JP3538796B2 - Silver halide color photographic materials - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a silver halide color photographic light-sensitive material (hereinafter, also simply referred to as "light-sensitive material").
More specifically, the present invention relates to a silver halide color photographic light-sensitive material which is excellent in color developing properties, light fastness and color reproducibility of the photographic material, and is also excellent in rapid processing.

[0002]

2. Description of the Related Art In a silver halide color photographic light-sensitive material for direct viewing, for example, a color photographic paper, a combination of a yellow coupler, a magenta coupler and a cyan coupler is usually used as a coloring agent for forming a dye image. Can be These couplers are required to have performances such as excellent coloring properties, good color reproducibility of dye images and good storage durability (light fastness). For materials, the printing process and the development process are becoming shorter and faster,
There has been an increasing demand for rapid processing.

A yellow coupler is used as one component of a color photographic light-sensitive material. In the art, a two-equivalent yellow coupler is used in order to obtain the maximum dye density and photographic sensitivity with a small amount of silver. In the case of, as an active site substituent, for example, JP-A-50-8765
No. 0, U.S. Pat. No. 3,408,194, etc., aryloxy group, oxazolyloxy group described in JP-A-51-131325, chroman-4-oxy group described in JP-A-51-139333, JP-A-52-43426, tetrazolyloxy group, nitrogen-containing heterocyclic group described in JP-A-52-115219, urazole group and hydantoin group described in JP-B-51-33410, U.S. Pat. No. 3,227,55
The arylthio group described in No. 4 is known.

On the other hand, with the progress of silver halide photographic light-sensitive materials, the demands on the performance of couplers have become more and more severe, and the improvement of color-forming efficiency has also been demanded for the 2-equivalent yellow couplers. For this reason, on the design of the coupler molecule, various attempts have been made, for example, improvement of the color development by introducing an alkoxycarbonyl group or an N-substituted or unsubstituted alkylsulfonamide group or an arylsulfonamide group into a ballast component has been proposed. However, it has not been sufficiently improved.

[0005]

SUMMARY OF THE INVENTION An object of the present invention is to provide a silver halide color photographic light-sensitive material which is excellent in color development, light fastness, color reproducibility and rapid processing. .

[0006]

The above object of the present invention is attained by the following constitutions.

(1) A photographic component layer including a blue-sensitive silver halide emulsion layer, a green-sensitive silver halide emulsion layer and a red-sensitive silver halide emulsion layer on a support, wherein the blue-sensitive silver halide emulsion layer A silver halide color photographic light-sensitive material comprising at least one yellow coupler represented by the following formula [I] or [II]:

[0008]

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[Wherein R ^A and R ^C represent an alkyl group;
R ^B represents a branched alkyl group, R ^E and R ^F is each represents a hydrogen atom or an alkyl group. ]

[0010]

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Wherein R ^A and R ^C represent an alkyl group;
R ^B represents a branched alkyl group, R ^G represents a hydrogen atom or an alkoxy group. (2) having a photographic component layer comprising a blue-sensitive silver halide emulsion layer, a green-sensitive silver halide emulsion layer and a red-sensitive silver halide emulsion layer on a support, wherein the blue-sensitive silver halide emulsion layer A blue-sensitive silver halide emulsion layer containing at least one yellow coupler represented by the general formula (I) or (II), and a water-insoluble and organic solvent-soluble homopolymer or copolymer. A silver halide color photographic light-sensitive material comprising at least one kind.

[0012]

[C]

Wherein R ^A and R ^C represent an alkyl group, and R ^B is a branched
R ^E and R ^F each represent a hydrogen atom or an alkyl
Represents a hydroxyl group. ]

[D]

Wherein R ^A and R ^C represent an alkyl group, and R ^B is a branched
R ^G represents a hydrogen atom or an alkoxy group.
You. Hereinafter, the present invention will be described in detail.

The yellow couplers represented by the general formulas (I) and (II) will be described.

