JPH04261532A - Silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To improve color reproduction performance in forming a yellow dye image by incorporating a dispersion containing fine lipophilic grains in a silver halide emulsion in the presence of a specified yellow coupler together with a water-insoluble homo- or copolymer soluble in organic solvents. CONSTITUTION:The silver halide emulsion contains a dispersion containing the fine lipophilic grains in the presence of the water-insoluble homo- or copolymer soluble in organic solvents together with at least one of the yellow couplers represented by formula I in which each of RA and RB is alkyl, cycloalkyl, or aryl: XA is acylamino or sulfornylamino; and ZA is a group to be released by coupling with the oxidation product of the color developing agent.

Description

[Detailed description of the invention]

0001

[Field of Industrial Application] The present invention relates to a silver halide photographic material that has good spectral absorption characteristics of the dye formed, excellent color reproducibility, excellent image storage stability, and high maximum density. be.

0002

BACKGROUND OF THE INVENTION In recent years, there has been an increasing demand from users for improved color reproducibility in order to faithfully reproduce the original colors of objects.

[0003] For example, in the case of a yellow coupler, unnecessary absorption in the long wavelength side of 500 nm or more is not sharply reduced with respect to the coloring dye formed, so it has the disadvantage 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, there has been a demand for improved color development in recent years, and for this purpose, various studies have been attempted on the design of coupler molecules for yellow couplers. For example, it has been proposed to improve color development by introducing hydrophilic groups such as alkoxycarbonyl groups, sulfonyl groups, N-substituted or unsubstituted alkylsulfonamide groups, and arylsulfonamide groups into the ballast component. .

[0005] However, when such a hydrophilic group is introduced into the ballast component of a yellow coupler, coloring properties are generally improved, but unnecessary absorption on the long wavelength side of the coloring dye further increases, resulting in poor color reproducibility. This will lead to deterioration, and there is also a tendency for light resistance to deteriorate.

For this reason, the reality is that a silver halide photographic material excellent in color development, color reproducibility and light fastness has not yet been found.

[0007]

OBJECTS OF THE INVENTION The first object of the present invention is to provide a silver halide photographic material with improved color reproducibility that forms a yellow dye image of excellent hue in which absorption on the long wavelength side is sharply reduced. There is a particular thing.

[0008] A second object of the present invention is to provide a silver halide photographic light-sensitive material with excellent preservability of yellow dye images.

A third object of the present invention is to have high color density;
The object of the present invention is to provide a silver halide photographic material that can provide a sufficient maximum density.

0010

SUMMARY OF THE INVENTION The above object of the present invention is to provide a silver halide photographic material having at least one silver halide emulsion layer on a support, in which the silver halide emulsion layer has the following general formula {Y- A dispersion in which at least one yellow coupler represented by I] is present in lipophilic fine particles in coexistence with at least one water-insoluble and organic solvent-soluble single or copolymer. This can be achieved using a silver halide photographic material with special characteristics. General formula [Y-I]

[0011]

embedded image [In the formula, RA and RB represent an alkyl group, a cycloalkyl group, or an aryl group. XA represents an acylamino group or a sulfonylamino group. ZA has the general formula [Y-I
I] and [Y-III] represent a group that can be separated by reaction with an oxidized product of a color developing agent. General formula [Y-II]

0012

[In the formula, RC and RD represent a hydrogen atom or a substituent, Y represents -N(RG)-, -O-, or -S(O)p- (wherein, RG is a hydrogen atom or represents a substituent, p is 0
Represents an integer from to 2. ). ] General formula [Y-III]

[0013]

embedded image [In the formula, RE and RF represent a hydrogen atom or a substituent, and W represents -O- or -S(O)r-. r represents an integer from 0 to 2. ]]

[0014]

[Specific constitution of the present invention] The yellow coupler represented by the general formula [Y-I] will be explained.

