JP2759277B2 - Silver halide photographic material - Google Patents

Description

Description: FIELD OF THE INVENTION The present invention relates to a silver halide color photographic material having excellent color reproducibility and image storability.

[Background of the Invention]

Conventionally, a combination of a yellow coupler, a magenta coupler, and a cyan coupler is used in a color photographic paper used for direct appreciation.

Among them, most of those conventionally widely used as magenta couplers were 5-pyrazolone rings. This 5
-Dyes formed from pyrazolone-based couplers have a yellow component due to the presence of unnecessary absorption near 430 nm, and have the disadvantage that colorful blue reproduction cannot be sufficiently performed.

In contrast, recently developed pyrosoloazole-based couplers differ from the conventionally used 5-pyrazolone-based magenta couplers in that the coloring dyes do not have side absorption around 430 nm, which is basically a factor in improving color reproducibility. And is advantageous.

However, magenta dyes obtained from pyrazoloazole-based magenta couplers have higher image storability than magenta dyes obtained from 5-pyrazolone-based magenta couplers,
In particular, it is known that light resistance is inferior, and improvement of this is strongly desired.

As a technology to improve the light resistance of couplers,
For example, JP-A-63-44658, JP-A-63-250648, JP-A-64-5
No. 37 and WO-88100723 disclose a technique of emulsifying and dispersing a water-insoluble and organic solvent-soluble polymer together with a coupler. When this technology is applied to a pyrazoloazole-based magenta coupler, light resistance can be improved, but when the storage condition of the sample is high temperature and high humidity,
Although the effect is not sufficient, there is also a problem that the use of the above-mentioned polymer causes a decrease in color development. Therefore, in order to maintain or improve the color developing property, a technique of coexisting a high boiling point organic solvent with a coupler or a polymer or introducing many hydrophilic groups (sulfonamide bond, ether bond, etc.) into a diffusion resistant group of the coupler is used. Can be However, in this case, during storage of the image, a part of the components constituting the lipophilic fine particles move to the surface of the photographic constituent layer to cause a sweating phenomenon (hereinafter referred to as sweating), which tends to cause a significant deterioration in image quality. Problems were clarified.

Thus, using a pyrazoloazole-based magenta coupler to improve the light fastness of silver halide photographic light-sensitive materials excellent in color reproduction, and to effectively prevent sweating and improve image preservation technology, There are still no satisfactory ones, and improvements are strongly desired.

[Object of the invention]

Accordingly, a first object of the present invention is to provide a silver halide photographic material having excellent color reproducibility.

A second object of the present invention is to provide a silver halide photographic light-sensitive material which is excellent in light fastness and has good image storability in which perspiration is prevented.

A third object of the present invention is to provide a silver halide photographic light-sensitive material having excellent color developability.

[Summary of the Invention]

An 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 at least one of the silver halide emulsion layers is represented by the following general formula [MI]. Silver halide photographic material characterized by containing lipophilic fine particles obtained by emulsifying and dispersing a magenta coupler having a molecular weight of 400 to 550 and a water-insoluble and organic solvent-soluble polymer compound in the coexistence. Achieved by

In the formula, Z represents a nonmetallic atom group necessary for forming a nitrogen-containing heterocyclic ring, and the ring formed by Z may have a substituent.

X represents a hydrogen atom or a group capable of leaving by reaction with an oxidized form of a color developing agent.

 R represents a hydrogen atom or a substituent.

 Next, the present invention will be described in more detail.

Molecular weight having a structure represented by the general formula [MI]
The magenta coupler of the present invention of 400 to 550 will be described.

In the formula, Z represents a nonmetallic atom group necessary for forming a nitrogen-containing heterocyclic ring, and the ring formed by Z may have a substituent.

X represents a hydrogen atom or a group capable of leaving by reaction with an oxidized form of a color developing agent.

 R represents a hydrogen atom or a substituent.

The substituent represented by R is not particularly limited, but typically includes groups such as alkyl, aryl, anilino, acylamino, sulfonamide, alkylthio, arylthio, alkenyl, and cycloalkyl. Atom and cycloalkenyl, alkynyl, heterocycle, sulfonyl, sulfinyl, phosphonyl, acyl,
Carbamoyl, sulfamoyl, cyano, alkoxy,
Aryloxy, heterocyclic oxy, siloxy, acyloxy, carbamoyloxy, amino, alkylamino, imide, ureido, sulfamoylamino, alkoxycarbonylamino, aryloxycarbonylamino, alkoxycarbonyl, aryloxycarbonyl, heterocyclic thio groups And spiro compound residues, bridged hydrocarbon compound residues, and the like.

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

As the aryl group represented by R, a phenyl group is preferable.

Examples of the acylamino group represented by R include an alkylcarbonylamino group and an arylcarbonylamino group.

Examples of the sulfonamide group represented by R include an alkylsulfonylamino group and an arylsulfonylamino group.

The alkyl component and the aryl component in the alkylthio group and the arylthio group represented by R include the alkyl group and the aryl group represented by R.

The alkenyl group represented by R has 2 to 32 carbon atoms, and the cycloalkyl group has 3 to 12 carbon atoms, particularly 5 carbon atoms.
To 7 are preferable, and the alkenyl group may be linear or branched.

The cycloalkenyl group represented by R has 3 carbon atoms.
~ 12, especially 5-7 are preferred.

As the sulfonyl group represented by R, an alkylsulfonyl group, an arylsulfonyl group, or the like; As the sulfinyl group, an alkylsulfinyl group, an arylsulfinyl group, or the like; As the phosphonyl group, an alkylphosphonyl group, an alkoxyphosphonyl group, an aryloxyphosphonyl group An acylcarbonyl group such as an alkylcarbonyl group or an arylcarbonyl group; a carbamoyl group such as an alkylcarbamoyl group or an arylcarbamoyl group; a sulfamoyl group such as an alkylsulfamoyl group or an arylsulfamoyl group; As an acyloxy group, an alkylcarbonyloxy group, an arylcarbonyloxy group, etc .; As a carbamoyloxy group, an alkylcarbamoyloxy group, an arylcarbamoyloxy group, etc .; a ureido group Such as alkyl ureido groups and aryl ureido groups; sulfamoylamino groups such as alkylsulfamoylamino groups and arylsulfamoylamino groups; and heterocyclic groups having 5 to 7 members are preferred. Is a 2-furyl group, a 2-thienyl group, a 2-pyrimidinyl group, a 2-benzothiazolyl group or the like; As the heterocyclic oxy group, those having a 5- to 7-membered heterocyclic ring are preferable, and for example, 3,4,5,6 -Tetratetrahydropyranyl-2-oxy group, 1-phenyltetrazole-5
A heterocyclic thio group is preferably a 5- to 7-membered heterocyclic thio group, for example, a 2-pyridylthio group, a 2-benzothiazolylthio group, a 2,4-diphenoxy-1,3,5- Triazole-6-thio group, etc .; siloxy group as trimethylsiloxy group, triethylsiloxy group, dimethylbutylsiloxy group, etc .; imide group as succinimide group, 3-heptadecylsuccinimide group, phthalimide group, glutarimide group Spiro compound residues include spiro [3.3] heptane-
1-yl and the like; bicyclo [2.2.1] as a bridged hydrocarbon compound residue
Heptan-1-yl, tricyclo [3.3.1.1 ^3,7 ] decan-1-yl, 7,7-dimethyl-bicyclo [2.2.1] heptane-1-yl and the like.

