JP2933400B2 - Silver halide photographic material - 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 photographic light-sensitive material which has excellent spectral absorption characteristics of dyes formed, excellent color reproducibility, excellent image storability, and a high maximum density. is there.

[0002]

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, unnecessary absorption on the long wavelength side of 500 nm or more is not sharply reduced with respect to a color-forming dye to be formed, so that color reproduction in yellow and green hues is insufficient. Was.

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

[0005] 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 color dye further increases, and the color reproducibility increases. This leads to deterioration, and also tends to deteriorate in light resistance.

For this reason, silver halide photographic materials excellent in color development, color reproducibility and light fastness have not been found yet.

[0007]

A first object of the present invention is to provide a silver halide photographic light-sensitive 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 high color density,
An object of the present invention is to provide a silver halide photographic light-sensitive material capable of obtaining a sufficient maximum density.

[0010]

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- It is necessary that at least one of the yellow couplers represented by the formula (I) contains a dispersion present in lipophilic fine particles in the state of coexistence with at least one of a water-insoluble and organic solvent-soluble homo- or copolymer. Characteristic silver halide photographic material (however, general formula [Y-I]
Is a compound represented by the following Y-1, Y-2 or Y-4, and the water-insoluble and organic solvent-soluble homo- or copolymer is poly (N-t
tert-butyl acrylamide), polycyclohexyl methacrylate-methyl methacrylate copolymer or poly (cyclohexyl methacrylate). General formula [Y-I]

[0011]

Embedded image [Wherein, R _A and R _B represent an alkyl group, a cycloalkyl group, or an aryl group. X _A represents an acylamino group or a sulfonylamino group. Z _A has the general formula [Y-I
And a group capable of leaving by reaction with an oxidized form of the color developing agent represented by [I] or [Y-III]. General formula [Y-II]

[0012]

Embedded image [Wherein, R _C and R _D represent a hydrogen atom or a substituent,
Y represents -N ( _RG )-, -O- or -S (O) p- (wherein, _RG represents a hydrogen atom or a substituent, and p represents an integer from 0 to 2). . General formula [Y-III]

[0013]

Embedded image Wherein R _E and R _F represent a hydrogen atom or a substituent;
W represents -O- or -S (O) _r- . r is from 0 to 2
Represents an integer up to. ]] Y-1 Y-2 Y-3

[0014]

DETAILED DESCRIPTION OF THE INVENTION The yellow coupler represented by the general formula [Y-I] will be described.

The alkyl group represented by R _A and R _B in the general formula [Y-I] includes a linear or branched alkyl group such as a methyl group, an ethyl group, an isopropyl group, a t-butyl group, and a -Dodecyl group, 1-hexylnonyl group and the like. Examples of the cycloalkyl group represented by R _A and R _B include a cyclopropyl group, a cyclohexyl group, and an adamantyl group. The alkyl group and cycloalkyl group represented by R _A and R _B may further have a substituent, for example, a halogen atom (eg, a chlorine atom, a bromine atom, etc.), an aryl group (eg, phenyl Group, p
-T-octylphenyl group, etc.), alkoxy group (eg, methoxy group, etc.), aryloxy group (eg, 2,4-di-t-amylphenoxy group, etc.), sulfonyl group (eg, methanesulfonyl group, etc.), acylamino group ( For example, an acetyl group, a benzoyl group, etc.), a sulfonylamino group (eg, n-dodecanesulfonylamino group, etc.), a hydroxy group and the like can be mentioned.