In the general formula [Y-I], RA and RB
Examples of the alkyl group represented by include linear or branched alkyl groups, such as methyl group, ethyl group, isopropyl group, t-butyl group, n-dodecyl group, and 1-hexylnonyl group. In addition, the cycloalkyl group represented by RA and RB includes a cyclopropyl group,
Examples include cyclohexyl group and adamantyl group. The alkyl group and cycloalkyl group represented by these RA and RB can further have a substituent,
Examples of substituents include halogen atoms (e.g. chlorine atom, bromine atom, etc.), aryl groups (e.g. phenyl group, p
-t-octylphenyl group, etc.), alkoxy group (e.g., methoxy group, etc.), aryloxy group (e.g., 2,4-di-t-amylphenoxy group, etc.), sulfonyl group (e.g., methanesulfonyl group, etc.), acylamino group ( Examples include an acetyl group, a benzoyl group, etc.), a sulfonylamino group (eg, n-dodecanesulfonylamino group, etc.), and a hydroxy group.

The aryl group represented by RA and RB in the above general formula [Y-I] includes a phenyl group and a naphthyl group. These aryl groups represented by RA and RB can further have a substituent, and examples of the substituent include a halogen atom (e.g., chlorine atom, bromine atom, etc.), a cyano group, a nitro group, an alkyl group (e.g., methyl group, trifluoromethyl group, isopropyl group, t-butyl group, n-dodecyl group, etc.), aryl group (e.g. phenyl group, pt-octylphenyl group, etc.), alkoxy group (e.g. methoxy group, etc.), aryl group Oxy group (e.g. 2,4-di-t-amylphenoxy group etc.), sulfonyl group (e.g. alkylsulfonyl group such as methanesulfonyl group, trifluoromethanesulfonyl group, and arylsulfonyl group such as p-toluenesulfonyl group), acylamino groups (e.g. acetylamino groups, alkylcarbonylamino groups such as myristoylamino groups, arylcarbonylamino groups such as benzoylamino groups), sulfonylamino groups (e.g. methanesulfonylamino groups, heptafluoropropanesulfonylamino groups,
Examples include alkylsulfonylamino groups such as n-hexadecylsulfonylamino groups, p-toluenesulfonyl groups, arylsulfonylamino groups such as pentafluorobenzenesulfonylamino), and hydroxy groups.

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

RB is preferably an alkyl group, with methyl being particularly preferred.

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

[0020]

[C7]

In the general formulas [A] to [F], RK represents an alkyl group, a cycloalkyl group, or an aryl group;
L and RN independently represent a hydrogen atom, an alkyl group,
Represents a cycloalkyl group or an aryl group. RM represents an unsubstituted alkyl group or cycloalkyl group.

Examples of the alkyl group and cycloalkyl group represented by RK, RL, RM, and RN include the same groups as the alkyl group and cycloalkyl group represented by RA and RB above. this house,
The alkyl group and cycloalkyl group represented by RK, RL, and RN can further have a substituent, and examples of the substituent include the substituents of the alkyl group and cycloalkyl group represented by RA and RB above. Substituents having the same meaning as the groups listed as can be mentioned.

[0023] Examples of the aryl groups represented by RK, RL, and RN include the same groups as the aryl groups represented by RA and RB above. These RK
The aryl group represented by , RL, and RN can further have a substituent, and examples of the substituent include the same groups as those listed as substituents for the aryl groups represented by RA and RB above. Substituents can be mentioned.

RM 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 alkylene groups and arylene groups. The alkylene group represented by L includes a cycloalkylene group, such as a methylene group, a 1,2-
Straight chain alkylene groups 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), a branched alkylene group such as 2,2-propylene group (dimethylmethylene group), or a 1,2-cyclohexylene group. In addition, these alkylene groups may further have a substituent, and examples of the substituent include the same groups as those listed as substituents for the alkyl group and cycloalkyl group represented by RA and RB above. The following substituents can be mentioned.

The arylene group represented by L includes arylene groups having 6 to 14 carbon atoms, such as 1,
2-phenylene group, 1,4-phenylene group, and 1,
Examples include 4-naphthylene group. These arylene groups may further have a substituent, and examples of the substituent include the same substituents as those listed as substituents for the aryl groups represented by RA and RB above. Can be done.

[0027] L is preferably an alkylene group, and the connecting moiety is a linear or branched alkylene group having 1 to 4 carbon atoms (for example, a 1,3-propylene group, a 1,1-propylene group, or a 1,1-propylene group). -pentylene group, etc.) are more preferred.

