JPH0690473B2 - Silver halide color photographic light-sensitive material - Google Patents

Description

TECHNICAL FIELD The present invention relates to a silver halide color photographic material, and more specifically, it has excellent color reproducibility and latent image stability after photographing. The present invention relates to a silver halide color photographic light-sensitive material.

(Prior Art) A silver halide color photographic light-sensitive material generally has a silver halide emulsion layer that is sensitive to each of the three primary colors of blue, green, and red, and each of them develops yellow, magenta, and cyan, resulting in so-called color reduction. Method is used to reproduce a color image, and thus the reproduced color image largely depends on the color-sensitive property of each layer and the spectral absorption property of color development. In general, these properties are not always the best in theory due to restrictions such as color developability on the compound used. In particular, the coloring hue of the magenta coupler is important for color reproduction, and various improvements have been made. Among them, the pyrazoloazole-based magenta coupler is particularly excellent in the spectral absorption property of the coloring hue.

For example, in order to improve the coloring hue of the magenta coupler,
In the pyrazolone type, anilino type magenta couplers (JP-A-49-74027, JP-A-49-111631 and the like) having superior spectral absorption characteristics have been developed rather than ureido type and acylamino type. Furthermore, a pyrazoloazole type magenta coupler (US Pat. No. 3,725,067 etc.) with less unnecessary side absorption has been developed. This type of coupler has a blue light range as compared with a color image obtained from a 5-pyrazolone type magenta coupler,
There is little unnecessary absorption in the red light range, not only is it advantageous for color reproduction, but the coupler itself is stable against light, heat, temperature,
Perhaps because it is difficult to decompose, the obtained image has little yellowing.

(Problems to be Solved by the Invention) As described above, the pyrazoloazole-based magenta coupler has 5
-Compared to pyrazolone-type magenta couplers, they have excellent properties, but on the other hand, those having high color-developing performance that can be put to practical use have a drawback that sensitivity is lowered between shooting and development. is doing.

General latent image regression after photographing is described, for example, in JH James's The Theory of the Photographic Process 4th Edition.
However, the above-mentioned latent image regression and deterioration of photographic property due to the pyrazoloazole-based magenta coupler are the first findings of the present inventors.

Therefore, the present invention takes advantage of the advantages of the pyrazoloazole-based magenta couplers (good color, difficulty in producing fading stains, etc.), and silver halide color photographic light-sensitive material having improved latent image degrading property, which is a drawback thereof. The purpose is to provide.

More specifically, a first object is to provide a color photographic light-sensitive material having a more excellent color reproducibility by using a magenta color image having a good spectral absorption characteristic.

A second object of the present invention is to provide a color photographic light-sensitive material which has a solid color image and has improved yellowing of a white background. A third object is to provide a photographic light-sensitive material with less latent image regression.

(Means for Solving the Problems) The inventors of the present invention have conducted extensive studies to develop a silver halide color photographic light-sensitive material satisfying such demands, and as a result, pyrazoloazole-based magenta having a specific structure. It has been found that this can be achieved by combining a coupler with certain quaternary salt type compounds. The present invention has been accomplished based on this finding.

That is, an object of the present invention is to have a layer containing at least one kind of magenta coupler represented by the following general formula (I), wherein at least one layer contains a compound represented by the following general formula (IIa) or (IIb). It was achieved by the following silver halide color photographic light-sensitive material.

General formula (I) (In the formula, Za and Zb are Or, it represents = N-, R ¹ and R ² represent a hydrogen atom or a substituent, and X represents a hydrogen atom or a group capable of splitting off by a coupling reaction with an oxidized product of an aromatic primary amine developing agent. When Za = Zb is a carbon-carbon double bond, it may be a part of an aromatic ring, and R ¹ , R ² or X may form a dimer or higher multimer. . However, R ¹
Or at least one of R ² is represents the group attached to the pyrazoloazole nucleus through a secondary or tertiary carbon, and R ¹ or R ² is at least one -NHSO ₂ - containing group. ) General formula (IIa) And the general formula (IIb) (In the formula, Z ¹ and Z ² each independently represent an atomic group necessary for forming an imidazole ring, a pyridine ring, a thiazole ring or a selenazole ring, and these may be combined. R ³ and R ⁵ Each represents an optionally substituted alkyl group, an alkenyl group, an aralkyl group or an aryl group, R ⁴ represents a hydrogen atom or an optionally substituted alkyl group, and R ³ and R ⁴ form a ring. L represents a divalent linking group, X ⁻ represents an acid anion, m represents 0 or 1, and n represents 0, 1 or 2.) In the general formula (IIa) or (IIb), The compounds represented will be explained in detail.

When the above compound forms an inner salt, m is 0, n
Is 0 or 1 when an inner salt is formed. n is 1
Is a case where a partial inner salt is formed.

The heterocyclic ring completed by Z ¹ and Z ² may have a substituent other than the 2-position or 3-position, and may be condensed with another carbocycle (5 to 7 members). Examples of the substituent include an alkyl group, an alkoxy group (both having 18 or less carbon atoms), and an aryl group (monocyclic or bicyclic). The condensed ring is, for example, a benzene ring, a naphthalene ring, a cyclohexene ring, an azulene ring or a cycloheptene ring. These heterocyclic nuclei may be further substituted.

For example, a halogen atom (eg chlorine, bromine), carbon number 1 to
18 alkyl groups (eg methyl group, ethyl group, heptadecyl group), alkoxy groups having 1 to 18 carbon atoms (eg methoxy group, ethoxy group, heptadecyloxy group), 2 carbon atoms
~ 18 alkoxycarbonyl group (eg methoxycarbonyl group, ethoxycarbonyl group), carboxy group, cyano group, trifluoromethyl group, nitro group, sulfo group, phenyl group (may be substituted), acyl having up to 18 carbon atoms Group (eg, acetyl group, alkylcarbonyl group such as propionyl group; eg, alkylsulfonyl group such as methylsulfonyl group), sulfamoyl group, sulfamoyl group mono- or di-substituted with alkyl group or aryl group (eg methylsulfamoyl group) Group, benzenesulfamoyl group), carbamoyl group (for example, methylcarbamoyl group, dimethylcarbamoyl group, ethylcarbamoyl group, phenylcarbamoyl group), hydroxy group,
It can have an alkylthio group having up to 18 carbon atoms as a substituent.

The alkyl group, alkenyl group, aralkyl group and aryl group represented by R ³ or R ⁵ preferably have 1 to 8 carbon atoms.

