photosensitive material are usually used. Although the layer has a structure in which the layers are laminated on the support in an appropriate number and order of layers,
The number of layers and the order of the layers may be appropriately changed depending on the emphasis performance and the purpose of use.

Examples of the magenta dye image-forming coupler that can be used in the present invention include 4-equivalent or 2-equivalent magenta dye image-forming couplers of 5-pyrazolone type, pyrazoloazole type, pyrazolinobenzimidazole type, indazolone type and cyanoacetyl type. These are, for example, U.S. Pat.Nos. 2,600,788, 3,061,432, 3,062,653
No. 3,127,269, 3,152,896, 3,311,476,
3,419,391, 3,519,429, 3,558,318, 3,6
No. 84,514, No. 3,705,896, No. 3,888,680, No. 3,907,57
No. 1, No. 3,928,044, No. 3,930,861, No. 3,930,816,
No. 3,933,500, JP-A-49-29639, JP-A-49-111631,
No. 49-129538, No. 51-112341, No. 52-58922, No. 5
5-62454, 55-118034, 56-38643, 56-1
35841, JP-B-46-60479, 52-34937, 55-2
Nos. 9421 and 55-35696, British Patent No. 1,247,493, Belgian Patent No. 792,525, and West German Patent No. 2,156,111.

As the cyan coupler that can be used in the present invention, a phenol compound, a naphthol compound, or the like can be used. For example, U.S. Pat.
929, 2,434,272, 2,474,293, 2,521,908
Nos. 2,895,826, 3,034,892, 3,311,476,
3,458,315, 3,476,563, 3,583,971, 3,5
91,383, 3,767,411, 4,004,929, West German Patent Application (OLS) 2,414,830, 2,454,329, JP-A-48-598
No. 38, No. 51-26034, No. 48-5055, No. 51-146828
And Nos. 52-69624 and 52-90932.

The silver halide emulsion used in the silver halide photographic light-sensitive material of the present invention (hereinafter, referred to as the silver halide emulsion of the present invention) includes silver bromide, silver iodobromide, silver iodochloride, and silver halide. Any of those used in ordinary silver halide emulsions such as silver bromide and silver chloride can be used.

The silver halide emulsion of the present invention is chemically sensitized by a sulfur sensitization method, a selenium sensitization method, a reduction sensitization method, a noble metal sensitization method, or the like.

The silver halide emulsion of the present invention can be optically sensitized to a desired wavelength region using a dye known as a sensitizing dye in the photographic industry.

The silver halide photographic light-sensitive material of the present invention includes a color fogging inhibitor, a hardener, a plasticizer, a polymer latex, an ultraviolet absorber, a formalin scavenger, a mordant, a development accelerator, a development retarder, a fluorescent brightener, and a mat. Agents, lubricants, antistatic agents, surfactants and the like can be optionally used.

The silver halide photographic light-sensitive material of the present invention can form an image by performing various color development processes.

[Examples] Specific examples of the present invention will be described below, but embodiments of the present invention are not limited thereto.

Example 1 (Adjustment of silver halide emulsion) Three kinds of silver halide emulsions shown in Table 1 were prepared by a neutral method and a simultaneous mixing method.

After completion of chemical sensitization, each of the silver halide emulsions was added with 5 × 10 ⁻³ mol of STB-1 shown below as an emulsion stabilizer per mol of silver halide.

(Preparation of silver halide color photographic light-sensitive material sample) Next, the following layers 1 to 7 were successively applied (simultaneously applied) on a paper support having both surfaces coated with polyethylene to prepare silver halide color photographic light-sensitive material 1. did. (In the following examples, the amount of addition is shown in terms of the amount per 1 m ² of the light-sensitive material.) Layer 1... Blue-sensitive silver halide emulsion of gelatin (1.2 g) and 0.29 g (silver conversion, same hereafter) (Em-1) and 1.0 mmol of a comparative yellow coupler (YA) and 0.015 g of 2,
0.3 in which 5-dioctylhydroquinone (HQ-1) is dissolved
A layer containing g of DOP (dioctyl phthalate).

Layer 2 Layer containing gelatin (0.9 g) and 0.24 DOP in which 0.04 g of HQ-1 is dissolved.

Layer 3: Gelatin (1.4 g), 0.2 g of green light-sensitive silver halide emulsion (Em-2) and 0.5 g of magenta coupler (M-
1) 0.25 g of light stabilizer (ST-2) and 0.01 g of HQ-1 dissolved in 0.3 g of DOP and 6 mg of the following filter dye (AI-
1) a layer containing

Layer 4: Gelatin (1.2 g) and 0.6 g of ultraviolet absorber (UV
1) and 0.3 g of DNP (dinonyl phthalate) containing 0.05 g of HQ-1 dissolved therein.