In the above general formula [C], B represents a group that can be substituted on the benzene ring, and examples thereof include an alkyl group, a cycloalkyl group, and an aryl group having the same definitions as the groups represented by RA and RB above. Also, halogen atoms (e.g. chlorine atom, bromine atom, etc.), cyano group, nitro group, hydroxy group, alkoxy group (e.g. methoxy group, etc.), aryloxy group (e.g. 2,4-di-t-amylphenoxy group, etc.) , acyloxy group (e.g. methylcarbonyloxy group, benzoyloxy group, etc.), alkylsulfonyl group (e.g. methanesulfonyl group, etc.), arylsulfonyl group (e.g. benzenesulfonyl group, p-toluenesulfonyl group, etc.), sulfamoyl group (e.g. N- propylsulfamoyl group, N-phenylsulfamoyl group, etc.), acylamino group (e.g. acetyl group, benzoyl group, 3-(2,4-di-t-amylphenoxy)butyroyl group, etc.), alkylsulfonylamino group ( For example, methanesulfonylamino group, dodecanesulfonylamino group, etc.)
, arylsulfonylamino group (e.g. benzenesulfonylamino group, etc.), carbamoyl group (e.g. N-methylcarbamoyl group, N-phenylcarbamoyl group, etc.), alkoxycarbonyl group (e.g. methoxycarbonyl group,
dodecyloxycarbonyl group, etc.), aryloxycarbonyl group (eg, phenoxycarbonyl group, etc.), and imide group (eg, succinimide group, etc.). n represents an integer of 0 to 3.

The group substituted for 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.

Examples of the substituents represented by RC and RD in the general formula [Y-II] include the same groups as the alkyl group, cycloalkyl group, and aryl group represented by RA and RB above. Can be done. The alkyl group, cycloalkyl group, and aryl group represented by these RC and RD can also have a substituent,
Examples of the substituent include the same substituents as those listed as substituents for the alkyl group, cycloalkyl group, and aryl group represented by RA and RB above. Furthermore, the substituents represented by RC and RD in the above general formula [Y-II] include, for example, a hetero group such as an alkoxy group, an aryloxy group, an alkylamino group, an anilino group, an alkylsulfonyl group, and an arylsulfonyl group. Substituents linked by atoms can also be mentioned. The substituents connected through these heteroatoms can also have a substituent, and examples of the substituents include those listed as substituents for the alkyl group, cycloalkyl group, and aryl group represented by RA and RB above. Substituents having the same meanings as the groups mentioned above can be mentioned.

RC is preferably a substituted or unsubstituted alkyl group.

RD 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 -
represents N(RG)-, -O-, and -S(O)p-,
Preferably it is -O-. p represents an integer from 0 to 2.

Examples of the substituent represented by RG in the above general formula [Y-II] include the same substituents as the above RC and RD. In addition, RG can further have a substituent, and examples of the substituent include the same substituents as those listed as substituents for the alkyl group, cycloalkyl group, and aryl group represented by RA and RB above. The following groups can be mentioned.

RG is preferably a hydrogen atom or an alkyl group, and when RG is an alkyl group, it may be bonded to RD to form a ring structure.

Examples of the substituents represented by RE and RF in the above general formula [Y-III] include the same substituents as RC and RD in the above general formula [Y-II]. Moreover, RE and RF can further have a substituent, and examples of the substituent include the same groups as those listed as substituents for the alkyl group, cycloalkyl group, and aryl group represented by RA and RB above. The following substituents can be mentioned. RE and RF
may be the same or different, and may also be bonded to each other to form a ring structure.

As RE and RF, aryl groups and alkyl groups are preferred, and alkyl groups are particularly preferred.

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

The two-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.

Further, 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 also be used in combination with another type of yellow coupler. can.

The yellow coupler according to the present invention is usually used in an amount of about 1 x 10-3 mol to about 1 mol, preferably 1 x 10-2 mol to 8 x 10-1 mol, per mol of silver halide. Can be used.