Examples of the alkyl group represented by R ³ and R ⁵ include a methyl group, an ethyl group, a propyl group, a butyl group, and a hexyl group, and examples of the alkenyl group represented by R ³ and R ⁵ include an allyl group. the aralkyl group represented by R ^3, R ^5, for example, benzyl group, phenethyl group, the aryl group represented by R ^3, R ⁵ include a phenyl group, R ³ and R ⁵ may be substituted Examples of the substituent include a halogen atom (eg, chlorine atom, bromine atom), cyano group, sulfonyl group, carboxy group, phospho group, alkoxycarbonyl group (eg, ethoxycarbonyl group), acyloxy group (eg, acetoxy group), alkoxy group. (Eg, methoxy group, ethoxy group), hydroxy group,
Alkylthio group (eg methylthio group), carbamoyl group, substituted carbamoyl group (eg dimethylcarbamoyl group, ethylcarbamoyl group, phenylcarbamoyl group), sulfamoyl group, substituted sulfamoyl group (eg dimethylsulfamoyl group, ethylsulfamoyl group) Moyl group, phenylsulfamoyl group), hetero residue (for example, 3-thiazolyl group, 3-benzothiazolyl group,
6-methoxy-3-benzothiazolyl group) and the like. As the alkyl group substituted with the above heterocyclic residue, the residue represented by the following general formula is useful.

In the formula, Z ¹ , R ⁴ , X ⁻ and m have the same meanings as in the general formula (IIa). A may have a branch or a substituent. Carbon number
Represents up to 18 alkylene groups. When R ³ represents an alkenyl group, the carbon atom bonded to the nitrogen atom is preferably saturated.

The alkyl group represented by R ⁴ has 1 to 6 carbon atoms, may have a branch, and may be substituted. In this case, the substituent which can be possessed is, for example, a halogen atom (eg chlorine atom), a hydroxy group, an alkoxy group having 1 to 5 carbon atoms (eg methoxy group), an alkylthio group having 1 to 5 carbon atoms (eg methylthio group), Carboxy group, sulfo group, alkoxycarbonyl group having 2 to 5 carbon atoms, 2 carbon atoms
~ 5 alkylcarbonyloxy groups (eg acetoxy groups) and the like.

Specific examples of the alkyl group represented by R ⁴ include a methyl group, an ethyl group, a propyl group, a butyl group, a methoxy group, a methyl group,
Acetoxymethyl group, methoxycarbonylmethyl group, chloromethyl group, bromomethyl group, 2-chloroethyl group,
2-bromoethyl group, hydroxyethyl group, methylthiomethyl group, methylthioethyl group, carboxyethylthiomethyl group.

The ring formed when R ³ and R ⁴ are bonded is preferably a 5- or 6-membered ring and may have an oxygen atom or a sulfur atom in the ring in addition to the nitrogen atom.

Specific examples of the ring formed by R ³ and R ⁴ are a pyrroline ring, a thiazoline ring, a tetrahydropyridine ring and the like.

The acid anion represented by X ⁻ may be an inorganic acid anion or an organic acid anion. For example, chlorine ion, bromine ion,
Inorganic acid anions such as element ions, sulfate ions, nitrate ions and perchlorate ions, and organic acid anions such as methylsulfate ion and paratoluenesulfonate ion may be used.

When the compound of formula (IIa) or formula (IIb) forms an intramolecular salt, it is not necessary to have an acid anion as a counter ion outside the molecule, and therefore n is 1 or 0.

In the general formula (IIb), the divalent linking group represented by L has 1 to 12 carbon atoms and may include a saturated or unsaturated ring (for example, a benzene ring), and has a branch or a substituent. Good.

A divalent hydrocarbon group is preferred. Examples of the substituent are a hydroxy group, a chlorine atom and a phenyl group. Those in which the carbon chain is interrupted by an oxygen atom or a sulfur atom are also included.
Specific examples of the divalent hydrocarbon group represented by L is an ethylene group, butylene group, a 1,4-phenylene _{group, -CH 2 CH 2 -O-CH} 2 CH 2 -, -CH 2 CH 2 -S-CH 2 CH ₂ − etc.

Among the compounds represented by the general formula (IIa), particularly useful compounds are represented by the following general formula (IIc).

(IIc) In the formula, W represents a sulfur atom or a selenium atom, and a sulfur atom is particularly preferable. R ³ , R ⁴ and X ^- have the same meaning in formula (IIa).

R ⁶ and R ⁷ are hydrogen atom, halogen atom (eg chlorine atom, bromine atom), nitro group, cyano group, sulfo group, carboxy group, alkoxycarbonyl group having 2 to 18 carbon atoms (eg ethoxycarbonyl group, butoxycarbonyl group) ),
C2-C18 acyl group (eg acetyl group), C1-C18 alkyl group (eg methyl group, ethyl group, n-
Butyl group, heptyl group, decyl group), alkoxy group having 1 to 18 carbon atoms (eg methoxy group, butoxy group, heptadecyloxy group), alkylthio group having 1 to 18 carbon atoms (eg methylthio group, butylthio group), carbon Number 2-18 acylamino group (for example, acetylamino group, capryloylamino group, heptadecanoylamino group), hydroxy group,
It represents a phenyl group which may be substituted or an aralkyl group having 7 to 12 carbon atoms. R ⁶ and R ⁷ may be bonded to each other (eg, methylenedioxy group, ethylenedioxy group).
R ⁶ and R ⁷ may form an aromatic ring such as a benzene ring. Particularly preferred compounds are those in which R ⁴ is a hydrogen atom in the general formula (IIc).

The compounds represented by the above general formulas (IIa) and (IIb) which can be used in the present invention are described in, for example, US Pat.
1,038, 2,334,864, 2,425,774, 2,500,110
No. 2,694,716 and the like. Next, specific examples of the above compounds will be shown.

Preferred embodiments of the present invention will be described below. A desirable ratio of the magenta coupler represented by the general formula (I) (hereinafter referred to as compound (I)) to 1 mol of silver halide in the magenta color forming layer is 0.05 to 5 mol. The weight ratio of the high boiling point solvent to the pyrazoloazole magenta coupler is preferably 0 to 6.0.

The addition layer of the compound represented by the general formula (IIa) or (IIb) (hereinafter referred to as compound (II)) may be any layer in the light-sensitive material, and may be divided into two or more layers and added. Good, but desirably added to the layer containing compound (I).