In the general formulas (I) and (II), the alkyl group represented by R ^A and R ^C is a linear or branched alkyl group, for example, a methyl group, an ethyl group,
Examples thereof include an isopropyl group, a t-butyl group, a dodecyl group, a 1-hexylnonyl group, a cyclopropyl group, a cyclohexyl group, and an adamantyl group. These R ^A and R ^C
The alkyl group represented by can further have a substituent, for example, a halogen atom (eg, a chlorine atom, a bromine atom, etc.), an aryl group (eg, a phenyl group, a pt-octylphenyl group, etc.) ), An alkoxyl group (eg, a methoxy group), an aryloxy group (eg, a 2,4-di-t-amylphenoxy group), a sulfonyl group (eg, a methanesulfonyl group), an acylamino group (eg, an acetyl group, a benzoyl group, etc.) ), A sulfonylamino group (for example, a dodecanesulfonylamino group and the like), a hydroxyl group and the like.

As R ^A , a branched alkyl group is particularly preferred, and a t-butyl group is particularly preferred.

R ^C is preferably an alkyl group, particularly preferably a linear or branched alkyl group having 10 or more carbon atoms.

In the general formulas (I) and (II), examples of the branched alkyl group represented by R ^B include:
Isopropyl group, sec-butyl group, iso-butyl group,
And a 2-ethylhexyl group. The R ^B is preferably an isopropyl group.

In the general formulas (I) and (II),
The alkyl groups represented by R ^E and R ^F,. 1 to carbon atoms
Ten linear and branched alkyl groups, for example, a methyl group, an ethyl group, a propyl group, an i-propyl group, a butyl group, a hexyl group and the like are mentioned, and a methyl group is particularly preferred.

In the general formula [II], examples of the alkoxy group represented by R ^G include a methoxy group, an ethoxy group, an isopropoxy group, and a hexyloxy group.

The silver halide color photographic light-sensitive material of the present invention more preferably contains at least one yellow coupler represented by the general formula [I].

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

[0022]

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[0023]

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Synthesis Example 1 (Synthesis of YI-1) 54.6 g of α-pivaloyl-2-isopropyloxy-5-n-hexadecyloxycarbonylacetanilide
Was dissolved in 160 ml of ethyl acetate, 13.5 g of sulfuryl chloride was added dropwise thereto, and the mixture was stirred for 1 hour, and then the solvent was removed under reduced pressure.

The obtained residue was dissolved in 200 ml of acetone, and 16.8 g of 5,5-dimethyl-2,4-oxazolidinedione and 18.0 g of potassium carbonate were added thereto, and the mixture was heated under reflux for 3 hours. After completion of the reaction, ethyl acetate was added, and the mixture was washed with a 5% aqueous potassium carbonate solution and dilute hydrochloric acid, and the organic layer was concentrated under reduced pressure. The obtained residue was recrystallized from methanol to obtain the desired coupler YI-1. Yield 55.
The structure of 4 g (yield 82%) was confirmed by NMR, IR and mass spectrum.

Exemplary couplers of the yellow coupler of the present invention other than the exemplary coupler YI-1 were also synthesized according to the above synthesis examples.

The general formula [I] or the general formula [I
The yellow couplers represented by I) can be used alone or in combination of two or more, and can be used in combination with another type of yellow coupler.

Further, the yellow coupler according to the present invention comprises:
Usually about 1 × 10 ^-3 mol to about 1 mol per mol of silver halide
Mol, preferably in the range of 1 × 10 ^-2 mol to 8 × 10 ^-1 mol.

The general formula [I] or the general formula [I
The yellow coupler represented by the formula (I) is contained in a blue-sensitive silver halide emulsion layer. It is preferable that the blue-sensitive silver halide emulsion layer contains at least one kind of a water-insoluble and organic solvent-soluble homopolymer or copolymer in view of particularly excellent light resistance.

Next, the water-insoluble and organic solvent-soluble homopolymer or copolymer of the present invention will be described in detail.

The homo- or copolymer of a water-insoluble and organic solvent-soluble (hereinafter, polymer, used in the present invention of the present invention
A polymer is the polymer used in the present invention, the Some <br/> intends. As), various ones 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 more specifically.