Examples of the group capable of leaving by reaction with an oxidized form of the color developing agent represented by X include a halogen atom (a chlorine atom, a bromine atom, a fluorine atom, etc.), alkoxy, aryloxy,
Heterocyclic oxy, acyloxy, sulfonyloxy, alkoxycarbonyloxy, aryloxycarbonyl,
Alkyloxalyloxy, alkoxyoxalyloxy, alkylthio, arylthio, heterocyclic thio, alkyloxythiocarbonylthio, acylamino, sulfonamide, nitrogen-containing heterocyclic ring linked by N atom, alkyloxycarbonylamino, aryloxycarbonylamino, carboxyl , (R ₁ ′ has the same meaning as R, Z ′ has the same meaning as Z, and R ₂ ′ and R ₃ ′ each represent a hydrogen atom, an aryl group, an alkyl group, or a heterocyclic group.) And preferably a halogen atom, particularly a chlorine atom.

Examples of the nitrogen-containing heterocyclic ring formed by Z or Z ′ include a pyrazole ring, an imidazole ring, a triazole ring, and a tetrazole ring. Examples of the substituent that the ring may have include those described above for R. Is mentioned.

The compound represented by the general formula [MI] is more specifically represented by the following general formulas [M-II] to [M-VII].

In the general formulas [M-II] to [M-VII], R _{1 to} R ₈
And X have the same meanings as R and X described above.

Among the general formulas [MI], preferred are those represented by the following general formula [M-VIII].

In the formula, R ₁ , X and Z ₁ have the same meanings as R, X and Z in the general formula [MI].

Among the magenta couplers represented by the general formulas [M-II] to [M-VII], those particularly preferred are those represented by the general formula [MI]
I] is a magenta coupler represented by

Most preferred as the substituents R and R ₁ on the heterocyclic ring are those represented by the following general formula [M-IX].

In the formula, R ₉ , R ₁₀ and R ₁₁ have the same meanings as R described above.

Further, two of R ₉ , R ₁₀ and R ₁₁ , for example, R ₉ and R ₁₀ are bonded to each other to form a saturated or unsaturated ring (eg, cycloalkane,
Cycloalkene, heterocyclic ring) may be formed, it may constitute the bridged hydrocarbon compound residue bound R ₁₁ further ring.

Preferred among Formula [M-IX] of, (i) R ₉ ~
When at least two of R ₁₁ are alkyl groups, (ii) R 11
One example R ₁₁ in the ₉ to R ₁₁ is a hydrogen atom, a, if the other two R ₉ and R ₁₀ form a cycloalkyl together with the root carbon atom bonded.

Further, among (i), preferred are two of R _{9 to} R _11.
One is an alkyl group and the other is a hydrogen atom or an alkyl group. Most preferred is when all three of R _{9 to} R ₁₁ are alkyl groups.

In general formula (M-I) formed by Z in the ring and Formula [M-VIII] ring substituent which may have formed by Z ₁ in, and Formula [M-II] -
R _{2 to} R ₈ in [M-VI] are represented by the following general formula [M-VI
X] is preferred.

The general formula [M-X] -R ¹ -SO ^₂ -R ₂ Formula wherein R ¹ is an alkylene group, R ² represents an alkyl group, a cycloalkyl group or an aryl group.

The alkylene group represented by R ¹ preferably has 2 or more carbon atoms in the straight-chain portion, more preferably 3 to 6, and may be linear or branched.

The alkyl group represented by R ² preferably has 6 to 20 carbon atoms and may be linear or branched.

The cycloalkyl group represented by R ² preferably have 5-6 membered.

The aryl group represented by R ² is preferably a phenyl group, and may further have a substituent.

The molecular weight of the magenta coupler represented by the general formula [M-1] needs to be 600 or less, but is most preferably 400 to
550.

Specific examples of the magenta coupler of the present invention represented by the general formula [MI] are shown below, but it should not be construed that the invention is limited thereto.

The coupler is described in Journal of the Chemical Society, Perkin I (1977), 2047-2052, U.S. Pat.
No. 5,067, JP-A-59-99437, JP-A-58-42045, JP-A-59-1
No. 62548, No. 59-171956, No. 60-33552, No. 60-4365
No. 9, No. 60-177292 and No. 60-190779 can be synthesized.

The coupler can be used in an amount of usually 1 × 10 ^-3 mol to 1 mol, preferably 1 × 10 ^-2 mol to 8 × 10 ^-1 mol, per mol of silver halide.

Further, the coupler of the present invention can be used in combination with another type of magenta coupler.

Next, the polymer compound according to the present invention (hereinafter referred to as a polymer,
, Etc.) will be specifically described.

(1) Vinyl Polymer and Copolymer The monomers forming the vinyl polymer and the copolymer will be described more specifically.
Methyl acrylate, ethyl acrylate, isopropyl acrylate, butyl acrylate, t-butyl acrylate, amyl acrylate, hexyl acrylate, 2-ethylhexyl acrylate, t-octyl acrylate, 2-chloroethyl acrylate, 4-chlorobutyl acrylate, cyanoethyl acrylate, 2
-Acetoxyethyl acrylate, dimethylaminoethyl acrylate, methoxybenzyl acrylate, cyclohexyl acrylate, tetrahydrofurfuryl acrylate, phenyl acrylate, 2,2-dimethyl-3
-Hydroxypropyl acrylate, 2-methoxyethyl acrylate, 2-ethoxyethyl acrylate, 2
I-propoxy acrylate, 2- (2-methoxyethoxy) ethyl acrylate, ω-methoxy polyethylene glycol acrylate (additional mole number n = 9), 1-
Bromo-2-methoxyethyl acrylate and the like.

Examples of methacrylates include methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, isobutyl methacrylate, amyl methacrylate, cyclohexyl methacrylate, benzyl methacrylate, octyl methacrylate, sulfopropyl methacrylate, N-ethyl-N-
Phenylaminoethyl methacrylate, dimethylaminophenoxyethyl methacrylate, furfuryl methacrylate, phenyl methacrylate, cresyl methacrylate, naphthyl methacrylate, 2-hydroxyethyl methacrylate, triethylene glycol monomethacrylate, 2-methoxyethyl methacrylate, 2-acetoxyethyl methacrylate, 2 -Ethoxyethyl methacrylate, 2- (2-methoxyethoxy) ethyl methacrylate, ω-methoxypolyethylene glycol methacrylate (additional mole number n = 6) and the like.

Examples of vinyl esters include vinyl acetate,
Examples include vinyl propionate, vinyl butyrate, vinyl isobutyrate, vinyl caproate, vinyl chloroacetate, vinyl methoxy acetate, vinyl phenyl acetate, vinyl benzoate, vinyl salicylate, and the like.

Examples of acrylamide include allylamide, ethylacrylamide, propylacrylamide, butylacrylamide, t-butylacrylamide, cyclohexylacrylamide, benzylacrylamide, hydroxymethylacrylamide, methoxyethylacrylamide, dimethylaminoethylacrylamide, phenylacrylamide, dimethylacrylamide, β- Cyanoethylacrylamide, N- (2-acetoacetoxyethyl) acrylamide, diacetoneacrylamide and the like; Examples of methacrylamide include methacrylamide,
Methyl methacrylamide, ethyl methacrylamide, propyl methacrylamide, butyl methacrylamide, t
-Butyl methacrylamide, cyclohexyl methacrylamide, benzyl methacrylamide, hydroxymethyl methacrylamide, methoxyethyl methacrylamide,
Examples thereof include dimethylaminoethyl methacrylamide, phenyl methacrylamide, dimethyl methacrylamide, β, cyanoethyl methacrylamide, and N- (2-acetoacetoxyethyl) methacrylamide.