The desirable addition amount of the compound (II) is 10 ^-7 mol to 10 ^-1 mol, and more preferably 10 ^-5 mol to 10 ^-2 mol, relative to 1 mol of silver halide in the layer containing the compound (I). Is the range.

In the magenta coupler represented by the above general formula (I) used in the present invention, Za is preferably And when Zb is ═N—, R ² is a group other than a substituted or unsubstituted aralkyl group.

In the compound represented by the general formula (I), a multimer is 1
It means one having two or more groups represented by the general formula (I) in the molecule, and a bis form and a polymer coupler are also included in this. Here, the polymer coupler has the general formula (I)
A homopolymer consisting only of a monomer having a moiety represented by (preferably a vinyl group, hereinafter referred to as a vinyl monomer) may be used, or a non-coupling compound that does not couple with an oxidized aromatic primary amine developing agent. You may make a copolymer with a color forming ethylene-like monomer.

Among the pyrazoloazole-based magenta couplers represented by the general formula (I), preferred are those represented by the following general formula (II
It is represented by I), (IV), (V), (VI) and (VII).

Among the couplers represented by the general formulas (III) to (VII),
Preferred for the purposes of the present invention are the general formulas (III), (V)
And (VI), more preferred are those represented by the general formula (V
It is represented by I).

In formulas (III) to (VII), R ¹¹ , R ¹² and R ¹³ may be the same or different and each is a hydrogen atom,
Halogen atom, alkyl group, aryl group, heterocyclic group,
Cyano group, alkoxy group, aryloxy group, heterocyclic oxy group, acyloxy group, carbamoyloxy group, silyloxy group, sulfonyloxy group, acylamino group,
Anilino group, ureido group, imide group, sulfamoylamino group, carbamoylamino group, alkylthio group, arylthio group, heterocyclic thio group, alkoxycarbonylamino group, aryloxycarbonylamino group, sulfonamide group, carbamoyl group, acyl group , A sulfamoyl group, a sulfonyl group, a sulfinyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, X is a hydrogen atom, a halogen atom, a carboxy group or an oxygen atom,
It represents a group capable of coupling off with a group bonded to carbon at the coupling position via a nitrogen atom or a sulfur atom.
R ¹¹ , R ¹² , R ¹³ or X may be a divalent group to form a bis form.

Further, it may be in the form of a polymer coupler in which the coupler residue represented by the general formulas (III) to (VII) is present in the main chain or side chain of the polymer, and is particularly derived from a vinyl monomer having a moiety represented by the general formula. Polymers are preferred, in which R ¹¹ , R ¹² , R ¹³ or X represents a vinyl group or a linking group.