Acrylic esters: for example, methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl 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, 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-iso
-Propoxyethyl acrylate, 2-butoxyethyl acrylate, 2- (2-methoxyethoxy) ethyl acrylate, 2- (2-butoxyethoxy) ethyl acrylate, ω-methoxypolyethylene glycol acrylate (additional mole number n = 9), 1- Bromo-2-methoxyethyl acrylate, 1,1-dichloro-2-ethoxyethyl acrylate; methacrylates: 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, Lolo benzyl 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 monomethacrylate, dipropylene glycol monomethacrylate, 2-methoxyethyl methacrylate, 3-methoxybutyl methacrylate, 2-acetoxyethyl methacrylate, 2-acetoacetoxyethyl methacrylate , 2-ethoxyethyl methacrylate, 2-iso Propoxyethyl methacrylate,
2-butoxyethyl methacrylate, 2- (2-methoxyethoxy) ethyl methacrylate, 2- (2-ethoxyethoxy) ethyl methacrylate, 2- (2-butoxyethoxy) ethyl methacrylate, ω-methoxypolyethylene glycol methacrylate (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, methyl acrylamide, ethyl acrylamide, propyl acrylamide, butyl acrylamide, tert-butyl acrylamide, cyclohexyl acrylamide, benzyl acrylamide, hydroxymethyl acrylamide, methoxyethyl Acrylamide, dimethylaminoethylacrylamide, phenylacrylamide, dimethylacrylamide, diethylacrylamide, β-cyanoethylacrylamide, N- (2-acetoacetoxyethyl) acrylamide, diacetoneacrylamide; methacrylamides: for example, methacrylamide, methylmethacrylamide, ethyl Methacryl Amide, propyl methacrylamide, butyl methacrylamide, ter
t-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: for example, dicyclopentadiene, ethylene, propylene, 1-butene, 1-pentene, vinyl chloride, vinylidene chloride, isoprene, chloroprene, butadiene, 2,3-dimethylbutadiene; Styrenes: for example, styrene, methylstyrene, dimethylstyrene, trimethylstyrene, ethylstyrene,
Isopropylstyrene, chloromethylstyrene, methoxystyrene, chlorostyrene, dichlorostyrene, bromostyrene, methyl vinylbenzoate; crotonic acid esters: for example, butyl crotonate, hexyl crotonate; itaconic acid diesters: for example, dimethyl itaconate; Diethyl itaconate, dibutyl itaconate; maleic acid diesters: for example, diethyl maleate, dimethyl maleate, dibutyl maleate; fumaric acid diesters: for example, diethyl fumarate, dimethyl fumarate, dibutyl fumarate; .

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-mentioned 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 such an extent that it does not become water-soluble (preferably 2
0% or less. ), Those that do not contain at all.
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
-Acrylamide-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) ).

The monomer having an acid group may be a salt of an alkali metal (for example, Na or K) or an ammonium ion.

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 can be obtained by a solution polymerization method, a bulk polymerization method, a suspension polymerization method, and a latex polymerization method. As the initiator used for these polymerizations, a water-soluble polymerization initiator and a lipophilic polymerization initiator are used.

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

Examples of the lipophilic polymerization initiator include azobisisobutyronitrile and 2,2'-azobis (2,4
-Dimethylvaleronitrile), 2,2'-azobis (4
-Methoxy-2,4-dimethylvaleronitrile), 1,
1'-azobis (cyclohexanone-1-carbonitrile), dimethyl 2,2'-azobisisobutyrate, 2,2 '
-Lipophilic azo compounds such as diethyl azobisisobutyrate, benzoyl peroxide, lauryl peroxide, diisopropylperoxydicarbonate, and di-tert-butyl peroxide.