In the general formula [Y-I], examples of the aryl group represented by R _A and R _B include a phenyl group and a naphthyl group. The aryl group represented by R _A and R _B can further have a substituent,
Examples of the substituent include a halogen atom (eg, a chlorine atom, a bromine atom, etc.), a cyano group, a nitro group, and an alkyl group (eg, a methyl group, a trifluoromethyl group, an isopropyl group, a t-butyl group, and an n-dodecyl group) Etc.), an aryl group (eg, phenyl group, pt-octylphenyl group, etc.), an alkoxy group (eg, methoxy group, etc.), an aryloxy group (eg, 2,4-di-t-amylphenoxy group, etc.), a sulfonyl group (For example, an alkylsulfonyl group such as a methanesulfonyl group and a trifluoromethanesulfonyl group, and an arylsulfonyl group such as a p-toluenesulfonyl group), an acylamino group (for example, an alkylcarbonylamino group such as an acetylamino group and a myristoylamino group, and a benzoylamino group) Arylcarbonylamino group), sulfonylua (E.g., an alkylsulfonylamino group such as a methanesulfonylamino group, a heptafluoropropanesulfonylamino group, an n-hexadecylsulfonylamino group, an arylsulfonylamino group such as a p-toluenesulfonyl group and pentafluorobenzenesulfonylamino), and And a hydroxy group.

R _A is preferably an alkyl group, more preferably a branched alkyl group, and particularly preferably a t-butyl group.

[0018] R _B is preferably an alkyl group, a methyl group is particularly preferred.

In the general formula [Y-I], X _A is an acylamino group or a sulfonylamino group, and more preferably, groups represented by the following general formulas [A] to [F].

[0020]

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In the general formulas [A] to [F], R _K represents an alkyl group, a cycloalkyl group or an aryl group;
_L and R _N independently represent a hydrogen atom, an alkyl group, a cycloalkyl group or an aryl group. R _M represents an unsubstituted alkyl group or cycloalkyl group.

Examples of the alkyl group and cycloalkyl group represented by R _K , R _L , R _M and R _N include, for example,
Examples include the groups having the same meanings as the alkyl group and cycloalkyl group represented by _A and R _B. Of these, R _K ,
R _L, and alkyl and cycloalkyl groups represented by R _N may also have a substituent, and examples of the substituent include, alkyl and cycloalkyl groups represented by the above R _A and R _B Substituents having the same meanings as the groups mentioned as the substituents can be exemplified.

The aryl group represented by R _K , R _L , and R _N includes, for example, the same groups as the aryl groups represented by R _A and R _B. These R _K ,
The aryl group represented by R _L and R _N may further have a substituent. Examples of the substituent include the above-mentioned R _A.
And the same substituents as the groups exemplified as the substituents of the aryl group represented by R _B.

R _M is preferably an alkyl group, more preferably a branched alkyl group.

In the above general formulas [C] and [D],
L represents a divalent linking group selected from an alkylene group and an arylene group. The alkylene group represented by L includes a cycloalkylene group, for example, a methylene group, 1,2-
Linear alkylene group such as ethylene group, 1,3-propylene group, or 1,4-butylene group, 1,1-propylene group (ethylmethylene group), 2,3-propylene group (1-methyl-1 , 2-ethylene group) or 2,2-
Examples include a branched alkylene group such as a propylene group (dimethylmethylene group) or a 1,2-cyclohexylene group. Further, these alkylene groups may further have a substituent, and examples of the substituent include the above-mentioned R _A.
And substituents as defined for the substituents of the alkyl group and the cycloalkyl group represented by R _B.

Examples of the arylene group represented by L include an arylene group having 6 to 14 carbon atoms.
2-phenylene group, 1,4-phenylene group, and 1,
4-naphthylene group and the like. These arylene groups may further have a substituent. Examples of the substituent include a substituent having the same meaning as the above-mentioned group for the aryl group represented by R _A and R _B. Can be mentioned.

L is preferably an alkylene group, and a linear or branched alkylene group having 1 to 4 carbon atoms in the linking portion (for example, 1,3-propylene group, 1,1-propylene group, or 1,1 -Pentylene group etc.) are more preferred.