More specifically, R ¹¹ , R ¹² and R ¹³ are each a hydrogen atom, a halogen atom (eg, chlorine atom, bromine atom, etc.), an alkyl group (eg, methyl group, propyl group, isopropyl group, t-butyl group, trifluoro group). Methyl group, tridecyl group, 2- [α- {3- (2-octyloxy-5-tert
-Octylbenzenesulfonamide) phenoxy} tetradecanamide] ethyl group, 3- (2,4-di-t-amylphenoxy) propyl group, allyl group, 2-dodecyloxyethyl group, 1- (2-octyloxy-5) −tert−
Octylbenzenesulfonamide) -2-propyl group,
1-ethyl-1- {4- (2-butoxy-5-tert-octylbenzenesulfonamide) phenyl} methyl group,
3-phenoxypropyl group, 2-hexylsulfonyl-
Ethyl group, cyclopentyl group, benzyl group, etc., aryl group (for example, phenyl group, 4-t-butylphenyl group, 2,4-di-t-amylphenyl group, 4-tetradecaneamidophenyl group, etc.), heterocycle Group (eg, 2-furyl group, 2-thienyl group, 2-pyrimidinyl group, 2-benzothiazolyl group, etc.), cyano group, alkoxy group (eg, methoxy group, ethoxy group, 2-methoxyethoxy group, 2-dodecyloxy) Ethoxy group, 2-methanesulfonylethoxy group, etc.), aryloxy group (eg, phenoxy group, 2-methylphenoxy group, 4-t-butylphenoxy group, etc.), heterocyclic oxy group (eg, 2-benzimidazolyloxy group, etc.) ), An acyloxy group (eg, acetoxy group, hexadecanoyloxy group, etc.), a carbamoyloxy group (eg, , N-phenylcarbamoyloxy group, N-ethylcarbamoyloxy group etc.), silyloxy group (eg trimethylsilyloxy group etc.), sulfonyloxy group (eg dodecylsulfonyloxy group etc.), acylamino group (eg acetamide group, benzamide) Group, tetradecanamide group, α-
(2,4-di-t-amylphenoxy) butyramide group,
γ- (3-t-butyl-4-hydroxyphenoxy) butyramide group, α- {4- (4-hydroxyphenylsulfonyl) phenoxy} decanamide group, etc., anilino group (for example, phenylamino group, 2-chloroanilino group, 2-chloro-5-tetradecanamido anilino group,
2-chloro-5-dodecyloxycarbonylanilino group, N-acetylanilino group, 2-chloro-5- {α-
(3-t-butyl-4-hydroxyphenoxy) dodecanamide} anilino group etc.), ureido group (eg phenylureido group, methylureido group, N, N-dibutylureido group etc.), imide group (eg N- Succinimide group, 3-benzylhydantoinyl group, 4- (2-ethylhexanoylamino) phthalimide group, etc.), sulfamoylamino group (for example, N, N-dipropylsulfamoylamino group, N-methyl-decyl Sulfamoylamino group, etc.), alkylthio group (eg, methylthio group, octylthio group, tetradecylthio group, 2-phenoxyethylthio group, 3-phenoxypropylthio group, 3- (4-
t-butylphenoxy) propylthio group, etc.), arylthio group (eg, phenylthio group, 2-butoxy-5-)
t-octylphenylthio group, 3-pentadecylphenylthio group, 2-carboxyphenylthio group, 4-tetradecanamidophenylthio group, etc.), heterocyclic thio group (eg, 2-benzothiazolylthio group, etc.), alkoxy Carbonylamino group (eg, methoxycarbonylamino group, tetradecyloxycarbonylamino group, etc.), aryloxycarbonylamino group (eg, phenoxycarbonylamino group, 2,4-di-tert-butylphenoxycarbonylamino group, etc.), sulfone An amide group (for example,
Methanesulfonamide group, hexadecanesulfonamide group, benzenesulfonamide group, p-toluenesulfonamide group, octadecanesulfonamide group, 2-methyloxy-5-t-butylbenzenesulfonamide group, etc.), carbamoyl group (for example, N-ethylcarbamoyl group, N, N-dibutylcarbamoyl group, N- (2-dodecyloxyethyl) carbamoyl group, N-methyl-dodecylcarbamoyl group, N- {3- (2,4-di-tert-amylphenoxy) ) Propyl} carbamoyl group, etc.), acyl group (eg, acetyl group, (2,4-di-tert-amylphenoxy) acetyl group, benzoyl group, etc.), sulfamoyl group (eg, N-ethylsulfamoyl group, N , N
-Dipropylsulfamoyl group, N- (2-dodecyloxyethyl) sulfamoyl group, N-ethyl-N-dodecylsulfamoyl group, N, N-diethylsulfamoyl group, etc., sulfonyl group (for example, methanesulfonyl) Base,
Octanesulfonyl group, benzenesulfonyl group, toluenesulfonyl group, etc.), sulfinyl group (eg, octansulfinyl group, dodecylsulfinyl group, phenylsulfinyl group, etc.), alkoxycarbonyl group (eg, methoxycarbonyl group, butyloxycarbonyl group, dodecyl) Carbonyl group, octadecylcarbonyl group, etc.), an aryloxycarbonyl group (for example, phenyloxycarbonyl group, 3-pentadecyloxy-carbonyl group, etc.), X is a hydrogen atom, a halogen atom (for example, a chlorine atom, a bromine atom, Groups such as iodine atom), carboxy group, or oxygen atom (eg, acetoxy group, propanoyloxy group, benzoyloxy group, 2,
4-dichlorobenzoyloxy group, ethoxooxaloyloxy group, pyrvinyloxy group, cinnamoyloxy group, phenoxy group, 4-cyanophenoxyl group, 4-methanesulfonamidophenoxy group, 4-methanesulfonylphenoxy group, α -Naphthoxy group, 3-pentadecylphenoxy group, benzyloxycarbonyloxy group, ethoxy group, 2-cyanoethoxy group, benzyloxy group,
2-phenethyloxy group, 2-phenoxyethoxy group,
5-phenyltetrazolyloxy group, 2-benzothiazolyloxy group, etc.), groups linked by nitrogen atoms (for example, benzenesulfonamide group, N-ethyltoluenesulfonamide group, heptafluorobutanamide group, 2, 3,4,5,6
-Pentafluorobenzamide group, octanesulfonamide group, p-cyanophenylureido group, N, N-diethylsulfamoylamino group, 1-piperidyl group, 5,5-
Dimethyl-2,4-dioxo-3-oxazolidinyl group,
1-benzyl-ethoxy-3-hydantoinyl group, 2N-
1,1-dioxo-3 (2H) -oxo-1,2-benzisothiazolyl group, 2-oxo-1,2-dihydro-1-pyridinyl group, imidazolyl group, pyrazolyl group, 3,5-diethyl- 1,2,4-triazol-1-yl, 5- or 6-
Bromo-benzotriazol-1-yl, 5-methyl-
1,2,3,4-triazol-1-yl group, benzimidazolyl group, 3-benzyl-1-hydantoinyl group, 1-benzyl-5-hexadecyloxy-3-hydantoinyl group, 5-methyl-1-tetrazolyl group Group), an arylazo group (eg, 4-methoxyphenylazo group, 4-pivaloylaminophenylazo group, 2-naphthylazo group, 3
-Methyl-4-hydroxyphenylazo group, etc.), a group linked by a sulfur atom (for example, phenylthio group, 2-carboxyphenylthio group, 2-methoxy-5-t-octylphenylthio group, 4-methanesulfonylphenylthio group). Group, 4-octanesulfonamidophenylthio group, 2-
Butoxyphenylthio group, 2- (2-hexanesulfonylethyl) -5-tert-octylphenylthio group, benzylthio group, 2-cyanoethylthio group, 1-ethoxycarbonyltridecylthio group, 5-phenyl-2,3, 4,5-
Tetrazolylthio group, 2-benzothiazolylthio group, 2
-Dodecylthio-5-thiophenylthio group, 2-phenyl-3-dodecyl-1,2,4-triazole-5-thio group, etc.).

In the coupler represented by formula (III), R ¹² and R ¹³ may combine to form a 5-membered to 7-membered ring.

When R ¹¹ , R ¹² , R ¹³ or X is a divalent group to form a bis derivative, preferably R ¹¹ , R ¹² and R ¹³ are substituted or unsubstituted alkylene groups (eg methylene group, ethylene Base 1,
10 _{decylene, -CH 2 CH 2 -O-CH} 2 CH 2 - , etc.), a substituted or unsubstituted phenylene group (e.g., 1,4-phenylene group, 1,3-phenylene group, -NHCO-R ¹⁴ -CONH- group (R ¹⁴ represents a substituted or unsubstituted alkylene group or phenylene group, for example, -NHCOCH
₂ CH ₂ CONH-, A —S—R ¹⁴ —S— group (R ¹⁴ represents a substituted or unsubstituted alkylene group, for example, —S—CH ₂ CH ₂ —S, And X represents a divalent group at an appropriate place from the above monovalent group.

Formulas (III), (IV), (V), (VI), and (VI
When what is represented by I) is contained in the vinyl monomer, the linking group represented by R ¹¹ , R ¹² , R ¹³ or X is an alkylene group (a substituted or unsubstituted alkylene group, for example,
Methylene group, ethylene group, 1,10-decylene group, -CH ₂ CH ₂
OCH ₂ CH ₂ — group), phenylene group (substituted or unsubstituted phenylene group, for example, 1,4-phenylene group, 1,3-phenylene group, -NHCO-, -CONH-, -O-, -OCO- and aralkylene groups (for example, Includes groups that are formed by combining those selected from.

The following are preferred linking groups.

_{-NHCO -, - CH 2 CH 2} -, -CONH-CH ₂ CH ₂ NHCO-, -CH ₂ CH ₂ O-CH ₂ CH ₂ -NHCO-, The vinyl group is represented by the general formula (III) (IV), (V), (VI)
Substituents other than those represented by and (VII) may be taken, and preferable substituents are a hydrogen atom, a chlorine atom or a lower alkyl group having 1 to 4 carbon atoms (eg, methyl group, ethyl group).

Monomers including those represented by the general formulas (III), (IV), (V), (VI) and (VII) are non-color-forming, ethylene-like mono-monomers that do not couple with the oxidation product of the aromatic primary amine developing agent. Copolymers may be made with the monomers.