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

[0044]

[Chemical formula 8]

[0045]

[Chemical formula 9]

[0046]

[Chemical formula 10]

[0047]

[Chemical formula 11]

[0048]

[Chemical formula 12]

The yellow coupler of the present invention represented by the general formula [Y-I] can be easily synthesized by conventionally known methods. Typical synthesis examples of the present invention are shown below. Synthesis example; synthesis of exemplary coupler (1)

[0050]

(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.
ml and 2.65 g of sodium carbonate were added and stirred vigorously. A solution of 17.8 g of 2-(2,4-di-t-amylphenoxy)butyric acid chloride dissolved in 25 ml of ethyl acetate was added dropwise thereto. After the addition was completed, the mixture was stirred at room temperature for 1 hour, and the organic layer was washed with a 5% aqueous potassium carbonate solution and diluted 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 4-equivalent coupler (A). Yield: 24.1 g (yield: 85%) (2) Synthesis of exemplary 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 under ice cooling. was dripped. After the dropwise addition, the mixture was stirred for 1 hour, and 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, 13.0 g of 3-benzyl-4-ethoxyhydantoin and 7.6 g of potassium carbonate were added thereto, and the mixture was heated under reflux for 3 hours. After filtering out insoluble matter, the mixture was washed with 5% aqueous potassium carbonate solution and diluted hydrochloric acid. After dehydration over magnesium sulfate, the solvent was removed under reduced pressure, and the residue was recrystallized from 100 ml of methanol to obtain the desired exemplary coupler (1). Yield: 19.1 g (yield: 56%).

The structure of exemplary coupler (1) is shown by NMR, I
Confirmed by R and mass spectrum.

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

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

Various types of water-insoluble and organic solvent-soluble homopolymers or copolymers can be used, and for example, the following can be preferably used. (1) Vinyl polymers and copolymers The monomers forming the vinyl polymers and copolymers of the present invention will be described in more detail.

Acrylic esters: For example, methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-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 (number of moles added = 9), 1-bromo-2-methoxyethyl acrylate, 1,1- Dichloro-2-ethoxyethyl acrylate; Methacrylic esters: Examples include 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, tetrahydrofurfuryl methacrylate, phenyl methacrylate, cresyl methacrylate, naphthyl methacrylate, 2-hydroxyethyl methacrylate, 4-hydroxybutyl methacrylate, triethylene glycol monomethacrylate, dipropylene glycol monomethacrylate, 2-methoxyethyl methacrylate, 3-methoxy Butyl 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 (additional mole number n= 6)
Vinyl esters: For example, vinyl acetate, vinyl propionate, vinyl butyrate, vinyl isobutyrate, vinyl caproate, vinyl chloroacetate, vinyl methoxy acetate, vinyl phenylacetate, vinyl benzoate, vinyl salicylate; Acrylamide: For example, acrylamide, methylacrylamide,
Ethylacrylamide, propylacrylamide, butylacrylamide, tert-butylacrylamide,
Cyclohexylacrylamide, benzylacrylamide, hydroxymethylacrylamide, methoxyethylacrylamide, dimethylaminoethylacrylamide, phenylacrylamide, dimethylacrylamide,
Diethylacrylamide, β-cyanoethylacrylamide, N-(2-acetoacetoxyethyl)acrylamide, diacetone acrylamide; Methacrylamides: For example, methacrylamide, methylmethacrylamide, ethylmethacrylamide, propylmethacrylamide, butylmethacrylamide, tert- Butylmethacrylamide, cyclohexylmethacrylamide, benzylmethacrylamide, hydroxymethylmethacrylamide, methoxyethylmethacrylamide, dimethylaminoethylmethacrylamide, phenylmethacrylamide, dimethylmethacrylamide, diethylmethacrylamide,
β-cyanoethyl methacrylamide, N-(2-acetoacetoxyethyl) methacrylamide; Olefins:
Examples include 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, vinylbenzoic acid methyl ester; crotonate esters: e.g. butyl crotonate, hexyl crotonate; itaconate diesters: e.g. dimethyl itaconate, diethyl itaconate, dibutyl itaconate; maleate diesters: For example, diethyl maleate, dimethyl maleate, dibutyl maleate; fumaric acid diesters: for example, diethyl fumarate, dimethyl fumarate,
Examples include 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: e.g. methyl vinyl ketone, phenyl vinyl ketone, methoxyethyl vinyl ketone; Vinyl heterocyclic compounds: e.g. , vinylpyridine, N-vinylimidazole, N-vinyloxazolidone, N-vinyltriazole, N-vinylpyrrolidone; glycidyl esters: for example, glycidyl acrylate, glycidyl methacrylate; unsaturated nitriles: For example, acrylonitrile, methacrylonitrile; etc. can be mentioned.