In the general formula [C], B represents a group that can be substituted on a benzene ring, and examples thereof include an alkyl group, a cycloalkyl group, and an aryl group as defined for the groups represented by R _A and R _B. Can be A halogen atom (eg, a chlorine atom, a bromine atom, etc.), a cyano group, a nitro group, a hydroxy group, an alkoxy group (eg, a methoxy group), an aryloxy group (eg, a 2,4-di-t-amylphenoxy group) An acyloxy group (eg, methylcarbonyloxy group, benzoyloxy group, etc.), an alkylsulfonyl group (eg, methanesulfonyl group, etc.), an arylsulfonyl group (eg, benzenesulfonyl group, p-toluenesulfonyl group, etc.), a sulfamoyl group (eg, N- Propylsulfamoyl group, N-phenylsulfamoyl group, etc.), acylamino group (eg, acetyl group, benzoyl group, 3- (2,4-di-t-amylphenoxy) butyroyl group, etc.), alkylsulfonylamino group ( For example, methanesulfonylamino group, dodecanesulfonylamino An arylsulfonylamino group (eg, benzenesulfonylamino group), a carbamoyl group (eg, N-methylcarbamoyl group, N-phenylcarbamoyl group, etc.), an alkoxycarbonyl group (eg, methoxycarbonyl group, dodecyloxycarbonyl group, etc.), An aryloxycarbonyl group (for example, a phenoxycarbonyl group) and an imide group (for example, a succinimide group) are also included. n represents the integer of 0-3.

The group which can be substituted on the benzene ring represented by B is preferably an alkyl group or a hydroxy group, and the alkyl group is more preferably a branched alkyl group such as a t-amyl group or a t-octyl group.

The substituents represented by R _C and R _D in the above general formula [Y-II] include, for example, R _A and R
Examples of the group include the same as the alkyl group, cycloalkyl group, and aryl group represented by _B. These R
An alkyl group represented by _C and _RD , a cycloalkyl group,
And the aryl group may have a substituent. Examples of the substituent include the same as those described above as the substituent of the alkyl group, the cycloalkyl group, and the aryl group represented by R _A and R _B. Can be mentioned. Further, examples of the substituent represented by R _C and R _D in the general formula [Y-II] include, for example, an alkoxy group, an aryloxy group, an alkylamino group, an anilino group, an alkylsulfonyl group, and an arylsulfonyl group. And a substituent linked by a hetero atom. The substituents linked by these hetero atoms may further have a substituent, and examples of the substituent include the alkyl, cycloalkyl, and aryl groups represented by R _A and R _B described above. And the same substituents as those described above.

R _C is preferably a substituted or unsubstituted alkyl group.

R _D is preferably an alkyl group, more preferably an alkyl group having 1 to 6 carbon atoms.

In the above general formula [Y-II], Y is -N
( _RG )-, -O-, and -S (O) p-, preferably -O-. p represents an integer from 0 to 2.

In the above general formula [Y-II], RG
Examples of the substituent include, for example, R _CAnd R_DSynonymous with
Substituents can be mentioned. Also R_GIs a further substituent
And the substituent may be, for example, the above-mentioned R
_AAnd R_BRepresented by an alkyl group, a cycloalkyl group,
And the same groups as the substituents of the aryl group
Substituents having the same meanings can be mentioned.

R _G is preferably a hydrogen atom or an alkyl group. When R _G is an alkyl group, R _G may be bonded to R _D to form a ring structure.

The substituent represented by R _E and R _F in the above general formula [Y-III] includes, for example, the above general formula [Y
-II], the same substituents as R _C and R _D can be mentioned. Further, R _E and R _F may further have a substituent, and examples of the substituent include the substituents of the alkyl group, cycloalkyl group, and aryl group represented by R _A and R _B described above. Substituents which have the same meanings as those described above. R _E and R _F may be the same or different from each other, and may be further bonded to each other to form a ring structure.

As R _E and R _F , an aryl group and an alkyl group are preferable, and an alkyl group is particularly preferable.

In the above general formula [Y-III], W is-
Represents O- and -S (O) r-, preferably -O-. r represents an integer from 0 to 2.

The 2-equivalent yellow coupler represented by the above general formula [Y-I] may be bonded at any substituent to form a bis form.

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 kinds, and can be used in combination with another kind of yellow coupler. it can.

The yellow coupler according to the present invention is 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. Can be used.

Next, the general formula [Y-
Specific examples of the 2-equivalent yellow coupler represented by I] are shown below, but the present invention is not limited thereto.