Acrylic acid, α is used as the non-color-forming ethylene-like monomer that does not couple with the oxidation product of the aromatic primary amine developing agent.
-Chloroacrylic acid, α-alkylacrylic acid (for example, methacrylic acid, etc.) and esters or amides derived from these acrylic acids (for example, acrylamide, n-butylacrylamide, t-butylacrylamide, diacetoneacrylamide, methacrylamide,
Methyl acrylate, ethyl acrylate, n-propyl acrylate, n-butyl acrylate, t-butyl acrylate, iso-butyl acrylate, 2-ethylhexyl acrylate, n-octyl acrylate, lauryl acrylate, methyl methacrylate, ethyl methacrylate, n-butyl methacrylate and β-hydroxymethacrylate), methylenedibisacrylamide, vinyl esters (eg vinyl acetate, vinyl propionate and vinyl laurate), acrylonitrile, methacrylonitrile, aromatic vinyl compounds (eg styrene and its derivatives, vinyltoluene,
Divinylbenzene, vinylacetophenone and sulfostyrene), itaconic acid, citraconic acid, crotonic acid,
There are vinylidene chloride, vinyl alkyl ether (for example, vinyl ethyl ether), maleic acid, maleic anhydride, maleic acid ester, N-vinyl-2-pyrrolidone, N-vinyl pyridine and 2- and 4-vinyl pyridine. Two or more kinds of the non-color-forming ethylenically unsaturated monomers used here can be used together.
For example, n-butyl acrylate and methyl acrylate,
Examples are styrene and methacrylic acid, methacrylic acid and acrylamide, and methyl acrylate and diacetone acrylamide.

As is well known in the art of polymer color couplers, the non-chromogenic, ethylenically unsaturated monomers for copolymerization with solid water-insoluble monomeric couplers are the physical and / or chemical properties of the copolymers formed such as Solubility, compatibility with photographic colloid composition binders such as gelatin, its flexibility,
It can be chosen such that the thermal stability etc. is positively affected.

The polymer coupler used in the present invention may be water-soluble or water-insoluble, and among them, the polymer coupler latex is particularly preferable.

Specific examples of the pyrazoloazole-based magenta couplers represented by the general formula (I) used in the present invention and the synthetic method thereof are described in JP-A-59-162548, 60-43659, 59-171956 and 60-59.
-172982, 60-33552 and U.S. Pat. No. 3,061,432.

Next, specific examples of typical magenta couplers among the magenta couplers represented by the general formula (I) are shown, but the present invention is not limited thereto.

Preferred embodiments of the present invention will be described below. The preferred ratio of the magenta coupler represented by the general formula (I) (hereinafter referred to as compound (I)) to 1 mol of silver halide in the magenta color forming layer is 0.05 to 5 mol. The weight ratio of the high boiling point solvent to the pyrazoloazole magenta coupler is preferably 0 to 6.0.

The addition layer of the compound represented by the general formula (IIa) or (IIb) (hereinafter referred to as compound (II)) may be any layer in the light-sensitive material, and may be divided into two or more layers and added. Good, but desirably added to the layer containing compound (I).

The desirable addition amount of the compound (II) is 10 ^-7 mol to 10 ^-1 mol, and more preferably 10 ^-5 mol to 10 ^-2 mol, relative to 1 mol of silver halide in the layer containing the compound (I). Is the range.

In the present invention, cyan and yellow couplers can be used in addition to the magenta coupler.

Typical of these are naphthol or phenolic compounds, and open or heterocyclic ketomethylene compounds. Specific examples of these cyan and yellow couplers that can be used in the present invention are Research Disclosure (RD) 17643 (December 1978), Item VII-D and 18717.
(November 1979).

The color coupler incorporated in the light-sensitive material preferably has a ballast group or is polymerized to be diffusion resistant. A two-equivalent color coupler in which a coupling active position is substituted with a leaving group can reduce the amount of coated silver rather than a four-equivalent color coupler having a hydrogen atom. A coupler in which the color-forming dye has a suitable diffusibility, a colorless coupler, or a DIR coupler which releases a development inhibitor upon coupling reaction or a coupler which releases a development accelerator can also be used.

A typical example of the yellow coupler that can be used in the present invention is an oil protect type acylacetamide coupler. A specific example is U.S. Pat. No. 2,407,21.
No. 0, No. 22,875,057 and No. 3,265,506. In the present invention, it is preferable to use a 2-equivalent yellow coupler, and U.S. Pat.Nos. 3,408,194 and 3,447,9 are used.
No. 28, No. 3,933,501 and No. 4,022,620 oxygen atom desorption type yellow couplers described in JP-B-58-10739, U.S. Patent No. 4,401,752, No. 4,326,0
No. 24, RD18053 (April 1979), British Patent No. 1,425,020
No. 2, West German Application Publication No. 2,219,917, No. 2,261,361
Typical examples thereof include nitrogen atom releasing yellow couplers described in 2,329,587 and 2,433,812. α-pivaloyl acetanilide type couplers are excellent in fastness of color forming dyes, especially light fastness, while α
-The benzoylacetanilide type coupler provides a high color density.

Cyan couplers that can be used in the present invention include oil-protective naphthol-based and phenol-based couplers, naphthol-based couplers described in U.S. Pat.No. 2,474,293, preferably U.S. Pat.Nos. 4,052,212 and 4
Representative examples thereof include oxygen atom desorption type two-equivalent naphthol couplers described in 4,146,396, 4,228,233 and 4,296,299. Further, specific examples of the phenol-based coupler, U.S. Patent Nos. 2,369,929 and 22,801,
171, No. 2,772,162, No. 2,895,826 and the like. Cyan couplers which are fast against humidity and temperature are preferably used in the present invention, and typical examples thereof include a phenol system having an alkyl group of ethyl group or more at the meta position of the phenol nucleus described in U.S. Pat.No. 3,772,002. Cyan coupler, U.S. Pat.
3,758,308, No. 24,126,396, No. 4,334,011, No. 24,327,173, West German Patent Publication No. 23,329,729 and Japanese Patent Application No. 58-42671, 2,5-diacylamino-substituted phenol couplers and U.S. Patents Third 3,446,622
Nos. 4,333,999, 4,451,559 and 4,42
Nos. 7,767 and the like include phenolic couplers having a phenylureido group at the 2-position and an acylamino group at the 5-position.

The various couplers used in the present invention may be used in combination of two or more kinds in the same layer of the light-sensitive layer in order to satisfy the properties required for the light-sensitive material, and the same compound may be used in two or more different layers. Can also be introduced.