Examples of the olefins include dicyclopentadiene, ethylene, propylene, 1-butene, 1-pentene, vinyl chloride, vinylidene chloride, isoprene, chloroprene, butadiene, and 2,3-dimethylbutadiene.

Examples of the styrenes include styrene, methyl styrene, trimethyl styrene, ethyl styrene, chloromethyl styrene, methoxy styrene, chloro styrene, dichloro styrene, and methyl vinyl benzoate.

Examples of crotonates include butyl crotonate, hexyl crotonate and the like.

Examples of itaconic acid diesters include dimethyl itaconate, diethyl itaconate, and dibutyl itaconate.

The maleic acid diesters include, for example, diethyl maleate, dimethyl maleate, dibutyl maleate and the like.

Examples of the fumaric acid diesters include diethyl fumarate, dimethyl fumarate, dibutyl fumarate, and the like.

Examples of other monomers include the following.

Allyl compounds such as allyl acetate, allyl caproate, allyl laurate, allyl benzoate and the like; vinyl ethers such as methyl vinyl ether,
Butyl vinyl ale, methoxy ethyl vinyl ether,
Dimethylaminoethyl vinyl ether and the like; vinyl ketones such as methyl vinyl ketone, phenyl vinyl ketone and methoxyethyl vinyl ketone; vinyl heterocyclic compounds such as vinyl pyridine and N-
Vinylimidazole, N-vinyloxazolidone, N-
Glycidyl esters such as glycidyl acrylate and glycidyl methacrylate; and unsaturated nitriles such as acrylonitrile and methacrylonitrile.

The polymer used in the present invention may be a homopolymer of the above monomers, or may be a copolymer composed of two or more kinds of monomers as required. Further, the polymer used in the present invention may contain a monomer having an acid group shown below to the extent that it does not become water-soluble, but is preferably
20% or less, more preferably not containing at all.

Acrylic acid, methacrylic acid, itaconic acid, maleic acid, monoalkyl itaconate, monoalkyl maleate, citraconic acid, styrenesulfonic acid, vinylbenzylsulfonic acid, acryloyloxyalkylsulfonic acid, acryloyloxyalkylsulfonic acid, methacryloyloxyalkylsulfone Examples include acid, acrylamidoalkylsulfonic acid, methacrylamidoalkylsulfonic acid, acryloyloxyalkylphosphate, methacryloyloxyalkylphosphate, and the like. These acids are alkali metals (eg, Na, K, etc.)
Alternatively, it may be a salt of ammonium ion.

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

The polymer formed from the above monomers is a solution polymerization method,
It is obtained by 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. As the water-soluble polymerization initiator, for example, potassium persulfate, ammonium persulfate, persulfates such as sodium persulfate, 4,
Sodium 4'-azobis-4-cyanovalerate, 2,2'-
A water-soluble azo compound such as azobis (2-amidinopropane) hydrochloride and hydrogen peroxide can be used. Examples of the lipophilic polymerization initiator include azobisisobutyronitrile, 2,2'-azobis-2,4-dimethylvaleronitrile), 1,1'-azobis (cyclohexanone-1-carbonitrile), Dimethyl 2'-azobisisobutyrate, 2,
Lipophilic azo compounds such as diethyl 2'-azobisisobutyrate, benzoyl peroxide, lauryl peroxide,
Examples thereof include diisopropyl peroxydicarbonate and di-t-butyl peroxide.

(2) Polyester Resin Obtained by Condensing Polyhydric Alcohol and Polybasic Acid As the polyhydric alcohol, HO—R ₁ —OH (R ₁ has 2 carbon atoms)
To about 12 hydrocarbon chain, especially glycols having an aliphatic hydrocarbon chain) comprising structure, or polyalkylene glycol is valid and polybasic _{acids, HOOC-R 2 -COOH (R} 2
Represents a simple bond or has a hydrocarbon chain having 1 to 12 carbon atoms).

Specific examples of polyhydric alcohols include ethylene glycol, diethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, trimethylolpropane, 1,4-butanediol, isobutylene diol,
1,5-pentanediol, neopentyl glycol, 1,6
-Hexanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, glycerin, diglycerin, triglycerin, 1-methylglycerin,
Erislit, mannit, sorbit and the like.

Specific examples of polybasic acids include oxalic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, cornic acid, azelaic acid, sebacic acid, decanedicarboxylic 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 is obtained from caprolactone, dimethylpropiolactone and the like.

(4) Other polymers Polycarbonate resin obtained by polycondensation of glycol or dihydric phenol with carbonic acid ester or phosgene, polyurethane resin obtained by polyaddition of polyhydric alcohol and polyvalent isocyanate, or polyamine And a polyamide resin obtained from a polybasic acid.

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

Ratio of polymer of the present invention to coupler (weight ratio)
Is preferably 1:20 to 20: 1, more preferably 1:10 to 1
0: 1.