[0044]

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[0045]

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[0046]

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[0047]

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[0048]

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The yellow coupler of the present invention represented by the general formula [Y-I] can be easily synthesized by a conventionally known method. Hereinafter, typical synthesis examples of the present invention will be described. Synthesis Example; Synthesis of Illustrative Coupler (1)

[0050]

Embedded image (1) Synthesis of 4-equivalent coupler (A) 13.2 g of α-pivaloyl-2-methoxy-5-aminoacetanilide was dissolved in 50 ml of ethyl acetate, and 50 ml of water was dissolved.
And 2.65 g of sodium carbonate, and the mixture was stirred vigorously. Here 2- (2,4-di-t-amylphenoxy)
A solution of 17.8 g of butyric chloride in 25 ml of ethyl acetate was added dropwise. After completion of the dropwise addition, the mixture was stirred at room temperature for 1 hour, and the organic layer was washed with a 5% aqueous potassium carbonate solution and dilute hydrochloric acid. After dehydration with magnesium sulfate, the solvent was removed under reduced pressure,
The residue was recrystallized from 100 ml of methanol to obtain the desired 4-equivalent coupler (A). Yield 24.1 g (yield 8
(2) Synthesis of Coupler (1) 24.1 g of the 4-equivalent coupler (A) obtained above was dissolved in 100 ml of chloroform, and 6.3 g of sulfuryl chloride was added dropwise under ice cooling. After dropping, stir for 1 hour,
The reaction solution was washed with water, dehydrated with magnesium sulfate, and the solvent was removed under reduced pressure.

The obtained residue was dissolved in 150 ml of acetone, and 3-benzyl-4-ethoxyhydantoin 1 was added thereto.
3.0 g and 7.6 g of potassium carbonate were added, and the mixture was heated under reflux for 3 hours. After filtering off insolubles, the mixture was washed with a 5% aqueous potassium carbonate solution and dilute hydrochloric acid. After dehydration with magnesium sulfate,
The solvent was removed under reduced pressure, and the residue was recrystallized from 100 ml of methanol to obtain the desired exemplified coupler (1). Yield 19.1 g (56% yield).

The structure of the exemplified coupler (1) is represented by NMR, I
It was confirmed by R and mass spectrum.

Exemplified couplers other than the exemplified coupler (1) were synthesized according to the above synthesis examples, starting from the corresponding raw materials.

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 are 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.

Acrylic esters: 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, 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-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 DOO, 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, 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-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-butylacrylamide, cyclohexylacrylamide, benzylacrylamide, hydroxymethylacrylamide, methoxyethylacrylamide, dimethylaminoethylacrylamide, phenylacrylamide, dimethylacrylamide, diethylacrylamide, β-cyanoethylacrylamide, N- (2-acetate Acetoxyethyl) acrylamide, diase Emissions acrylamide; methacrylamide: Tatoeba, 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-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; .

The following are examples of other monomers.

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, methoxy Ethyl vinyl ketone; vinyl heterocyclic compound: for example, vinyl pyridine, N-vinyl imidazole, N-vinyl oxazolidone, N-vinyl triazole, N-vinyl pyrrolidone; glycidyl esters: for example, glycidyl acryle
And glycidyl methacrylate; unsaturated nitriles: for example, acrylonitrile and methacrylonitrile;

The polymer used in the present invention may be a homopolymer of the above-mentioned monomers or, if necessary, a copolymer composed 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 (for example, monomethyl itaconate); monoalkyl maleate (for example, monomethyl maleate); Acids; Styrenesulfonic acid; Vinylbenzylsulfonic acid; Acryloyloxyalkylsulfonic acid (eg, acryloyloxymethylsulfonic acid); Methacryloyloxyalkylsulfonic acid (eg, methacryloyloxymethylsulfonic acid, methacryloyloxyethylsulfonic acid, methacryloyloxypropylsulfone) Acid); acrylamidoalkylsulfonic acid (eg, 2-acrylamido-2-methylethanesulfonic acid, 2-acrylamido-2-methylpropanesulfonic acid, 2-acrylic acid) Methacrylamidoalkylsulfonic acid (for example, 2-methacrylamido-2-methylethanesulfonic acid, 2-methacrylamido-2-methylpropanesulfonic acid, 2-methacrylamido-2-methyl) Butanesulfonic acid); acryloyloxyalkyl phosphate (eg, acryloyloxyethyl phosphate, 3
-Acryloyloxypropyl-2-phosphate);
Methacryloyloxyalkyl phosphate (for example,
Methacryloyloxyethyl phosphate, 3-methacryloyloxypropyl-2-phosphate) and the like.