The coupler used in the present invention can be introduced into the light-sensitive material by various known dispersion methods, for example, a solid dispersion method, an alkali dispersion method, preferably a latex dispersion method, more preferably an oil-in-water dispersion method, etc. are typical examples. be able to. In the oil-in-water dispersion method, a high-boiling point organic solvent having a boiling point of 175 ° C. or higher and a low-boiling point so-called auxiliary solvent are dissolved in a single liquid or a mixed liquid of both, and then water or gelatin is added in the presence of a surfactant. Finely dispersed in an aqueous medium such as an aqueous solution. Examples of high boiling organic solvents are described in U.S. Pat.No. 2,322,027
No. etc.

The standard amount of the color coupler used is in the range of 0.001 to 1 mol per mol of the light-sensitive silver halide, preferably 0.01 to 0.5 mol for the yellow coupler and 0.002 to 0.3 mol for the cyan coupler.

The silver halide emulsion used in the present invention usually comprises a water-soluble silver salt (eg silver nitrate) solution and a water-soluble halogen salt (eg potassium bromide, potassium chloride, potassium iodide alone or a mixture thereof) gelatin solution. It is manufactured by mixing in the presence of an aqueous polymer solution.

The silver halide grains may have different layers from the inside and the surface layer, may have a multi-phase structure having a junction structure, or may have a uniform phase as a whole. Moreover, they may be mixed. For example, in the case of silver chlorobromide grains having different phases, it may be a grain having a silver bromide-rich nucleus or a single layer or a plurality of layers in the grain, which is higher than the average halogen composition. Further, it may be a grain having a nucleus rich in silver chloride from the average halogen composition or a single or multiple layers in the grain.

The average grain size of silver halide grains (in the case of spherical grains or grains close to spheres, the average grain size based on the projected area with the grain size as the grain size in the case of cubic grains) is 2μ or less. 0.1 μ or more is preferable, but 1 μ or less and 0.15 μ or more is particularly preferable. The particle size distribution may be narrow or wide.

So-called monodisperse silver halide emulsions can be used in the present invention. The degree of monodispersity is preferably 15% or less, and particularly preferably 10% or less, by the coefficient of variation obtained by dividing the standard deviation derived from the grain size distribution curve of silver halide by the average grain size. In order to satisfy the target gradation of the light-sensitive material, two or more kinds of monodisperse silver halide emulsions having different grain sizes are mixed in the same layer or different layers in an emulsion layer having substantially the same color sensitivity. Can be applied in multiple layers. Further, two or more kinds of polydisperse silver halide emulsions or a combination of monodisperse emulsions and polydisperse emulsions can be mixed or laminated and used.

The silver halide grains used in the present invention may have a regular crystal such as a cube, octahedron, dodecahedron or tetradecahedron, and may have an irregular shape such as a sphere. It may have an (irregular) crystal form, or may have a composite form of these crystal forms. Further, tabular grains may be used, and particularly, an emulsion in which tabular grains having a length / thickness ratio value of 5 or more, particularly 8 or more occupy 50% or more of the total projected area of the grains may be used. It may be an emulsion composed of a mixture of these various crystal forms. These various emulsions may be either a surface latent image type which forms a latent image mainly on the surface or an internal latent image type which forms a latent image inside the grains.

The photographic emulsion used in the present invention is described in "Chemie and Physique Photographiqu" by P. Grafkides.
e) (Published by Paul Montell, 1967), GF Duffin, "Photograhic Emulsion Chemistr"
y) (Published by Focal Press, 1966), VL Zelikmann et al., "Making and Coating of Photographic Emulsions" (Making and Coati
ng Photographic Emulsion) (Focal Press, Inc., 1964) and the like. That is, any of an acidic method, a neutral method, an ammonia method, etc. may be used, and as a method of reacting a soluble silver salt and a soluble halogen salt, a one-sided mixing method, a simultaneous mixing method,
Any combination of them may be used. A method of forming grains in the presence of excess silver ions (so-called reverse mixing method) can also be used. It is also possible to use a conversion method in which a halogen salt is added so as to form a less soluble silver halide. As one of the simultaneous mixing methods, it is also possible to use a method of keeping pAg constant in the liquid phase in which silver halide is produced, that is, a so-called controlled double jet method. According to this method, a silver halide emulsion having a regular crystal form and a substantially uniform grain size can be obtained.

In the process of silver halide grain formation or physical ripening,
Cadmium salt, zinc salt, lead salt, thallium salt, iridium salt or its complex salt, rhodium salt or its complex salt, iron salt or iron complex salt may coexist.

The silver halide emulsion is usually used for coating after physical ripening, desalting and chemical ripening after grain formation.

Known silver halide solvents (e.g., ammonia, Rodancari et al., U.S. Pat. No. 3,271,157, JP-A-51-12360).
JP-A-53-82408, JP-A-53-144319, JP-A-54-
The thioethers and thione compounds described in 100717 or JP-A-54-155828 can be used for precipitation, physical aging and chemical aging. In order to remove the soluble silver salt from the emulsion after physical ripening, a Nudel water washing, a flocculation sedimentation method, an ultrafiltration method or the like is used.

The photographic emulsion used in the present invention can be spectrally sensitized with methine dyes and the like, if necessary.

The photographic emulsion used in the present invention may contain various compounds for the purpose of preventing fog during the manufacturing process of the light-sensitive material, storage or photographic processing, or stabilizing photographic performance.

The light-sensitive material produced by using the present invention, as a color antifoggant or color mixing inhibitor, is a hydroquinone derivative, an aminophenol derivative, an amine, a gallic acid derivative, a catechol derivative, an ascorbic acid derivative, a colorless coupler, a sulfonamidephenol. You may contain a derivative etc.

Various anti-fading agents can be used in the light-sensitive material of the present invention.

In the light-sensitive material of the present invention, an ultraviolet absorber can be added to the hydrophilic colloid layer.

The light-sensitive material of the present invention contains one or more surfactants for various purposes such as coating aid, antistatic property, slipperiness improvement, emulsion dispersion, adhesion prevention and photographic property improvement (for example, development acceleration, contrast enhancement, sensitization). But it's okay.

In the light-sensitive material of the present invention, in addition to the above-mentioned additives, various stabilizers, stain inhibitors, developers or their precursors,
A development accelerator or its precursor, a lubricant, a mordant, a matting agent, an antistatic agent, a plasticizer, or other various additives useful for a photographic light-sensitive material may be added. Typical examples of these additives are Research Disclosure 17643 (197
December 8) and 18716 (November 1979).