Specific examples of the polymer used in the present invention are shown below,
It is not limited to these. (The composition of the copolymer is shown by weight ratio.) A-1 Poly (N-sec-butylacrylamide) A-2 Poly (Nt-butylacrylamide) A-3 Diacetone acrylamide-methyl methacrylate copolymer (25:75) A-4 polycyclohexyl methacrylate A-5 Nt-butylacrylamide-methyl methacrylate copolymer (60:40) A-6 poly (N, N-dimethylacrylamide) A-7 poly (t- (Butyl methacrylate) A-8 Polyvinyl acetate A-9 Polyvinyl propionate A-10 Polymethyl methacrylate A-11 Polyethyl methacrylate A-12 Polyethyl acrylate A-13 Vinyl acetate-vinyl alcohol copolymer (90: 1)
0) A-14 polybutyl acrylate A-15 polybutyl methacrylate A-16 polyisobutyl methacrylate A-17 polyisopropyl methacrylate A-18 polyoctyl acrylate A-19 butyl acrylate-acrylamide copolymer (95: 5) A-20 Stearyl methacrylate-acrylic acid copolymer (90:10) A-21 Methyl methacrylate-vinyl chloride copolymer (70:30) A-22 Methyl methacrylate-styrene copolymer (9
0:10) A-23 Methyl methacrylate-ethyl acrylate copolymer (50:50) A-24 Butyl methacrylate-methyl methacrylate-styrene copolymer (50:20:30) A-25 Vinyl acetate-acrylamide copolymer (85: 1
5) A-26 Vinyl chloride-vinyl acetate copolymer (65:35) A-27 Methyl methacrylate-acrylonitrile copolymer (65:35) A-28 Butyl methacrylate-pentyl methacrylate-N-vinyl-2-pyrrolidone A-29 Methyl methacrylate-butyl methacrylate-isobutyl methacrylate-acrylic acid copolymer (3:38:24)
7: 29: 25: 9) A-30 Butyl methacrylate-acrylic acid copolymer (95: 5) A-31 Methyl methacrylate-acrylic acid copolymer (95: 5) A-32 Benzyl methacrylate-acrylic acid copolymer A-33 butyl methacrylate-methyl methacrylate-benzyl methacrylate-acrylic acid copolymer (35: 3)
5: 25: 5) A-34 Butyl methacrylate-methyl methacrylate-benzyl methacrylate copolymer (40:30:30) A-35 Diacetone acrylamide-methyl methacrylate copolymer (50:50) A-36 Methyl vinyl ketone -Isobutyl methacrylate copolymer (55:45) A-37 Ethyl methacrylate-butyl acrylate copolymer (70:30) A-38 Diacetone acrelamide-butyl acrylate copolymer (60:40) A-39 methyl Methacrylate-styrene methacrylate-diacetone acrylamide copolymer (40:40:20) A-40 Butyl acrylate-styrene methacrylate-diacetone acrylamide copolymer (70:20:10) A-41 Stearyl methacrylate-methyl methacrylate-acryl Acid copolymer (50:40:10) A-42 Methyl methacrylate-styrene-bi N-sulfonamide copolymer (70:20:10) A-43 Methyl methacrylate-phenyl vinyl ketone copolymer (70:30) A-44 Butyl acrylate-methyl methacrylate-
Butyl methacrylate copolymer (35:35:30) A-45 Butyl methacrylate-N-vinyl-2-pyrrolidone copolymer (90:10) A-46 Polypentyl acrylate A-47 Cyclohexyl methacrylate-methyl methacrylate-propyl methacrylate Copolymer (37: 29: 3
4) A-48 Polypentyl methacrylate A-49 Methyl methacrylate-butyl methacrylate copolymer (65:35) A-50 Vinyl acetate vinyl propionate copolymer (75:25) A-51 Butyl methacrylate-3-acrylic A-52 butyl methacrylate-methyl methacrylate-acrylamide copolymer (35:35:30) A-53 butyl methacrylate-methyl methacrylate-vinyl chloride copolymer (97: 3) (37:36:27) A-54 butyl methacrylate-styrene copolymer (8
2:12) A-55 t-butyl methacrylate-methyl methacrylate copolymer (70:30) A-56 poly (N-t-butyl methacrylamide) A-57 N-t-butyl acrylamide-methyl phenyl methacrylate copolymer Combined (60:40) A-58 Methyl methacrylate-acrylonitrile copolymer (70:30) A-59 Methyl methacrylate-methyl vinyl ketone copolymer (38:72) A-60 Methyl methacrylate-styrene copolymer ( 7
5:25) A-61 methyl methacrylate-hexyl methacrylate copolymer (70:30) A-62 butyl methacrylate-acrylic acid copolymer (85:15) A-63 methyl methacrylate-acrylic acid copolymer (80: 20) A-64 methyl methacrylate-acrylic acid copolymer (90:10) A-65 methyl methacrylate-acrylic acid copolymer (98: 2) A-66 methyl methacrylate-N-vinyl-2-pyrrolidone copolymer (90:10) A-67 butyl methacrylate-vinyl chloride copolymer (90:10) A-68 butyl methacrylate-styrene copolymer (7
0:30) A-69 1,4-butanediol-adipate polyester A-70 Ethylene glycol-sebacate polyester A-71 polycaprolactam A-72 polypropiolactam A-73 polydimethylpropiolactone A-74 N- t-butylacrylamide-dimethylaminoethylacrylamide copolymer (85:15) A-75 Nt-butylmethacrylamide-vinylpyridine copolymer (95: 5) A-76 diethyl maleate-butyl acrylate copolymer (65:35) A-77 Nt-butylacrylamide-2-methoxyethyl acrylate copolymer (55:45) A-78 ω-methoxypolyethylene glycol methacrylate (addition mole number n = 6) -methyl methacrylate (40 : 60) A-79 ω-methoxy polyethylene glycol acrylate (additional mole number n = 9) -Nt -Butylacrylamide (25:75) A-80 Poly (2-methoxyethyl acrylate) A-81 Poly (2-methoxyethyl methacrylate) A-82 Poly [2- (2-methoxyethoxy) ethyl acrylate] A-832 -(2-butoxyethoxy) ethyl acrylate-methyl methacrylate (58:42) A-84 poly (oxycarbonyloxy-1,4-phenyleneisobutylidene-1,4-phenylene) A-85 poly (oxyethyleneoxycarbonyl) The dispersion obtained by emulsifying and dispersing the present invention is obtained by dissolving a coupler and a water-insoluble and organic solvent-soluble polymer compound in a low-boiling point and / or a water-soluble organic solvent, if necessary,
After emulsifying and dispersing using a dispersing means such as a stirrer, a homogenizer, a colloid mill, a flow jet mixer, and an ultrasonic device using a surfactant in a hydrophilic binder such as an aqueous gelatin solution, a desired hydrophilic colloid layer is formed. It may be added inside. The low-boiling point and / or water-soluble organic solvent may be removed from the adjusted dispersion by distillation, noodle washing or ultrafiltration. Examples of low-boiling organic solvents include ethyl acetate, butyl acetate, ethyl propionate,
Tert-butyl alcohol, methyl ethyl ketone, methyl isobutyl ketone, β-ethoxyethyl acetate-methyl cellosolve acetate, cyclohexanone and the like. Also, as the water-soluble organic solvent, methyl alcohol,
Ethyl alcohol, acetone, tetrahydrofuran and the like can be mentioned. These organic solvents can be used in combination of two or more as necessary.

Alternatively, in the presence of a coupler, the monomer component of the homopolymer or copolymer obtained by suspension polymerization, solution polymerization or bulk polymerization is dispersed in a hydrophilic binder in the same manner. The method described in JP-A-60-107642 may be used.

The above-mentioned dispersion contains a high-boiling organic solvent, and frequently used high-boiling organic solvents also include phenol derivatives, phthalate esters, phosphate esters, citrate esters, benzoic acid which do not react with the oxidized form of the developing agent. ester,
Organic solvents having a boiling point of 150 ° C. or higher, such as alkylamides, fatty acid esters and trimesic acid esters, are used.

In the present invention, the high-boiling organic solvent has a dielectric constant of 6.
Those having a value of less than 0 are preferably used.

As the high boiling point organic solvent preferably used in the present invention, any compound having a dielectric constant of less than 6.0 can be used. The lower limit is not particularly limited, but the dielectric constant is 1.9.
The above is preferred. Examples thereof include esters such as phthalic acid esters and phosphoric acid esters having a dielectric constant of less than 6.0, organic acid amides, ketones, and hydrocarbon compounds.

In the present invention, a high boiling organic solvent having a vapor pressure at 100 ° C. of preferably 0.5 mmHg or less is preferred. More preferably, phthalic acid esters or phosphoric acid esters in the high-boiling organic solvent are used. The organic solvent may be a mixture of two or more kinds, and in this case, the mixture only needs to have a dielectric constant of less than 6.0. The dielectric constant in the present invention indicates a dielectric constant at 30 ° C.

The phthalic acid ester advantageously used in the present invention includes those represented by the following general formula [HA].

In the formula, R _H1 and R _H2 each represent an alkyl group, an alkenyl group or an aryl group. Where R _H1 and R _H2
The total number of carbon atoms of the group represented by is 9 to 32.
More preferably, the total number of carbon atoms is 16 to 24.

The alkyl groups represented by R _H1 and R _H2 in the general formula [HA] are linear or branched, and include, for example, butyl, pentyl, hexyl, heptyl, octyl, nonyl, and decyl groups. , Undecyl group, dodecyl group,
Tridecyl group, tetradecyl group, pentadecyl group, hexadecyl group, heptadecyl group and the like, octadecyl group and the like.