(2) Polyester Resin Obtained by Condensing Polyhydric Alcohol and Polybasic Acid Polyols include HO-R ₁ -OH (R ₁ is a hydrocarbon having 2 to about 12 carbon atoms, especially Glycols having a structure of (aliphatic hydrocarbons) or polyalkylene glycols are effective, and as the polybasic acid, HOOC-
Those having R ₂ —COOH (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,
Examples thereof include 1,12-dodecanediol, 1,13-tridecanediol, 1,14-tetradecanediol, glycerin, diglycerin, triglycerin, 1-methylglycerin, erythritol, mannitol, sorbit and the like.

Specific examples of the polybasic acid include oxalic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, cornic acid, azelaic acid, sebacic acid, nonanedicarboxylic acid,
Decanedicarboxylic acid, undecanedicarboxylic acid, dodecanedicarboxylic acid, fumaric acid, maleic acid, itaconic acid,
Examples thereof include citraconic acid, phthalic acid, isophthalic acid, terephthalic acid, tetrachlorophthalic acid, metaconic acid, isohimeric acid, cyclopentadiene-maleic anhydride adduct, and rosin-maleic anhydride adduct.

(3) Polyester Obtained by Ring-Opening Polymerization These polyesters include β-propiolactone, ε-
It can be obtained from caprolactone, dimethylpropiolactone and the like.

(4) Other polycarbonate resins obtained by polycondensation of glycol or dihydric phenol with carbonate or phosgene, polyurethane resins or polyamines obtained by polyaddition of polyhydric alcohol and polyisocyanate Examples thereof include 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 100,000.

Specific examples of the polymer used in the present invention are shown below, but it should not be construed that the invention is limited thereto. (The composition of the copolymer is shown 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 (90:10) P-1 ) 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 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 Combined (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 (8
5:15) 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 (3
8:38:24) P-29) Methyl methacrylate-n-butyl methacrylate-isobutyl-methacrylate-acrylic acid copolymer (37: 29: 25: 9) P-30) n-butyl methacrylate-acrylic acid (95: 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: 3
0:30) 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:
40:20) P-40) n-butyl acrylate-stearyl methacrylate-diacetone acrylamide copolymer (7
0:20:10) 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: 3)
5:30) 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 (37:29:34) 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-acryloxy Sodium butane-1-sulfonate copolymer (9
7: 3) P-52) n-butyl methacrylate-methyl methacrylate-acrylamide copolymer (35: 35: 3)
0) 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-butyl acrylamide-methylphenyl methacrylate copolymer (60:40) P -58) Methyl methacrylate-acrylonitrile copolymer (70:30) P-59) Methyl methacrylate-methyl vinyl ketone copolymer (38:72) P-60) Methyl methacrylate-styrene copolymer (75:25) P-61) Methyl methacrylate-hexyl methacrylate (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 (98: 2) P-65) Methyl methacrylate-N-vinyl-2-
Pyrrolidone copolymer (90:10) P-66) n-butyl methacrylate-vinyl chloride copolymer (90:10) P-67) n-butyl methacrylate-styrene copolymer (70:30) P-68) 1,4-butanediol-adipic polyester P-69) ethylene glycol-sebacic polyester P-70) polycaprolactam P-71) polypropiolactam P-72) polydimethylpropiolactone P-73) N-tert- Butylacrylamide-dimethylaminoethylalamide copolymer (85:15) P-74) N-tert-butylmethacrylamide-vinylpyridine copolymer (95: 5) P-75) Diethyl maleate-n-butyl acrylate Copolymer (65:35) P-76) N-tert-butyla Riruamido -2
- methoxyethyl acrylate copolymer (55:45) in the present invention, the polymer of the present invention is to oxidant coupling of an aromatic primary amine developing agent, while coexisting with the coupler to form a dye It is preferably used as a dispersion present in the lipophilic fine particles. The dispersion is obtained by dissolving in a high boiling organic solvent substantially water-insoluble at least one polymer of the coupler and the present invention is emulsified and dispersed in a hydrophilic protective colloid.