The invention is also applicable to multilayer multicolor photographic materials having at least two different spectral sensitivities on the support. Multilayer natural color photographic materials usually have at least one red-sensitive emulsion layer, one green-sensitive emulsion layer and one blue-sensitive emulsion layer on a support.
The order of these layers can be arbitrarily selected as required. Each of the above emulsion layers may be composed of two or more emulsion layers having different sensitivities, and a non-photosensitive layer may be present between two or more emulsion layers having the same photosensitivity.

The light-sensitive material according to the present invention, in addition to the silver halide emulsion layer,
Protective layer, intermediate layer, filter layer, antihalation layer,
It is preferable to appropriately provide an auxiliary layer such as a back layer.

In the photographic light-sensitive material of the present invention, the photographic emulsion layer and other layers are coated on a flexible support such as a plastic film, paper or cloth usually used for a photographic light-sensitive material or a rigid support such as glass, pottery or metal. To be done.

The support used in the present invention is preferably a baryter paper or a polyethylene-supported paper support containing a white pigment (for example, titanium oxide) in polyethylene.

The present invention can be applied to various light-sensitive materials. Typical examples include color negative films for general use or movies, color reversal films for slides or televisions, color papers, color positive films and color reversal papers. The present invention can also be applied to a black-and-white light-sensitive material using a three-color coupler mixture described in Research Disclosure 17123 (July 1978).

The color developing solution used for the development processing of the light-sensitive material of the present invention is preferably an alkaline aqueous solution containing an aromatic primary amine type color developing agent as a main component. As the color developing agent, a p-phenylenediamine compound is preferably used, and a typical example thereof is 3-methyl-4-amino-N, N-
Diethylaniline, 3-methyl-4-amino-N-ethyl-N-β-hydroxyethylaniline, 3-methyl-
4-Amino-N-ethyl-N-β-methanesulfonamidoethylaniline, 3-methyl-4-amino-N-ethyl-N-β-methoxyethylaniline and their sulfates, hydrochlorides or p-toluenesulfone Examples thereof include acid salts.

Color developers include pH buffers such as alkali metal carbonates, borates or phosphates, development inhibitors such as bromides, iodides, benzimidazoles, benzothiazoles or mercapto compounds or antifoggants. Etc. are generally included.

The photographic emulsion layer after color development is usually bleached. The bleaching process may be performed at the same time as the fixing process, or may be performed individually. Examples of the bleaching agent include compounds of polyvalent metals such as iron (III), cobalt (III), chromium (VI), and copper (II), peracids, quinones, and nitroso compounds. Typical bleaching agents are ferricyanide; dichromate; organic complex salts of iron (III) or cobalt (III) such as ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, nitrilotriacetic acid, 1,3-diamino-2-
Aminopolycarboxylic acids such as propanol tetraacetic acid or complex salts of organic acids such as citric acid, tartaric acid and malic acid;
Persulfate; manganate; nitrosophenol and the like can be used. Of these, ethylenediaminetetraacetic acid iron (III) salt and persulfate are preferable from the viewpoint of rapid treatment and environmental pollution. Further, the ethylenediaminetetraacetic acid iron (III) complex salt is particularly useful in a stand-alone bleaching solution as well as in a bath bleach-fixing solution.

If necessary, various accelerators may be used in combination with the bleaching solution and the bleach-fixing solution.

After the bleach-fixing process or the fixing process, a washing process is usually performed. Various known compounds may be added to the washing process for the purpose of preventing precipitation and saving water. For example, in order to prevent precipitation, water softeners such as inorganic phosphoric acid, aminopolycarboxylic acid, organic phosphoric acid, bactericides and antifungal agents that prevent the generation of various bacteria, algae and mold, magnesium salts and aluminum. A hardening agent typified by a salt, or a surfactant for preventing drying load and unevenness can be added if necessary. Alternatively, compounds described in LE West “Water Quality Criteria”, “Science and Engineering of Photography” (Photo.Sci.Eng.), Volume 6, pages 344 to 359 (1965), etc. are added. May be. It is particularly effective to add a chelating agent or an antifungal agent.

In the water washing step, it is general to carry out countercurrent water washing of two or more tanks to save water. Furthermore, instead of the water washing step, JP-A-57-8
You may implement the multistage countercurrent stabilization process process as described in No. 543. Various compounds are added to the stabilizing bath for the purpose of stabilizing the image. For example, adjust the membrane pH (eg pH3
~ 8) various buffering agents (for example, borate, metaborate, borax, phosphate, carbonate, potassium hydroxide, sodium hydroxide, ammonia water, monocarboxylic acid, dicarboxylic acid, polycarboxylic acid) Typical examples include formalin and the like). In addition, water softener (inorganic phosphoric acid, aminopolycarboxylic acid, organic phosphoric acid, aminopolyphosphonic acid, phosphonocarboxylic acid, etc.), bactericide (benzisothiazolinone, irithiazolone, 4-thiazolinebenzimidazole), if necessary. , Halogenated phenols, etc.), surfactants, optical brighteners, hardeners and the like, and two or more kinds of the same or different target compounds may be used in combination.

Further, it is preferable to add various ammonium salts such as ammonium chloride, ammonium nitrate, ammonium sulfate, ammonium phosphate, ammonium sulfite, and ammonium thiosulfate as a film pH adjuster after the treatment.

The silver halide light-sensitive material of the present invention may contain a color developing agent for the purpose of simplifying and accelerating the processing. For incorporation, it is preferable to use various precursors of color developing agents.

The silver halide light-sensitive material of the present invention may contain various 1-phenyl-3-pyrazolidones in order to accelerate color development, if necessary.

Typical compounds thereof are JP-A-56-64339 and JP-A-57-144.
547, 57-211147, 58-50532, 58-50536,
58-50533, 58-50534, 58-50535 and 58
-115438, etc.

The various processing solutions used in the present invention are used at 10 ° C to 50 ° C, but it is preferable to develop at a temperature of 33 ° C to 38 ° C. Also, West German Patent No. 2,226,77 for silver saving of photosensitive materials
Treatment with cobalt intensification or hydrogen peroxide intensification as described in No. 0 or US Pat. No. 3,674,499 may be performed.

If necessary, a heater, a temperature sensor, a liquid level sensor, a circulation pump, a filter, a floating pig, a squeegee, etc. may be provided in each treatment bath.