The aryl group represented by R _H1 and R _H2 is a phenyl group,
A naphthyl group and the like; and an alkenyl group includes a hexenyl group, a heptenyl group and an octadecenyl group. These alkyl group, alkenyl group and aryl group may have a single or plural substituents. Examples of the substituent of the alkyl group and alkenyl group include a halogen atom, an alkoxy group, an aryl group and an aryloxy group. Alkenyl group, alkoxycarbonyl group, and the like.Examples of the substituent of the aryl group include a halogen atom, an alkyl group, an alkoxy group, an aryl group, an aryloxy group,
An alkenyl group and an alkoxycarbonyl group can be exemplified. Two or more of these substituents may be introduced into an alkyl group, an alkenyl group or an aryl group.

Phosphate esters advantageously used in the present invention include those represented by the following general formula [HB].

In the formula, R _H3 , R _H4 and R _H5 each represent an alkyl group, an alkenyl group or an aryl group. Where R
The total number of carbon atoms represented by _H3 , _RH4 and _RH5 is from 24 to 54.

The alkyl groups represented by R _H3 , R _H4 and R _H5 in the general formula [HB] include, for example, butyl, pentyl, hexyl,
Heptyl group, octyl group, nonyl group, decyl group, undecyl group, dodecyl group, tridecyl group, tetradecyl group,
Pentadecyl, hexatedyl, heptadecyl, octadecyl, nonadecyl and the like.

These alkyl group, alkenyl group and aryl group may have a single or plural substituents. Preferably, R _H3 , R _H4 and R _H5 are alkyl groups, for example, 2-ethylhexyl group, n-octyl group, 3,5,5-
Trimethylhexyl group, n-nonyl group, n-decyl group,
Examples thereof include a sec-decyl group, a sec-dodecyl group, a t-octyl group and the like.

Specific examples of the high boiling point organic solvent are shown below, but the present invention is not limited thereto.

Exemplary organic solvent In the present invention, the high boiling organic solvent can be used in the range of 0.01 mol to 10 mol, preferably 0.05 mol to 5 mol, per 1 mol of silver halide.

The silver halide used in the present invention includes silver chloride,
Any silver halide such as silver bromide, silver iodide, silver chlorobromide, silver iodobromide, silver chloroiodide and the like are included.

Silver halide grains preferably used in the present invention, 90
It preferably has a silver chloride content of not less than 10 mol%, a silver bromide content of not more than 10 mol%, and a silver iodide content of not more than 0.5 mol%. More preferably, the silver bromide content is 0.
1 to 2 mol% of silver chlorobromide.

The silver halide grains may be used alone or as a mixture with other silver halide grains having different compositions. Further, it may be used by mixing with silver halide grains having a silver chloride content of 90 mol% or less.

Further, in a silver halide emulsion layer containing silver halide grains having a silver chloride content of 90 mol% or more,
The proportion of silver halide grains having a silver chloride content of 90 mol% or more of the total silver halide grains contained in the emulsion layer is 60 wt% or more, preferably 80 wt% or more.

The composition of the silver halide grains may be uniform from the inside to the outside of the grains, or the inside and outside compositions of the grains may be different. When the inside and outside compositions of the particles are different, the composition may change continuously or may be discontinuous.

The grain size of the silver halide grains is not particularly limited, but is preferably 0.2 to 1.6 μm, more preferably 0.25 to 1.2 μm, in consideration of other photographic properties such as rapid processing property and sensitivity.
m. In addition, the said particle diameter can be measured by various methods generally used in the said technical field. A typical method is the "Land size analysis method" of Loveland (ASTM Symposium on Right.
Microscopy, 1955, pp. 94-122) or "Theory of Photographic Processing" (Mies and James, 3rd ed.)
Edition, Chapter 2 of Macmillan Publishing Company (1966)).

The particle size can be measured using the projected area of the particle or the approximate diameter. If the particles are substantially uniform, the particle size distribution can represent this fairly accurately as diameter or projected area.

The particle size distribution of the silver halide grains may be polydisperse or monodisperse. Monodisperse silver halide grains having a coefficient of variation of preferably 0.22 or less, more preferably 0.15 or less, in the particle size distribution of the silver halide grains are preferred. Here, the coefficient of variation is a coefficient indicating the breadth of the particle size distribution, and is defined by the following equation.

Here, ri represents the particle size of each particle, and ni represents its number. The particle size referred to here is the diameter of a spherical silver halide grain, or the diameter of a cubic or non-spherical grain,
It represents the diameter when the projected image is converted into a circular image having the same area.

In the present invention, the silver halide grains used in the emulsion may be obtained by any of an acidic method, a neutral method and an ammonia method. The particles may be grown at one time, or may be grown after seed particles have been formed.

The method of producing the seed particles and the method of growing may be the same or different.

The form in which the soluble silver salt and the soluble halide salt are reacted may be any of a forward mixing method, a reverse mixing method, a simultaneous mixing method and a combination thereof, but a method obtained by the simultaneous mixing method is preferable. Further, as one form of the double jet method, a pAg-controlled double jet method described in JP-A-54-48521 can be used.

If necessary, a silver halide solvent such as thioether may be used. Further, a compound such as a mercapto group-containing compound, a nitrogen-containing heterocyclic compound or a sensitizing dye may be added at the time of forming silver halide grains or after the completion of grain formation.

The silver halide grains used in the present invention may have any shape. One preferred example is $ 10
It is a cube having a 0 ° plane as the crystal surface. Also, U.S. Pat.Nos. 4,183,756 and 4,225,666, JP-A-55-26
No. 589, Japanese Patent Publication No. 55-42737, etc., and the Journal of Photographic Science (J. Photg)
r. Sci), 21 , 39 (1973), etc., particles having shapes such as octahedral, tetrahedral, and dodecahedral can be prepared and used. Further, particles having a twin plane may be used.

As the silver halide grains used in the present invention, grains having a single shape may be used, or grains having various shapes may be mixed.

In the present invention, the silver halide grains used in the emulsion are formed in a step of forming and / or growing the grains.
Metal ions can be added using cadmium salts, zinc salts, lead salts, thallium salts, iridium salts or complex salts, rhodium salts or complex salts, iron salts or complex salts, and can be included inside the particles and / or on the surface of the particles, In addition, by placing it in a suitable reducing atmosphere, a reduction sensitizing nucleus can be provided inside the grains and / or on the grain surface.

In the emulsion containing silver halide grains, unnecessary soluble salts may be removed after the growth of the silver halide grains is completed, or the emulsion may be kept contained. The removal of the salts can be carried out based on the method described in Research Disclosure No. 17643.

In the present invention, the silver halide grains used in the emulsion may be grains whose latent image is mainly formed on the surface or grains mainly formed inside the grain.
Preferably, the latent image is a particle mainly formed on the surface.

In the present invention, the emulsion is chemically sensitized by a conventional method. That is, a compound containing sulfur capable of reacting with silver ions,
A sulfur sensitization method using active gelatin, a selenium sensitization method using a selenium compound, a reduction sensitization method using a reducing substance, a noble metal sensitization method using gold or another noble metal compound, or the like can be used alone or in combination.

In the present invention, the emulsion can be optically sensitized to a desired wavelength region by using a sensitizing dye.

As the sensitizing dye, a cyanine dye, a merocyanine dye, a complex cyanine dye, a complex merocyanine dye, a holopolar cyanine dye, a hemicyanine dye, a styryl dye, a hemioxazole dye, and the like can be used.