Here, the 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 and being immiscible with water, such as a phenol derivative, a phthalate ester or a phosphate ester. Esters, organic acid amides, carbamates, kents and the like. These are disclosed in U.S. Pat. Nos. 2,322,027 and 2,35.
No. 3,262, No. 2,533,514, No. 2,8
No. 01,170, No. 2,801,171, No. 2,
No. 835,579, No. 2,852,383, No. 2,870,012, No. 2,991,171, No. 3,287,134, No. 3,554,755,
Nos. 3,676,137 and 3,676,142
No. 3,700,454, No. 3,748,14
No. 1, No. 3,779,765 and No. 3,837,
No. 863.

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

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

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

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

The organic solvents described above can be used in combination of two or more.

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

An aqueous gelatin solution is preferably used as the hydrophilic protective colloid.

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

In the above, the mixing ratio of the coupler, the homo- or copolymer, the high-boiling solvent and the auxiliary solvent such as the low-boiling solvent or the water-miscible organic solvent is such that the coupler, the homo- or copolymer and the high-boiling solvent are mixed. The viscosity may be selected so that the solution dissolved in the auxiliary solvent has a viscosity suitable for being easily dispersed in the hydrophilic colloid. The value at this time depends on the solubility of the coupler used, the type of the polymer and the degree of polymerization, 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: 2.
10 to 2: 1. The ratio (weight ratio) of the low boiling solvent to the polymer is from 1:10 to 10: 1, preferably from 1: 4 to 1.
5: 1.

The light-sensitive silver halide emulsion layer of the silver halide color photographic light-sensitive material of the present invention contains a silver halide emulsion.

The silver halide emulsions of the present invention include silver chloride, silver bromide, silver iodide and mixed silver halides such as silver chlorobromide, silver iodobromide, silver chloroiodide and silver chloroiodobromide. Can be applied. These silver halide emulsions are produced by a usual method, and include an ammonia method, a neutral method,
An acid method, a halogen conversion method, a function addition method, a uniform precipitation method, or the like can be applied. Regardless of the average diameter of the particles,
It is preferably from 0.01 to 5 μm. Two or more silver halide emulsions formed separately may be used as a mixture.

The silver halide emulsion used in the present invention is
Chemical sensitization can be performed using a usual method. Chemical sensitization includes a gold sensitization method using a gold complex salt, a reduction sensitization method using a reducing substance, a sulfur-containing compound capable of reacting with silver ions and a so-called sulfur sensitization method using active gelatin, A sensitization method using a salt of a noble metal belonging to Table VIII can be used.

The silver halide emulsion used in the present invention is
Spectral sensitization can be performed. The method can be carried out by using cyanine dyes such as monomethine cyanine, pentamethine cyanine, merocyanine and carbocyanine alone or in combination, or by combining them with a styryl dye or an aminostilbene compound.

The silver halide emulsion used in the present invention includes a stabilizer, an antifoggant, a surfactant, an antifoaming agent, an antistatic agent, a hardener, a film property improving agent, a whitening agent, and a stain inhibitor. ,
Additives such as ultraviolet absorbers and irradiation inhibitors can be included. These various additives are described in Research Disclosure 176
Vol. All those described in 17643 (1978) can be used.

The support of the color photographic light-sensitive material of the present invention comprises
It can be appropriately selected according to the purpose. For example, a cellulose acetate film, a polyethylene terephthalate film, a polystyrene film, a polycarbonate film, or a laminate thereof, paper, baryta paper, α-
Paper, synthetic paper, glass, coated with olefin polymer,
There are metals and the like.

In the above color photographic light-sensitive material, gelatin is advantageously used as a binder or protective colloid, but other hydrophilic colloids such as gelatin derivatives, graft polymers of gelatin with other polymers, hydroxy Ethylcellulose, carboxymethylcellulose, cellulose derivatives such as cellulose sulfates, polyvinyl alcohol, polyvinyl alcohol partial acetal, poly-N-vinylpyrrolidone, polyacrylic acid, polymethacrylic acid, homo- or copolymers such as polyacrylamide Such various kinds of synthetic hydrophilic polymer substances can be used in combination.

[0067]

EXAMPLES Hereinafter, the present invention will be described in detail with reference to examples, but embodiments of the present invention are not limited thereto.