The polymer used in the present invention may be a homopolymer of the above-mentioned monomers, or, if necessary, a copolymer consisting of two or more types of monomers. Furthermore, the polymer used in the present invention may contain a monomer having an acid group to the extent that it does not become water-soluble (preferably 2
It is 0% or less. ), it is preferable that it does not contain it at all.

Monomers having the above acid group include acrylic acid; methacrylic acid; itaconic acid; maleic acid; monoalkyl itaconate (for example, monomethyl itaconate);
; monoalkyl maleate (e.g. monomethyl maleate); citraconic acid; styrene sulfonic acid; vinylbenzyl sulfonic acid; acryloyloxyalkyl sulfonic acid (e.g. acryloyloxymethyl sulfonic acid)
; methacryloyloxyalkyl sulfonic acid (e.g.
methacryloyloxymethylsulfonic acid, methacryloyloxyethylsulfonic acid, methacryloyloxypropylsulfonic acid); acrylamide alkylsulfonic acid (e.g., 2-acrylamido-2-methylethanesulfonic acid, 2-acrylamido-2-methylpropanesulfonic acid, 2- acrylamide-2-methylbutanesulfonic acid); methacrylamide-alkylsulfonic acid (e.g., 2-methacrylamido-2-methylethanesulfonic acid, 2-methacrylamido-2-methylpropanesulfonic acid, 2-methacrylamido-2-methyl butanesulfonic acid); acryloyloxyalkyl phosphates (e.g., acryloyloxyethyl phosphate, 3-acryloyloxypropyl-2-phosphate); methacryloyloxyalkyl phosphates (e.g., methacryloyloxyethyl phosphate, 3-methacryloyloxypropyl-2-phosphate) etc. can be mentioned.

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

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

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

Examples of water-soluble polymerization initiators include 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 can be used.

Examples of the lipophilic polymerization initiator include 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'-
Examples include lipophilic azo compounds such as diethyl azobisisobutyrate, benzoyl peroxide, lauryl peroxide, diisopropyl peroxydicarbonate, and di-tert-butyl peroxide. (2) Polyester resin obtained by condensing a polyhydric alcohol and a polybasic acid. As the polyhydric alcohol, HO-R1 -OH (R1
Glycols or polyalkylene glycols having a structure of hydrocarbons having 2 to about 12 carbon atoms, especially aliphatic hydrocarbons are effective, and polybasic acids include HO
Those having OC-R2-COOH (R2 represents a simple bond or a hydrocarbon having 1 to 12 carbon atoms) are effective.

Specific examples of polyhydric alcohols include ethylene glycol, diethylene glycol, triethylene glycol, 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,
Examples include diglycerin, triglycerin, 1-methylglycerin, erythritol, mannitol, sorbitol, and the like.

Specific examples of polybasic acids include oxalic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, corkic acid, azelaic acid, sebacic acid, nonanedicarboxylic acid,
Decanedicarboxylic acid, undecanedicarboxylic acid, dodecanedicarboxylic acid, fumaric acid, maleic acid, itaconic acid,
Examples include citraconic acid, phthalic acid, isophthalic acid, terephthalic acid, tetrachlorophthalic acid, methaconic acid, isohimelic acid, cyclopentadiene-maleic anhydride adduct, and rosin-maleic anhydride adduct. (3) Polyesters Obtained by Ring-Opening Polymerization These polyesters are obtained from β-propiolactone, ε-caprolactone, dimethylpropiolactone, and the like. (4) Other polycarbonate resins obtained by polycondensation of glycols or dihydric phenols with carbonic esters or phosgene, polyurethane resins obtained by polyaddition of polyhydric alcohols and polyvalent isocyanates, or polyvalent amines and polybasic acids. Examples include polyamide resins obtained from.