The dye-forming coupler used in the silver halide photographic light-sensitive material of the present invention is usually selected so that a dye absorbing the light in the emulsion spectrum of the emulsion layer is formed for each emulsion layer. A yellow dye-forming coupler is used in the emulsion layer, a magenta coupler dye-forming coupler is used in the green-sensitive emulsion layer, and a cyan dye-forming coupler is used in the red-sensitive emulsion layer. However, a silver halide color photographic light-sensitive material may be prepared in a manner different from the above-mentioned combination depending on the purpose.

In the present invention, an acylacetanilide coupler can be preferably used as the yellow dye-forming coupler. Of these, benzoylacetanilide and pivaloylacetoanilide compounds are advantageous.

In the present invention, the cyan dye-forming coupler is preferably a cyan coupler represented by the following general formula [I] or [II].

In the formula, R ¹ represents an alkyl group or an aryl group. R ² represents an alkyl group, a cycloalkyl group, an aryl group or a heterocyclic group. R ³ represents a hydrogen atom, a halogen atom, an alkyl group or an alkoxy group. R ³ may form a ring together with R ¹ . Z ¹ represents a hydrogen atom or a group capable of leaving by reaction with an oxidized form of an aromatic primary amine color developing agent.

In the formula, R ⁴ represents a ballast group. R ⁵ has 1 to 6 carbon atoms
Represents an alkyl group. Z ² represents a hydrogen atom or a group which can be eliminated by a reaction with an oxidized aromatic primary amine color developing agent.

In the cyan coupler represented by the general formula (I), the alkyl group represented by R ¹ preferably has ¹ to 32 carbon atoms, and these may be linear or branched, and those having a substituent may also be used. Including.

The aryl group represented by R ¹ is preferably a phenyl group, including those having a substituent.

The alkyl group represented by R ² preferably has 1 to 32 carbon atoms. These alkyl groups may be linear or branched, and include those having a substituent.

The cycloalkyl group represented by R ² has 3 to 12 carbon atoms.
Are preferred, and these cycloalkyl groups include those having a substituent.

The aryl group represented by R ² is preferably a phenyl group, including those having a substituent.

The heterocyclic group represented by R ² is preferably a 5- to 7-membered heterocyclic group, including those having a substituent, and may be condensed.

R ² represents a hydrogen atom, a halogen atom, an alkyl group or an alkoxy group, and the alkyl group and the alkoxy group include those having a substituent, and R ₉ is preferably a hydrogen atom.

Further, the ring formed by R ¹ and R ³ together is preferably a 5- to 6-membered ring, and examples thereof include: And the like.

Examples of the group capable of leaving by reaction with an oxidized form of the color developing agent represented by Z ¹ in the general formula [I] include a halogen atom, an alkoxy group, an aryloxy group, an acyloxy group, a sulfonyloxy group, an acylamino group, a sulfonyl group. Examples thereof include an amino group, an alkoxycarbonyloxy group, an aryloxycarbonyloxy group, and an imide group (including those having a substituent), and are preferably a halogen atom, an aryloxy group, or an alkoxy group.

Particularly preferred among the above-mentioned cyan couplers are those represented by the following general formula [IA].

In the formula, R _A1 represents a phenyl group substituted with at least one halogen atom, and these phenyl groups further include those having a substituent other than a halogen atom. R _A2 has the same meaning as R ^{1 in} formula [I]. X _A represents a halogen atom, an aryloxy group or an alkoxy group, including those having a substituent.

Hereinafter, typical specific examples of the cyan coupler represented by the general formula [I] are shown.

Further specific examples of the cyan coupler described above include, for example,
Japanese Patent Application No. 61-21853, pp. 26-35, JP-A-60-225
No. 155, page 7, lower left column to page 10, lower right column, JP-A-60-2
No. 22853, page 6, upper left column to page 8, lower right column;
9-185335, page 2, lower left column to page 9, upper left column, including 2,5-diacylamino cyan couplers,
It can be synthesized according to the methods described in these specifications and publications.

In the present invention, the addition amount of the cyan coupler is preferably from 2 × 10 ^-3 to 8 × 10 ^-1 mol, particularly preferably from 1 × 10 ^{-2 to} 5 × 10 ^-1 mol, per mol of silver halide. .

In the cyan coupler represented by the general formula (II), the alkyl group represented by R ⁵ may be linear or branched,
Those having a substituent are also included. R ⁵ is preferably an alkyl group having 2 to 6 carbon atoms.

The ballast group represented by R ⁴ is an organic group having a size and shape sufficient to give the coupler molecules sufficient bulk to prevent the coupler from substantially diffusing from the layer to which the coupler is applied to other layers. It is.

Preferred as the ballast group are those represented by the following general formula.

R _B1 represents an alkyl group having 1 to 12 carbon atoms;
Represents an aryl group such as a phenyl group, and the aryl group includes those having a substituent.

Z ² has the same meaning as Z ¹ in formula (I).

Next, specific examples of the coupler represented by the general formula [II] are shown, but the invention is not limited thereto.

Specific examples of cyan couplers that can be preferably used in the present invention, including these, are JP-B-49-11572,
JP-A Nos. 61-3142, 61-9652, 61-9563, and 61
-39045, 61-50136, 61-99141, 61-105
No. 545.

The cyan dye-forming coupler represented by the general formula [II] is used in an amount of usually 1 × 10 ^-3 mol to 1 mol, preferably 1 × 10 ^-2 mol to 8 × 10 ^-1 mol, per mol of silver halide. Can be used.

As the binder (or protective colloid) used in the silver halide photographic light-sensitive material of the present invention, gelatin is advantageously used. In addition, gelatin derivatives, graft polymers of gelatin and other polymers, proteins, sugars A hydrophilic colloid such as a derivative, a cellulose derivative, or a synthetic hydrophilic polymer such as a homopolymer or a copolymer can also be used.

The silver halide photographic light-sensitive material of the present invention further comprises a hardening agent, an anti-turbidity agent, an image stabilizer, an ultraviolet absorber, a plasticizer, a latex, a surfactant, a matting agent, a lubricant, an antistatic agent and the like. Additives can be optionally used.

The silver halide photographic light-sensitive material of the present invention can form an image by performing a color development process known in the art.

The color developing agents used in the color developing solution in the development processing of the silver halide photographic light-sensitive material of the present invention include aminophenol-based and p-phenylenediamine-based derivatives widely used in various color photographic processes. .

In addition to the above-mentioned primary aromatic amine-based color developing agent, a known developer component compound can be added to the color developing solution applied to the development processing of the silver halide photographic light-sensitive material of the present invention. .

The pH value of the color developer is usually 7 or higher, most usually about 10 to 13.

The color development temperature is usually 15 ° C. or higher, and is generally 20 to
It is in the range of 50 ° C. For rapid development, it is preferred to carry out at 30 ° C. or higher.

Further, the silver halide photographic light-sensitive material of the present invention is preferably processed with a color developing solution containing no benzyl alcohol.

The silver halide photographic light-sensitive material of the present invention, after color development,
Bleaching and fixing are performed. The bleaching process may be performed simultaneously with the fixing process.

 After the fixing process, a washing process is usually performed.

Further, as an alternative to the water washing treatment, a stabilization treatment may be performed, or both may be used in combination.

〔Example〕

Hereinafter, specific examples of the present invention will be described, but embodiments of the present invention are not limited thereto.