Layer 5: gelatin (1.4 g), 0.20 g of a red-sensitive silver halide emulsion (Em-3), and 0.54 g of a cyan coupler (C-
1) 0.3 g in which 0.01 g of HQ-1 and 0.3 g of ST-1 were dissolved
Containing DOP.

Layer 6: Layer containing gelatin (1.1 g), 0.3 g of DOP in which 0.2 g of UV-1 is dissolved, and 5 mg of the following filter dye (AI-2).

Layer 7: Layer containing gelatin (1.0 g) and 0.05 g of sodium 2,4-dichloro-6-hydroxytriazine.

Further, among the above-mentioned layer constitutions, the types and amounts of the yellow coupler, the high boiling point organic solvent and the water-insoluble and organic solvent-soluble homo- or copolymer in Layer 1 are shown in Table 2, and the silver halide photosensitive material is shown in Table 2. (Nos. 2 to 17) were created.

The obtained sample was used as a sensitometer KS-7 (manufactured by Konica Corporation).
After exposure using a wedge and processing according to the following color development processing step, an optical densitometer (manufactured by Konica Corporation)
Using PDA-65 type), the maximum density (Dma
x) was measured.

Further, the maximum absorption wavelength λmax when the density of the yellow dye image is 1.0, and the density at the wavelength of 500 nm at that time.
_DG was measured.

Further, the obtained sample was subjected to a fading test for 14 days using a fade meter, and the light resistance was evaluated by obtaining the residual ratio (%) of the dye image at an initial density of 1.0.

 The results are shown in Table-3.

[Processing process] Temperature Time Color development 34.7 ± 0.3 ° C 45 seconds Bleaching and fixing 34.7 ± 0.5 ° C 50 seconds Stabilization 30-34 ° C 90 seconds Drying 60-80 ° C 60 seconds [Color developing solution] Pure water 800ml Triethanolamine 8g N, N-diethylhydroxyamine 5g Potassium chloride 2g N-ethyl-N-β-methanesulfonamidoethyl-
3-methyl-4-aminoaniline sulfate 5 g Sodium tetrapolyphosphate 2 g Potassium carbonate 30 g Potassium sulfite 0.2 g Fluorescent whitening agent (4,4'-diaminostilbendisulfonic acid derivative) 1 g Adjust to pH 10.2.

[Bleaching and fixing solution] Ethylenediaminetetraacetic acid ferric ammonium dihydrate 60 g Ethylenediaminetetraacetic acid 3 g Ammonium thiosulfate (70% solution) 100 ml Ammonium sulfite (40% solution) 27.5 ml Adjusted to pH 5.7 with potassium carbonate or glacial acetic acid, Add water to bring the total volume to 1.

[Stabilizing solution] 5-chloro-2-methyl-4-isothiazoline-3-
ON 1 g 1-hydroxyethylidene-1,1-diphosphonic acid 2 g Add water to make 1 and adjust to pH with sulfuric acid or potassium hydroxide
Adjust to 7.0.

As is apparent from Table 3, samples No.5~17 using a polymer of the yellow coupler and the invention of the present invention is chromogenic has good, superior color reproducibility for D _G has decreased, Further, it can be seen that the light resistance is remarkably improved.

[Effect of the Invention] In the silver halide photographic light-sensitive material of the present invention, the spectral absorption characteristics of the formed yellow dye are improved, and as a result, the color reproducibility can be greatly improved. In addition, the image storability of the yellow dye can be further improved,
It has high color development and a sufficient maximum density.

Continuation of the front page (58) Field surveyed (Int.Cl. ⁶ , DB name) G03C 7/36

Claims (1)

(57) [Claims] 1. A silver halide photographic material having at least one silver halide emulsion layer on a support, wherein a yellow coupler represented by the following general formula [Y-I] is contained in said silver halide emulsion layer. (However, except for a yellow coupler represented by the following formula [Y]), wherein at least one of water-insoluble and organic solvent-soluble homo- or copolymers is present together with at least one of the lipophilic fine particles. A silver halide photographic light-sensitive material, characterized by containing a dispersion existing in a silver halide photographic material. [Wherein, R _A represents an alkyl group or a cycloalkyl group;
R _B represents an alkyl group, R _C represents a group that can be substituted on a benzene ring, R _D represents an unsubstituted alkyl group, and J represents ( _RE represents a hydrogen atom, an alkyl group, an aryl group, or a heterocyclic group.), And X ₁ can be released upon coupling with an oxidized developing agent. (Wherein, Z ₁ represents a group of non-metallic atoms necessary for forming a 5- or 6-membered ring together with a nitrogen atom), and n represents 0 or 1. Formula [Y]