The number average molecular weight of the polymer used in the present invention is not particularly limited, but is preferably 200,000 or less, more preferably 5,000 or more and 100,000 or less.

Specific examples of the polymer used in the present invention are shown below, but the invention is not limited thereto. (The composition of the copolymer is shown in weight ratio.) P-1) Poly(N-sec-butylacrylamide) P-2) Poly(N-tert-butylacrylamide) P-3) Diacetone acrylamide-methyl methacrylate 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) 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 (
38:38:24) 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:
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)
:40:20) 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-vinylsulfonamide copolymer (70:20:10) P-4
3) 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 (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-acryloxybutane-1 - Sodium sulfonate copolymer (
97:3) 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-butylacrylamide-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 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-adipic acid polyester P-70) Ethylene glycol-sebacic acid polyester P-71) Polycaprolactam P-72) Polypropiolactam P-73) Polydimethylpropiolactone P-74
) N-tert-butyl acrylamide-dimethylaminoethyl acrylamide 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, at least one yellow coupler represented by the general formula [Y-I] that forms a dye by coupling with an oxidized product of an aromatic primary amine developing agent is water-insoluble. and the dispersion present in the lipophilic fine particles in coexistence with at least one of the homopolymer or copolymer that is soluble in an organic solvent substantially contains the coupler and at least one of the homopolymer or copolymer. It is obtained by dissolving it in a water-insoluble high-boiling organic solvent and emulsifying and dispersing it in a hydrophilic protective colloid.

[0071] Here, the substantially water-insoluble high-boiling organic solvent has a melting point of 100°C or less and a boiling point of 140°C.
Examples of the above water-immiscible compounds include phenol derivatives, esters such as phthalate esters and phosphate esters, organic acid amides, carbamates, Kents, and the like. These are U.S. Pat. No. 2,322,027, U.S. Pat.
No. 353,262, No. 2,533,514, No. 2
, No. 801,170, No. 2,801,171, No. 2,835,579, No. 2,852,383, No. 2,870,012, No. 2,991,171 ,
Same No. 3,287,134, Same No. 3,554,755, Same No. 3,676,137, Same No. 3,676,142
No. 3,700,454, No. 3,748,14
No. 1, No. 3,779,765 and No. 3,837
, No. 863.

[0072] In order to aid the above-mentioned dissolution, a low boiling point organic solvent or an organic solvent miscible with water can be used.

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

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

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

[0076] Furthermore, two or more of the above-mentioned organic solvents can also be used in combination.

[0077] In order to emulsify and disperse in a hydrophilic protective colloid to form lipophilic fine particles, a dispersion aid such as a surfactant is used, and a stirrer, homogenizer, colloid mill, flow jet mixer, ultrasonic device, etc. are used. Spread. A step of removing the low boiling point organic solvent may be included simultaneously with the dispersion.

[0078] As the hydrophilic protective colloid, an aqueous gelatin solution is preferably used.

[0079] The average particle diameter of the lipophilic fine particles is 0.04.
It is preferably from μ to 2μ, more preferably from 0.06μ to 0.4μ. The particle size can be measured using Coulter Model N4 manufactured by Coulter Co., Ltd., UK.

In the present invention, the mixing ratio of the coupler, the homopolymer or copolymer, the high boiling point solvent and the auxiliary solvent such as the low boiling point solvent or the organic solvent miscible with water, The viscosity may be selected so that the solution obtained by dissolving the cosolvent in the cosolvent has a suitable viscosity so that it can be easily dispersed in the hydrophilic colloid. The value at this time varies depending on the solubility of the coupler used, the type of polymer, and the degree of polymerization, and cannot be determined uniformly, but 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 point solvent to the coupler used is 1:20 to 5:1, preferably 1:
The ratio is 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
The ratio is 5:1.

In the present invention, the general formula [Y-I]
A dispersion in which at least one yellow coupler represented by the formula is present in lipophilic fine particles in the coexistence of one of water-insoluble and organic solvent-soluble single or copolymers is a blue-sensitive silver halide emulsion. Preferably, it is added to the layer.