Example 1 (Preparation of Silver Halide Emulsion) Six types of silver halide emulsions shown in Table 1 were prepared by a neutral method and a double jet method.

After the completion of chemical sensitization, each of the silver halide emulsions was added with the following STB-1 as an emulsion stabilizer in an amount of 2 × 10 ^-4 mol per mol of silver halide.

(Preparation of a silver halide color photographic light-sensitive material) Each layer having the constitution shown in Table 1 was formed on a support obtained by laminating polyethylene on one side of a paper support and polyethylene containing titanium oxide on the other side of the first layer. To prepare a multilayer silver halide color photographic light-sensitive material. The coating solution was prepared as follows.

First layer coating solution 60 ml of ethyl acetate was added and dissolved in 26.7 g of yellow coupler (Y-1), 0.67 g of stain inhibitor (HQ-1) and 13.3 g of high boiling point organic solvent (DNP). A 200% aqueous 10% gelatin solution containing 10 ml of sodium naphthalenesulfonate was emulsified and dispersed using a homogenizer to prepare a yellow coupler dispersion.

This dispersion was mixed with a blue-sensitive silver chlorobromide emulsion (10 g of Em-1 in terms of silver) and a gelatin solution for coating to prepare a first layer coating solution.

The coating liquids for the second to seventh layers were prepared in the same manner as in the first layer coating liquid. However, the magenta coupler dispersion used for the third layer coating solution was prepared as follows.

Magenta coupler dispersion (dispersion of document No. 112) Magenta coupler (M-21) 12.0 g, dye image stabilizer (ST-1) 6.0 g, dye image stabilizer (ST-2) 3.0 g, stain inhibitor (HQ -1) 40 g of ethyl acetate was added to 0.3 g, 9.0 g of a high boiling organic solvent (DOP) and 9.0 g of the exemplary compound (A-2) of the present invention having an average molecular weight of about 60,000 to dissolve the solution. A magenta coupler dispersion was prepared by emulsifying and dispersing in 200 ml of a 10% aqueous gelatin solution containing 10 ml of sodium sulfonate using a homogenizer. Further, the following compound (H-1) was added as a hardening agent for gelatin at 0.08 g / m ² .

The obtained sample was subjected to wedge exposure using green light using a sensitometer KS-7 (manufactured by Konica Corporation), processed according to the following color development process, and then evaluated as follows.

[Processing step] Color development 3 minutes 30 seconds Temperature 33 ° C Bleaching and fixing 1 minute 30 seconds Temperature 33 ° C Water washing 3 minutes Temperature 33 ° C Formulation of color developing solution N-ethyl-N-β-methanesulfonamidoethyl-3
-Methyl-4-aminoaniline sulfate 4.9 g hydroxylamine sulfate 2.0 g potassium carbonate 25.0 g sodium bromide 0.6 g anhydrous sodium sulfite 2.0 g benzyl alcohol 13 ml polyethylene glycol (average degree of polymerization 400) 3.0 ml Add water to make 1 And adjust to pH 10.0 with sodium hydroxide.

Formulation of bleach-fixing solution Sodium salt of iron (III) ethylenediaminetetraacetate 6.0 g Ammonium thiosulfate 100 g Sodium bisulfite 10 g Sodium metabisulfite 3 g Add water to adjust the pH to 1, and adjust the pH to 7.0 with aqueous ammonia.

<Light resistance> The obtained sample was stored under sunlight (exposure table) for one month under the conditions of 60 ° C and 70% RH, and the density reduction rate (%) of the dye image at an initial density of 1.0 was evaluated. .

<Sensitivity> Expressed as the reciprocal of the exposure required to obtain a density of 0.8, and expressed as a relative sensitivity when the sensitivity of the reference sample is taken as 100.

<Sweating> The obtained sample was stored at 85 ° C. and 60% RH for 10 days.
The gloss deterioration due to perspiration of the oil on the sample surface was visually evaluated.

◎ "Sweating" is not seen.

○ "Sweating" is hardly observed.

△ Slight "sweating" is observed, but acceptable as a product.

× "Sweating" is quite noticeable and not a product.

XX "Sweating" severely impairs image quality.

 Table 2 shows the results.

As is clear from Table 2, in Samples Nos. 101 to 109 using the comparative couplers, Samples Nos. 102, 105 and 108 using only the polymer compound of the present invention were all light-fast against samples using no polymer compound. Is improved, but the effect is small, and the sensitivity is reduced. Samples Nos. 103, 106, and 109, which used a high boiling point organic solvent in combination, had a small decrease in sensitivity, but had perspiration and image quality was impaired. On the other hand, when the magenta coupler of the present invention was used, Sample Nos. 111, 113 and 11 of the present invention using the polymer compound of the present invention were used.
It can be seen that samples Nos. 5 to 120 are all good samples in which sweating is suppressed, the effect of improving light resistance is large, and the decrease in sensitivity is small. Furthermore, when compared among the samples of the present invention, the polymer compound of the present invention and the dielectric constant preferably used in the present invention are shown.
Samples No. 111 and 11 using a high boiling point organic solvent of less than 6.0
Samples Nos. 3 and 115 to 118 are sensitive to Sample No. 111 not using a high-boiling organic solvent, and Samples Nos. 119 and 120 using a high-boiling organic solvent having a dielectric constant of 6.0 or more. It can be seen that they are excellent in light resistance. Also, the molecular weight
Sample N using the magenta coupler of the present invention of 550 or less
o.111, 113 and 115 to 120 were found to be excellent samples having no perspiration, and the sample No. using the preferred magenta coupler of the present invention having a substituent represented by the general formula (MX) was used. It can be seen that samples 115 to 120 are excellent in sensitivity.

Example-2 Blue-sensitive silver chlorobromide emulsion Em- of the first layer in Example-1
1. The green-sensitive bromide emulsion Em-2 of the third layer and the red-sensitive silver chlorobromide emulsion Em-3 of the fifth layer were em-emitters Em-4, Em-5 and Em-
6 and a multilayer silver halide color photographic material was prepared in the same manner as in Example 1 except that the magenta coupler, the polymer compound and the high boiling point organic solvent in the third layer were further changed as shown in Table 3. .

The obtained sample was subjected to wedge exposure in the same manner as in Example 1, and processed according to the following color development processing step, followed by the same evaluation as in Example-1.

 The results are shown in Table-3.

[Processing process] Temperature Time Color development 35.0 ± 0.3 ° C 45 seconds Bleaching and fixing 35.0 ± 0.5 ° C 45 seconds Stabilization 30-34 ° C 90 seconds Drying 60-80 ° C 60 seconds Color developing solution Pure water 800ml Triethanolamine 10g N, N -Diethylhydroxyamine 5 g Potassium bromide 0.02 g Potassium chloride 2 g Potassium sulfite 0.3 g 1-hydroxyethylidene 1,1-diphosphonic acid 1.0 g Ethylenediaminetetraacetic acid 1.0 g Catechol-3,5-disulfonic acid disodium salt 1.0 g N-ethyl -N-β-methanesulfonamidoethyl-3-methyl-4-aminoaniline sulfate 4.5 g Fluorescent whitening agent (4-4′-cyaminostilbene disulfonic acid derivative) 1.0 g Potassium carbonate 27 g Adjust to pH = 10.10.

Bleaching and fixing solution Ethylenediaminetetraacetic acid Ferric ammonium dihydrate 60g Ethylenediaminetetraacetic acid 3g Ammonium thiosulfate (70% aqueous solution) 100ml Ammonium sulfite (40% aqueous solution) 27.5ml Add water to 1 and adjust the pH to 1 with potassium carbonate or glacial acetic acid.
Adjust to 6.2.