Example 1 Polyethylene laminated on one side of a paper support and polyethylene on the other side laminated with polyethylene containing titanium oxide. On the support, each layer having the following constitution was replaced with a polyethylene layer containing titanium oxide. Was coated on the side of No. 1 to prepare Samples 1 to 16 of a multilayer silver halide color photographic light-sensitive material. The coating solution was prepared as follows.

First layer coating solution 26.7 g of yellow coupler (described in Table 3), 10.0 g of dye image stabilizer (ST-1), 6.67 g of dye image stabilizer (ST-2), additives (HQ-1) 0.67
g, anti-irradiation dye (AI-3) 0.33
g, HBS-1 (DBP) 3.33 g, HBS-2 (D
(BP or polymer of the present invention) (listed in Table 3) Ethyl acetate (60 ml) was added to and dissolved in 3.33 g, and this solution was added to 220 ml of a 10% aqueous gelatin solution containing 7 ml of 20% surfactant (SU-1). The mixture was emulsified and dispersed using an ultrasonic homogenizer to prepare a yellow coupler dispersion. This dispersion was mixed with a blue-sensitive silver halide emulsion (containing 8.68 g of silver) prepared under the following conditions to prepare a first layer coating solution.

The coating liquids for the second to seventh layers were prepared in the same manner as the coating liquid for the first layer.

As a hardening agent, (H) was added to the second and fourth layers.
-1) and (H-2) were added to the seventh layer. Surfactants (SU-2) and (SU-3) were added as coating aids to adjust the surface tension. With regard to the amount of addition of silver halide photographic light-sensitive material is particularly shows the number of grams per 1 m ² unless otherwise noted.

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[Table 1]

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[Table 2]

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(Method for Preparing Blue-Sensitive Silver Halide Emulsion) 4
The following (solution A) and (solution B) were pAg = 6.5 and pH = 3 in 1000 ml of a 2% aqueous gelatin solution kept at 0 ° C.
And added simultaneously over 30 minutes while controlling to 0.
Solution) and (Solution D) were simultaneously added over 180 minutes while controlling pAg = 7.3 and pH = 5.5. The pH was controlled using an aqueous solution of sulfuric acid or sodium hydroxide.
For control of pAg, a control solution having the following composition was used. The composition of the control solution is a mixed halide salt aqueous solution composed of sodium chloride and potassium sulfide, the ratio of chloride ion to bromide ion is 99.8: 0.2, and the concentration of the control solution is
When mixing (Solution A) and (Solution B), 0.1 mol / L is used, and when mixing (Solution C) and (Solution D), 1 mol / L is used.
Liters.

[0082] (A liquid)   3.42 g of sodium chloride   Potassium bromide 0.03g   200 ml with water Finished.

[0083] (B liquid)   Silver nitrate 10g   200 ml with water Finished.

[0084] (Liquid C)   Sodium chloride 102.7g   1.0 g of potassium bromide   600 ml with water Finished.

[0085] (D liquid)   Silver nitrate 300g   600 ml with water Finished.

After the addition is completed, Demol N manufactured by Kao Atlas Co., Ltd.
a Desalting was performed using a 5% aqueous solution and a 2.0% aqueous solution of magnesium sulfate, and then mixed with an aqueous gelatin solution to have an average particle size of 0.85 μm, a coefficient of variation (σ / F) = 0.07, and containing silver chloride. Cubic Emulsion EMP with a Percentage of 99.5 Mole%
-1 was obtained.

The emulsion EMP-1 was chemically ripened at 50 ° C. for 90 minutes using the following compounds to obtain a blue-sensitive silver halide emulsion (Em-B).

Sodium thiosulfate 0.8 mg / mol AgX Chloroauric acid 0.5 mg / mol AgX Stabilizer STAB-1 6 × 10 ⁻⁴ mol / mol AgX Sensitizing dye BS-1 4 × 10 ⁻⁴ mol / mol AgX Sensitizing dye BS-2 1 × 10 ⁻⁴ mol / mol AgX (Preparation method of green-sensitive silver halide emulsion) (solution A) and (B)
Liquid) and the addition time of (liquid C) and (liquid D) in the same manner as in EMP-1 except that the average particle diameter was 0.4.
A monodisperse cubic emulsion EMP-2 having a thickness of 3 μm, a coefficient of variation (σ / F) = 0.08 and a silver chloride content of 99.5 mol% was obtained.