The dispersion may also contain compounds that do not need to be adsorbed onto the surface of the silver halide crystals, such as image stabilizers, color antifoggants, ultraviolet absorbers, fluorescent brighteners, oil-soluble dyes, etc. It can also be distributed.

[0084] JP-A-59-125732, No. 62
It is preferable to simultaneously disperse the image stabilizer described in Japanese Patent No.-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., but especially when applied to color photographic paper used for direct viewing. The effects of the present invention are effectively exhibited.

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

Magenta dye image forming couplers that can be used in the present invention include 4-equivalent or 2-equivalent magenta dye image-forming couplers such as 5-pyrazolone, pyrazoloazole, pyrazolinobenzimidazole, indazolone, and cyanoacetyl. forming couplers, these include:
For example, U.S. Patent Nos. 2,600,788 and 3,061
, No. 432, No. 3,062,653, No. 3,127,
No. 269, No. 3,152,896, No. 3,311,4
No. 76, No. 3,419,391, No. 3,519,42
No. 9, No. 3,558,318, No. 3,684,514
No. 3,705,896, No. 3,888,680, No. 3,907,571, No. 3,928,044,
3,930,861, 3,930,816, 3,933,500, JP 49-29639, 49-111631, 49-129538, 5
No. 1-112341, No. 52-58922, No. 55-
No. 62454, No. 55-118034, No. 56-38
No. 643, No. 56-135841, Special Publication No. 1977-60
No. 479, No. 52-34937, No. 55-29421
No. 55-35696, British Patent No. 1,247,4
No. 93, 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, phenol compounds, naphthol compounds, etc. can be used. Specific examples include U.S. Patent Nos. 2,369,929, 2,434,272, 2,474,293, 2,521,908,
, No. 895,826, No. 3,034,892, No. 3,
No. 311,476, No. 3,458,315, No. 3,4
No. 76,563, No. 3,583,971, No. 3,59
No. 1,383, No. 3,767,411, No. 4,004
, No. 929, West German Patent Application (OLS) 2,414,83
No. 0, No. 2,454,329, Japanese Unexamined Patent Publication No. 48-5983
No. 8, No. 51-26034, No. 48-5055, No. 51-146828, No. 52-69624, No. 52
Examples include those described in No.-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) contains silver bromide, silver iodobromide, silver iodochloride as silver halide. Any of those used in conventional silver halide emulsions can be used, such as silver, silver chlorobromide and silver chloride.

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 range using a dye known as a sensitizing dye in the photographic industry.

The silver halide photographic material of the present invention includes:
Color antifoggant, hardener, plasticizer, polymer latex, ultraviolet absorber, formalin scavenger, mordant,
Development accelerators, development retarders, optical brighteners, matting agents, lubricants, antistatic agents, surfactants, and the like can be optionally used.

Images can be formed using the silver halide photographic material of the present invention by performing various color development treatments.

[0094]

EXAMPLES Specific examples of the present invention will be described below, but the embodiments of the present invention are not limited thereto. Example 1 (Preparation of silver halide emulsions) Three types 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, STB-1 shown below was added as an emulsion stabilizer to each silver halide emulsion at 5×10 −3 mol per mol of silver halide.

[0096]

[Chemical formula 14]

(Preparation of silver halide color photographic light-sensitive material sample) Next, the following layers 1 to 7 were sequentially coated (simultaneously coated) on a paper support coated with polyethylene on both sides to form a silver halide color photographic light-sensitive material. 1 was produced. (In the following examples, the amount added is shown per 1 m2 of photosensitive material.) Layer 1: Gelatin (1.2 g) and 0.29 g (in terms of silver,
Comparison of blue-sensitive silver halide emulsion (Em-1) with 1.0 mmol of yellow coupler (Y-A) and 0.015 g of 2,5-dioctylhydroquinone (H
A layer containing 0.3 g of DOP (dioctyl phthalate) in which Q-1) was dissolved.

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

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

Layer 4...gelatin (1.2g) and 0.6g
of ultraviolet absorber (UV-1) and 0.05g of HQ-1
A layer containing 0.3 g of DNP (dinonylphthalate) dissolved therein.