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

The monomers forming the polymer used in the present invention are preferably acrylate, methacrylate, acrylamide and methacrylamide.

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-4cyanovalerate, and 2,2'-azobis (2 Water-soluble azo compounds such as (amidinopropane) hydrochloride, and hydrogen peroxide.

As the lipophilic polymerization initiator, for example, azobisisobutyronitrile, 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 As the polyhydric alcohol, HO-R ₁ -OH (R ₁ is a hydrocarbon having 2 to about 12 carbon atoms, particularly an aliphatic hydrocarbon) Hydrogens)
Glycols or polyalkylene glycols having the following structure are effective, and as the polybasic acid, HOOC
Those having —R ₂ —COOH (R ₂ represents a mere 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, and sorbit.

Specific examples of polybasic acids 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) Polyesters obtained by ring-opening polymerization These polyesters are β-propiolactone, ε-
It can be 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 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 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) Acetic acid Vinyl-acrylamide Polymer (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: 4)
0) 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 copolymer (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-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-sebacate polyester P-71) polycaprolactam P-72) polypropiolactam P-73) polydimethylpropiolactone P-74) N-tert- Butylacrylamide-dimethylaminoethylacrylamide copolymer (85: 1
5) 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, at least one of the yellow couplers represented by the above general formula [Y-I], which forms a dye by coupling with an oxidized aromatic primary amine developing agent, is water-insoluble. The dispersion which is present in the lipophilic fine particles in the state of coexisting with at least one kind of an organic solvent-soluble homopolymer or copolymer substantially comprises the coupler and at least one of the homopolymer or the copolymer. It is obtained by dissolving in a water-insoluble high boiling organic solvent and emulsifying and dispersing 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 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 U.S. Pat. Nos. 2,322,027,
No. 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. 3,554,75
No. 5, 3,676,137 and 3,676,1
No. 42, No. 3,700,454, No. 3,748,
No. 141, 3,779,765 and 3,8
No. 37,863.

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 above-mentioned organic solvents can be used in combination of two or more kinds.

To obtain lipophilic fine particles by emulsifying and dispersing in a hydrophilic protective colloid, a dispersing aid such as a surfactant is used and a stirrer, a homogenizer, a colloid mill, a flow jet mixer, an ultrasonic device or the like is used. 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
μ to 2 μ is preferred, and more preferably 0.06 μ to 0.4 μ. The particle diameter can be measured by Coulter Model N4 manufactured by Coulter, UK.

In the present invention, the mixing ratio of the coupler, the homo- or copolymer, the high-boiling solvent and the co-solvent such as the low-boiling solvent or the water-miscible organic solvent is determined by the amount of the coupler, homo- or copolymer, high-boiling solvent May be selected so as to have a viscosity suitable for easily dispersing a solution obtained by dissolving in a hydrophilic solvent into a hydrophilic colloid. The value at this time depends on the solubility of the coupler used, the type and the degree of polymerization of the polymer, and cannot be determined uniformly. For example, the ratio (weight ratio) of the polymer to the coupler 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: 1.
10 to 2: 1. The ratio (weight ratio) of the low boiling point solvent to the polymer is 1:10 to 10: 1, preferably 1: 4 to
5: 1.

In the present invention, the above general formula [Y-I]
A dispersion in which at least one of the yellow couplers represented by the formula (I) is present in the lipophilic fine particles in the state of coexisting with a water-insoluble and organic solvent-soluble homo- or copolymer, is a blue-sensitive silver halide emulsion. Preferably, it is added to the layer.