EMP-2 was prepared by using the following compound.
Chemical ripening was performed at 5 ° C. for 120 minutes to obtain a green-sensitive silver halide emulsion (Em-G).

Sodium thiosulfate 1.5 mg / mol AgX chloroauric acid 1.0 mg / mol AgX Stabilizer STAB-1 6 × 10 ⁻⁴ mol / mol AgX Sensitizing dye GS-1 4 × 10 ⁻⁴ mol / mol AgX (Method for Preparing Red-Sensitive Silver Halide Emulsion) (A Solution) and (B)
Liquid) and the addition time of (liquid C) and (liquid D), except that the average particle size was 0.5
A monodispersed cubic emulsion EMP-3 having 0 μm, a coefficient of variation (σ / F) = 0.08, and a silver chloride content of 99.5 mol% was obtained.

EMP-3 was prepared by using the following compound.
Chemical ripening was performed at 0 ° C. for 90 minutes to obtain a red-sensitive silver halide emulsion (Em-R).

Sodium thiosulfate 1.8 mg / mol AgX chloroauric acid 2.0 mg / mol AgX Stabilizer STAB-1 6 × 10 ⁻⁴ mol / mol AgX Sensitizing dye RS-1 1 × 10 ⁻⁴ mol / mol AgX

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(Equation 1)

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The sample thus obtained was evaluated by the following method.

<< Evaluation of Relative Sensitivity and Maximum Density (Dmax) >> Each sample was subjected to gradation exposure for sensitometry for 0.5 seconds through a blue filter, and then subjected to a development process described later. The obtained sample was used as an optical densitometer (PK manufactured by Konica Corporation).
DA-65) to determine the sensitivity (relative sensitivity) and the maximum density (Dmax).

<< Evaluation of Light Resistance >> Each sample was irradiated with a xenon fade meter for 10 days, and then the concentration was measured to examine the light resistance.

The light fastness is represented by the percentage of the dye remaining after the light fastness test with respect to the initial density of 1.0.

<< Evaluation of Processing Variability (Dmax ') >> The obtained sample was exposed to light in the same manner as described above, and thereafter, the CD-D, which is a color developing agent of a color developing solution during the development process described below, was used. The same procedure was followed except that the amount of 3 was changed to 3.5 g / liter, and the maximum density (Dmax ') of the blue-sensitive layer was measured.

<< Evaluation of Color Reproducibility >> Samples 1 and 2
For 0, color reproducibility was evaluated by the following method.

First, a color negative film (Konica Color LV-400: manufactured by Konica Corporation) and a camera (Konica F
T-1 MOTOR (manufactured by Konica Corporation) was used to photograph a Macbeth color checker. Subsequently, color negative development processing (CNK-4: manufactured by Konica Corporation) was performed, and the obtained negative image was converted to a Konica Color Printer CL-P.
Sample No. 2000 (manufactured by Konica Corporation).
Prints were made to a size of 82 mm × 117 mm on Nos. 1 to 20, and practical prints were obtained in the same manner as described above. Printer conditions at the time of printing were set for each sample so that the gray on the color checker became gray on the print.

The obtained practical prints were visually evaluated for color reproducibility.

<< Development >> The processing conditions are as follows.

Processing Step Temperature Time Color development 35.0 ± 0.3 ° C. 45 seconds Bleaching and fixing 35.0 ± 0.5 ° C. 45 seconds Stabilization 30-34 ° C. 90 seconds Drying 60-80 ° C. 60 seconds Color developing solution Pure water 800 ml Triethanolamine 10 g N, N-diethylhydroxylamine 5 g Potassium bromide 0.02 g Potassium chloride 2 g Potassium sulfite 0.3 g 1-Hydroxyethylidene-1,1-diphosphonic acid 1.0 g Ethylenediaminetetraacetic acid 1 0.0 g catechol-3,5-disulfonate disodium salt 1.0 g diethylene glycol 10 g N-ethyl-N-β-methanesulfonamidoethyl-3-methyl-4-aminoaniline sulfate (CD-3) 4.5 g fluorescence Brightener (4,4'-diaminostilbene sulfonic acid derivative) 1.0 g Potassium carbonate 27 g Water To make the total volume 1 liter and adjust to pH = 10.10.