Stabilizing solution 5-chloro-2-methyl-4-isothiazolin-3-one 1.0 g ethylene glycol 1.0 g 1-hydroxyethylidene-1,1-diphosphonic acid 2.0 g ethylenediaminetetraacetic acid 1.0 g ammonium hydroxide (20% aqueous solution) 3.0 g Ammonium sulfite 3.0 g Fluorescent whitening agent (4,4'-diaminostilbenzisulfonic acid derivative) 1.5 g Add water to make 1 and add sulfuric acid or potassium hydroxide to pH =
Adjust to 7.0.

As is clear from Table-3, in the samples using the comparative coupler, the samples using only the polymer compound of the present invention have improved light fastness as compared with the samples not using the polymer compound, but the effect is high. Is small and the sensitivity is reduced. A sample using a high-boiling organic solvent in combination has a small decrease in sensitivity, but has perspiration and impairs image quality.
In contrast, when the magenta coupler of the present invention is used,
It can be seen that all of the samples of the present invention using the polymer compound of the present invention have suppressed sweating properties, a large effect of improving light resistance, and a small decrease in sensitivity. Furthermore, when compared among the samples of the present invention, a sample in which a polymer compound of the present invention and a high-boiling organic solvent having a dielectric constant of less than 6.0 preferably used in the present invention are used in combination is a sample in which a high-boiling organic solvent is not used in combination. It can be seen that the sensitivity is excellent. Further, the sample using the magenta coupler of the present invention having a molecular weight of 550 or less was found to be an excellent sample having no sweating property, and the sample having the substituent represented by [MX] in the general formula was used. It can be seen that the sample using the preferred magenta coupler of the present invention is excellent in sensitivity. Also, the magenta coupler of sample No. 215 was changed to M-4, M-16, M-18, M-20, M-21,
The effects of the present invention were also obtained for samples in which the polymer compounds were replaced with A-5 and A-77, respectively.

Example 3 The magenta coupler in the third layer of the sample No. 209 of Example 2 was changed to a comparative coupler 6 shown below, and the amount of the green-sensitive silver chlorobromide emulsion in the third layer was converted to silver. A sample No. 301 was obtained in the same manner as in Example 2 except that the amount was 0.31 g / m ² .

Next, a negative film obtained by photographing and developing a color checker (manufactured by Macbeth) with Konica Color GX100 (manufactured by Konica Corporation) was adjusted to the gray tone, and then printed on the above sample Nos. 209 and 301. Then, the color reproducibility in each hue was evaluated.

As a result, it was found that sample No. 212 was more favorable for blue, red and magenta.

Example 4 Equimolar silver nitrate aqueous solution and potassium bromide aqueous solution were simultaneously added to a gelatin aqueous solution at 50 ° C. for 50 minutes by a double jet method to obtain an emulsion comprising cubic silver bromide particles having an average particle size of 0.15 μm. Obtained. This emulsion is further mixed with an aqueous solution of silver nitrate and a mixed aqueous solution of sodium chloride and potassium bromide (molar ratio 1: 1).
At the same time, a cubic core / shell emulsion comprising a silver bromide core having an average particle size of 0.225 μm and a silver chlorobromide shell (EM
P-1) was adjusted.

A core / shell type emulsion as shown in Table 4 below was prepared by changing the addition time of an aqueous solution of silver nitrate and an aqueous solution of a halogen salt in addition to the above emulsion.

Using the obtained emulsions EMP-1 to EMP-4 as supports, an emulsion layer having the composition shown in Table 5 and a non-emulsion layer in order from the first layer were formed on a paper support having a thickness of 140 μm and coated on both sides with polyethylene. And a backing layer were applied to directly produce a positive color photosensitive material.

In the table, the amount of addition is shown in mg / dm ² . However, silver halide emulsion and yellow colloidal silver are silver equivalent values.

In the emulsion layer side and the back layer, HA-1,
HA-2 was used.

(Additives used) The light-sensitive material prepared as described above was subjected to green exposure through a wedge, and then processed according to the following processing steps. Example 1 of the obtained data
The light resistance and the perspiration were evaluated in the same manner as described above. Table 6 shows the obtained results.

Processing step (processing temperature and processing time) (1) Immersion (color developing solution) 38 ° C for 8 seconds (2) Fog exposure-10 seconds at 1 lux (3) Color developing 38 ° C for 2 minutes (4) Bleaching and fixing 35 ° C 60 Seconds (5) Stabilization treatment 25-30 ° C 1 minute 30 seconds (6) Drying 75-80 ° C 1 minute (Processing solution composition) Color developing solution Benzyl alcohol 10ml Ethylene glycol 15ml Potassium sulfite 2.0g Potassium bromide 1.5g Sodium chloride 0.2 g potassium carbonate 30.0 g hydroxylamine sulfate 3.0 g polyphosphoric acid (TPPS) 2.5 g N-ethyl-N-β-methanesulfonamidoethyl-3-methyl-4-aminoaniline sulfate 5.0 g fluorescent brightener (4 1,4'-diaminostil benzisulphonic acid derivative) 1.0 g Potassium hydroxide 2.0 g Water is added to make the total volume 1 and adjusted to pH 10.20.

Bleach-fix solution Ethylenediaminetetraacetic acid Ferric ammonium dihydrate 60g Ethylenediaminetetraacetic acid 3g Ammonium thiosulfate (70% solution) 100ml Ammonium sulfite (40% solution) 27.5ml Add water to make the total volume 1 and add potassium carbonate or glacial acetic acid. Adjust to pH 7.1.

Stabilizing solution 5-chloro-2-methyl-4-isothiazolin-3-one 1.0 g ethylene glycol 10 g 1-hydroxyethylidene-1,1-diphosphonic acid 2.5 g bismuth chloride 0.2 g magnesium chloride 0.1 g ammonium hydroxide (28% aqueous solution) 2.0 g Sodium nitrilotriacetate 1.0 g Add water to make the total amount 1 and adjust to pH 7.0 with ammonium hydroxide or sulfuric acid.

 In addition, the stabilization process was a countercurrent system having a two-tank configuration.

As is clear from Table 6, when the comparative coupler is used, the use of the polymer compound of the present invention improves the light resistance but deteriorates the degree of perspiration. On the other hand, when the coupler and the polymer compound of the present invention are used, the effect of improving the light resistance is large, and the sweating property is also effectively prevented.

〔The invention's effect〕

According to the present invention, a silver halide photographic light-sensitive material excellent in color reproducibility and light fastness and preventing deterioration of image quality due to perspiration is obtained.

Claims (1)

(57) [Claims] 1. A silver halide photographic material having at least one silver halide emulsion layer on a support, wherein at least one of said silver halide emulsion layers has the following general formula [M
-I] a halogen characterized by containing lipophilic fine particles obtained by emulsifying and dispersing a magenta coupler having a molecular weight of 400 to 550 and a water-insoluble and organic solvent-soluble polymer compound. Silver halide photographic material. General formula [MI] [In the formula, Z represents a group of nonmetallic atoms necessary for forming a nitrogen-containing heterocyclic ring, and the ring formed by Z may have a substituent. X represents a hydrogen atom or a group capable of leaving by reaction with an oxidized form of a color developing agent. R represents a hydrogen atom or a substituent. ]