In the dispersion, compounds which do not need to be adsorbed on the silver halide crystal surface, such as image stabilizers, color fogging inhibitors, ultraviolet absorbers, fluorescent brighteners, oil-soluble dyes, etc., are simultaneously contained. It can be dispersed.

JP-A-59-125732 and 62
It is preferable to simultaneously disperse the image stabilizer described in JP-A-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 provided for direct viewing. The effect of the present invention is effectively exhibited.

The silver halide photographic light-sensitive material of the present invention such as the color photographic paper may be of a single color or of 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 layers have 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 layers may be appropriately changed depending on the priority performance and the purpose of use.

The magenta dye image forming couplers usable in the present invention include 4-pyrazolone, pyrazoloazole, pyrazolinobenzimidazole, indazolone and cyanoacetyl 4- or 2-equivalent magenta dye images. Forming couplers, which are
For example, U.S. Pat. Nos. 2,600,788 and 3,062
1,432, 3,062,653, 3,12
7,269, 3,152,896, 3,31
Nos. 1,476, 3,419,391, 3,51
9,429, 3,558,318, 3,68
4,514, 3,705,896 and 3,88
8,680, 3,907,571, 3,92
8,044, 3,930,861, 3,93
Nos. 0,816 and 3,933,500,
Nos. 29639, 49-111631, and 49-12
Nos. 9538, 51-112341, 52-589
No. 22, No. 55-62454, No. 55-118034
No. 56-38643, No. 56-135841,
JP-B-46-60479, JP-B-52-34937, JP-B-55-29421, JP-A-55-35696, British Patent No. 1,247,493, Belgian Patent 792,52
No. 5, West German Patent No. 2,156,111.

As the cyan coupler which can be used in the present invention, a phenolic compound, a naphthol compound and the like can be used. Specific examples thereof include U.S. Pat. Nos. 2,369,929, 2,434,272, 2,474,293, 2,521,908, 2,895,826, and 3, Nos. 034,892, 3,311,476, 3,458,315, 3,476,563, 3,583,971, 3,591,383, 3,767, Nos. 411 and 4,004,929, West German Patent Application (OLS) 2,4
No. 14,830, No. 2,454,329, JP-A-48
-59838, 51-26034, 48-50
No. 55, No. 51-146828, No. 52-69624
And No. 52-90932.

The silver halide emulsion used in the silver halide photographic light-sensitive material of the present invention (hereinafter referred to as silver halide emulsion of the present invention) includes silver bromide, silver iodobromide, iodochloride as silver halide. Any of silver, silver chlorobromide, silver chloride and the like used in usual silver halide emulsions 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
Color antifoggant, hardener, plasticizer, polymer latex, ultraviolet absorber, formalin scavenger, mordant, development accelerator, development retarder, fluorescent brightener, matting agent,
A lubricant, an antistatic agent, a surfactant 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.

[0094]

EXAMPLES Specific examples of the present invention will be described below, but the embodiments of the present invention are not limited to these examples. Example 1 (Preparation 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.

[0095]

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

[0096]

Embedded image

(Preparation of silver halide color photographic light-sensitive material sample) Next, the following layers 1 to 7 were successively coated (simultaneously coated) on a paper support coated on both sides with polyethylene, and the silver halide color photographic light-sensitive material was prepared. 1 was produced. (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: gelatin (1.2 g) and 0.29 g (in terms of silver;
The same applies hereinafter) to a blue-sensitive silver halide emulsion (Em-1), 1.0 mmol of a comparative yellow coupler (YA) and 0.015 g of 2,5-dioctylhydroquinone (H
A layer containing 0.3 g of DOP (dioctyl phthalate) in which Q-1) is dissolved.

Layer 2: Gelatin (0.9 g) and 0.04
A layer containing 0.2 g of DOP dissolved in 0.2 g of HQ-1.