[0101] Layer 5...Gelatin (1.4g) and 0.20g
g red-sensitive silver halide emulsion (Em-3) and 0.54
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 (1.1g) and 0.2
A layer containing 0.3 g of DOP in which g of UV-1 was dissolved and 5 mg of the following filter dye (AI-2).

[0103] Layer 7...Gelatin (1.0g) and 0.0
5 g of sodium 2,4-dichloro-6-hydroxytriazine.

[0104]

[Chemical formula 15]

[0105]

[Chemical formula 16]

Furthermore, the types and amounts of the yellow coupler, high boiling point organic solvent, and water-insoluble and organic solvent-soluble homopolymer or copolymer in layer 1 of the above layer structure are shown in Table 2, and the silver halide Photosensitive materials (Nos. 2 to 21) were prepared.

[0107]

[Table 2]

The obtained sample was subjected to wedge exposure using a photosensitometer model KS-7 (manufactured by Konica Corporation), and then processed according to the following color development process. The maximum density (Dmax) of the blue-sensitive emulsion layer was measured using a blue-sensitive emulsion layer (Model 65).

[0109] Also, the maximum absorption wavelength λmax when the density of the yellow dye image is 1.0, and the wavelength 50 at that time.
The concentration DG at 0 nm was measured.

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

The results are shown in Table 3. [Color developer] Pure water

800ml triethanolamine
8g
N,N-diethylhydroxyamine
5g
potassium chloride

2g N-ethyl-N-β
-Methanesulfonamidoethyl-3-methyl-
4-aminoaniline sulfate

5g Sodium tetrapolyphosphate

2g potassium carbonate

30g potassium sulfite
0.
2g Fluorescent brightener (4,4'-diaminostilbendisulfonic acid derivative) 1g Add pure water to make a total volume of 1 liter, and adjust the pH to 10.05. [Bleach-fix solution] Ethylenediaminetetraacetic acid ferric ammonium dihydrate 60g Ethylenediaminetetraacetic acid
3g ammonium thiosulfate (70% solution)
100ml ammonium sulfite (4
0% solution)
27.5ml Potassium carbonate or glacial acetic acid to pH 5.7
Adjust to 1 liter and add water to make a total volume of 1 liter. [Stabilizing liquid] 5-chloro-2-methyl-4-isothiazolin-3-one 1 g 1-hydroxyethylidene-1,1-diphosphonic acid 2 g
Add water to make 1 liter, and adjust the pH to 7.0 with sulfuric acid or potassium hydroxide.

[0112]

[Table 3]

As is clear from Table 3, sample No. 1 using the yellow coupler of the present invention and the polymer of the present invention. 5～
It can be seen that Sample No. 21 has good color development, excellent color reproducibility due to reduced DG, and also has significantly improved light resistance.

[0114]

Effects of the Invention In the silver halide photographic material of the present invention, the spectral absorption characteristics of the yellow dye formed are improved, and as a result, color reproducibility can be greatly improved. Furthermore, the image storage stability of the yellow dye can be improved, and the coloring property is also high and a sufficient maximum density can be obtained.

Claims (1)

[Claims] 1. A silver halide photographic material having at least one silver halide emulsion layer on a support, in which the silver halide emulsion layer contains a compound having the following general formula [Y-I]
It is characterized by containing a dispersion in which at least one kind of yellow coupler represented by is present in lipophilic fine particles in a state in which at least one kind of a water-insoluble and organic solvent-soluble single or copolymer is present. A silver halide photographic light-sensitive material. General formula [Y-I] [Formula 1] [In the formula, RA and RB represent an alkyl group, a cycloalkyl group, or an aryl group. XA represents an acylamino group or a sulfonylamino group. ZA has the general formula [Y-I
I] and [Y-III] represent a group that can be separated by reaction with an oxidized product of a color developing agent. General formula [Y-II] [Formula 2, RC and RD represent a hydrogen atom or a substituent, and Y represents -N(RG)-, -O- or -S(O)p-] In the formula, RG represents a hydrogen atom or a substituent, and p represents an integer from 0 to 2). ] General formula [Y-III] [In the formula, RE and RF represent a hydrogen atom or a substituent, and W represents -O- or -S(O)r-. r represents an integer from 0 to 2. ]]