Bleaching / fixing solution Ethylenediaminetetraacetic acid ammonium ferric ammonium dihydrate 60 g Ethylenediaminetetraacetic acid 3 g Ammonium thiosulfate (70% aqueous solution) 100 ml Ammonium sulfite (40% aqueous solution) 27.5 ml Water was added to bring the total volume to 1 liter. Adjust to pH = 5.7 with potassium or glacial acetic acid.

Stabilizing solution 5-chloro-2-methyl-4-isothiazolin-3-one 0.2 g 1,2-benzisothiazolin-3-one 0.3 g ethylene glycol 1.0 g 1-hydroxyethylidene-1,1 -Diphosphonic acid 2.0 g o-phenylphenol sodium 1.0 g ethylenediaminetetraacetic acid 1.0 g ammonium hydroxide (20% aqueous solution) 3.0 g fluorescent brightener (4,4'-diaminostilbenesulfonic acid derivative) 1.5 g The total volume is adjusted to 1 liter by adding water, and the pH is adjusted to 7.0 with sulfuric acid or potassium hydroxide.

Table 3 shows the results.

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[Table 3]

The color reproducibility (hue, saturation) of Sample No. 3 to 3 (poor) 1 to 5 (excellent)

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As is clear from Table 3, the samples using the yellow coupler of the present invention are excellent in color development (sensitivity, maximum density), processing variability and color reproducibility.

Further, it can be seen that light fastness is greatly improved by using the polymer of the present invention in combination.

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According to the present invention, it is possible to provide a silver halide color photographic light-sensitive material which is excellent in color-forming properties, light fastness, color reproducibility and processing variability of the light-sensitive material.

Continuation of the front page (56) References JP-A-7-152127 (JP, A) JP-A-5-72693 (JP, A) JP-A-4-362263 (JP, A) JP-A-4-274235 (JP) JP-A-3-125140 (JP, A) JP-A-5-100384 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) G03C 7/36 G03C 7/00 520 G03C 7/396

Claims (2)

(57) [Claims] 1. A blue-sensitive silver halide emulsion layer on a support,
It has a photographic constituent layer including a green-sensitive silver halide emulsion layer and a red-sensitive silver halide emulsion layer, and the blue-sensitive silver halide emulsion layer has a yellow color represented by the following formula (I) or (II): A silver halide color photographic material comprising at least one coupler. Embedded image Wherein, R ^A and R ^C represents an alkyl group, R ^B represents a branched alkyl group, R ^E and R ^F is each represents a hydrogen atom or an alkyl group. [Chemical formula 2] Wherein, R ^A and R ^C represents an alkyl group, R ^B represents a branched alkyl group, R ^G represents a hydrogen atom or an alkoxy group. ] 2. A blue-sensitive silver halide emulsion layer on a support,
Having photographic constituent layers including a green-sensitive silver halide emulsion layer and red-sensitive silver halide emulsion layer, represented by the following general formula該青sensitive silver halide emulsion layer [I] or formula [II] A silver halide color photograph comprising at least one yellow coupler, and wherein the blue-sensitive silver halide emulsion layer contains at least one water-insoluble and organic solvent-soluble homopolymer or copolymer. Photosensitive material. [A] Wherein R ^A and R ^C represent an alkyl group, and R ^B is a branched
R ^E and R ^F each represent a hydrogen atom or an alkyl
Represents a hydroxyl group. ] [Of B] Wherein R ^A and R ^C represent an alkyl group, and R ^B is a branched
R ^G represents a hydrogen atom or an alkoxy group.
You. ]