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

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

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

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

Layer 7: Gelatin (1.0 g), 0.0
A layer containing 5 g of sodium 2,4-dichloro-6-hydroxytriazine.

[0104]

Embedded image

[0105]

Embedded image

Further, 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 of the above-mentioned layer constitution are shown in Table 2, and the silver halide is shown in Table 2. Photosensitive materials (Nos. 2 to 17) were prepared.

[0107]

[Table 2]

The obtained sample was exposed to a wedge using a sensitometer KS-7 (manufactured by Konica Corporation), processed according to the following color development process, and then subjected to an optical densitometer (PDA-manufactured by Konica Corporation). 65 type), the maximum density (Dmax) of the blue-sensitive emulsion layer was measured.

The maximum absorption wavelength λmax when the density of the yellow dye image is 1.0, and the wavelength 50 at that time.
Concentration was measured D _G at 0 nm.

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.

Table 3 shows the results. [Color developing solution] Pure water 800 ml Triethanolamine 8 g N, N-diethylhydroxyamine 5 g Potassium chloride 2 g N-ethyl-N-β-methanesulfonamidoethyl-3-methyl-4-aminoaniline sulfate 5 g Tetrapolyphosphoric acid Sodium 2 g Potassium carbonate 30 g Potassium sulfite 0.2 g Fluorescent whitening agent (4,4'-diaminostilbene disulfonic acid derivative) 1 g Pure water is added to adjust the total volume to 1 liter, and the pH is adjusted to 10.05. [Bleach-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. And water to make a total volume of 1 liter. [Stabilizing solution] 5-chloro-2-methyl-4-isothiazolin-3-one 1 g 1-hydroxyethylidene-1,1-diphosphonic acid 2 g Water was added to make 1 liter, and the pH was adjusted to 7 with sulfuric acid or potassium hydroxide. Adjust to zero.

[0112]

[Table 3]

As is clear from Table 3, Sample Nos. 5 to 1 using the yellow coupler of the present invention and the polymer of the present invention were used.
7 is good coloring property, excellent color reproducibility because the D _G has decreased, it can be seen that the further light resistance is significantly improved.

[0114]

According to 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. Further, the image storability of the yellow dye can be further improved, the coloring property is high, and a sufficient maximum density can be obtained.

──────────────────────────────────────────────────の Continuation of the front page (72) Inventor Yoko Nagaoka 1 Sakuracho, Hino-shi, Tokyo Konica Corporation (56) References JP-A-3-209463 (JP, A) (58) Fields surveyed ( Int.Cl. ⁶ , DB name) G03C 7/36 G03C 7/392

Claims (1)

(57) [Claims] 1. A silver halide photographic material having at least one silver halide emulsion layer on a support,
In the silver halide emulsion layer, at least one of yellow couplers represented by the following general formula [Y-I] coexists with at least one of a water-insoluble and organic solvent-soluble homo- or copolymer, and A silver halide photographic material comprising a dispersion present in oily fine particles. However, the yellow coupler represented by the general formula [Y-I] is a compound represented by the following Y-1, Y-2 or Y-4, and the water-insoluble and organic solvent-soluble homo- or copolymer is a polyether. (N-tert-butylacrylamide), polycyclohexyl methacrylate-methyl methacrylate copolymer or poly (cyclohexyl methacrylate). General formula [Y-I] [Wherein, R _A and R _B represent an alkyl group, a cycloalkyl group, or an aryl group. X _A represents an acylamino group or a sulfonylamino group. Z _A has the general formula [Y-I
And a group capable of leaving by reaction with an oxidized form of the color developing agent represented by [I] or [Y-III]. General formula [Y-II] [Wherein, R _C and R _D represent a hydrogen atom or a substituent,
Y represents -N ( _RG )-, -O- or -S (O) _p- (wherein, _RG represents a hydrogen atom or a substituent, and p represents an integer from 0 to 2). . General formula [Y-III] Wherein R _E and R _F represent a hydrogen atom or a substituent;
W represents -O- or -S (O) _r- . r is from 0 to 2
Represents an integer up to. ]] Y-1 Y-2 Y-3