(Effect of the Invention) The silver halide color photographic light-sensitive material of the present invention can prevent deterioration of photographic properties due to latent image regression. Further, the silver halide color photographic light-sensitive material of the present invention has a strong color image and has a large effect of improving white background contamination. Further, the silver halide color photographic light-sensitive material of the present invention gives a magenta color image having good spectral absorption characteristics. As a result, a photographic image having excellent color reproducibility is formed.

Examples The present invention will be described in detail below based on specific examples, but the present invention is not limited thereto.

Example 1 A color photographic light-sensitive material was prepared by coating the following first to eleventh layers on a paper support laminated on both sides with polyethylene. On the coating side of the first layer of polyethylene, titanium white is contained as a white pigment and a slight amount of ultramarine is contained as a bluish dye.

(Photosensitive layer composition) The components and the coating amounts shown in g / m ² are shown below. For silver halide, the coating amount in terms of silver is shown.

1st layer (antihalation layer) Black colloidal silver ...... 0.10 Gelatin ...... 2.00 2nd layer (low sensitivity red sensitive layer) Silver iodobromide emulsion spectrally sensitized with red sensitizing dye (* 5 and * 4) (3.5 mol% silver iodide, average grain size 0.7μ) …… .0.
15 Gelatin: 1.00 Cyan coupler (* 3): 0.30 Anti-fading agent (* 2): 0.15 Coupler solvent (* 18 and * 1): 0.06 Third layer (high sensitivity red sensitive layer) Red sensitizing dye Silver iodobromide emulsion spectrally sensitized by (* 5 and * 4) (8.0 mol% silver iodide, average grain size 0.7μ) .... Silver
0.10 Gelatin ...... 0.50 Cyan coupler (* 3) ...... 0.10 Anti-fading agent (* 2) ...... 0.05 Coupler solvent (* 18 and * 1) ...... 0.02 4th layer (intermediate layer) Yellow colloidal silver ...... 0.02 Gelatin …… 1.00 Color mixing inhibitor (* 14) …… 0.08 Color mixing inhibitor solvent (* 13) …… 0.16 Polymer latex (* 6) …… 0.10 Fifth layer (low sensitivity green sensitive layer) Green sensitizing dye (* 12) ) Silver spectrally sensitized silver iodobromide emulsion (silver iodide 2.5 mol%, average grain size 0.4 μ) ... silver 0.20
Gelatin: 0.70 Magenta coupler (* 11): 0.40 Anti-fading agent A (* 10): 0.05 Anti-fading agent B (* 9): 0.05 Anti-fading agent C (* 8): 0.02 Coupler solvent (* 7) 0.15 6th layer (high-sensitivity green-sensitive layer) Silver iodobromide emulsion spectrally sensitized with a green sensitizing dye (* 12) (3.5 mol% silver iodide, average grain size 0.9μ). Silver 0.20
Gelatin: 0.70 Magenta coupler (* 11): 0.40 Anti-fading agent A (* 10): 0.05 Anti-fading agent B (* 9): 0.05 Anti-fading agent C (* 8): 0.02 Coupler solvent (* 7) ...... 0.15 7th layer (yellow filter layer) Yellow colloidal silver ...... 0.20 Gelatin ...... 1.00 Color mixing inhibitor (* 14) ...... 0.06 Color mixing inhibitor solvent (* 13) ...... 0.24 8th layer (low sensitivity) Blue-sensitive layer) Silver iodobromide emulsion spectrally sensitized with a blue sensitizing dye (* 16) (silver iodide 2.5 mol%, average grain size 0.5μ) ... Silver 0.20
Gelatin 0.50 Yellow coupler (* 15) 0.20 Coupler solvent (* 18) 0.05 0.05 9th layer (high sensitivity blue sensitive layer) Silver iodobromide spectrally sensitized with blue sensitizing dye (* 16) Emulsion (silver iodide 2.5 mol%, average grain size 1.4μ) ... Silver 0.20
Gelatin: 0.50 Yellow coupler (* 15): 0.20 Coupler solvent (* 18): 0.05 Layer 10 (UV absorbing layer) Gelatin: 1.50 UV absorber (* 19): 1.00 UV absorber solvent (* 18) …… 0.30 Color mixing inhibitor (* 17) …… 0.08 11th layer (protective layer) Gelatin …… 1.00 Hardener (* 20) …… 0.17 The compounds used here are as follows: * 1 Dioctyl phthalate * 2 2- (2-hydroxy-3-sec-butyl-5-
t-butylphenyl) benzotriazole * 3 2- [α- (2,4-di-t-amylphenoxy)
Butanamide] -4,6-dichloro-5-ethylphenol * 4 5,5'-dichloro-3,3'-di (3-sulfobutyl) -9-ethylthiacarbonylcyanine sodium salt * 5 triethylammonium-3- [ 2- {2- [3
-(3-Sulfopropyl) naphtho (1,2-d) thiazoline-2-ylidenemethyl] -1-butenyl} -3-naphtho (1,2-d) thiazolino] propane sulfonate * 6 Polyethyl acrylate * 7 Phosphoric acid Trioctyl ester * 8 2,4-di-t-hexylhydroquinone * 9 Di- (2-hydroxy-3-t-butyl-5-methylphenyl) methane * 10 3,3,3 ', 3'-tetramethyl -5,6,5 ', 6'-Tetrapropoxy-1,1'-bisspiroindane * 11 1- (2,4,6-trichlorophenyl) -3- (2
-Chloro-5-tetradecanamido) anilino-2-pyrazolino-5-one * 12 5,5'-diphenyl-9-ethyl-3,3'-disulfopropyloxacarbocyanine Na salt * 13 Phosphoric acid-o- Cresyl ester * 14 2,4-di-t-octylhydroquinone * 15 α-pivaloyl-α-[(2,4-dioxo-1-
Benzyl-5-ethoxyhydantoin-3-yl) -2
-Chloro-5- (α-2,4-dioxo-t-amylphenoxy) butaneamino] acetanilide * 16 triethylammonium 3- [2- (3-benzylrhodanin-5-ylidene) -3-benzoxazolinyl] Propane sulfonate * 17 2,4-di-sec-octylhydroquinone * 18 Trinonyl phosphoric acid ester * 19 5-Chloro-2- (2-hydroxy-3-t-butyl-5-t-octyl) phenylbenztriazole * 20 1,4-Bis (vinylsulfonylacetamido) ethane The sample produced as described above was designated as sample number 101, and was used as a comparative control sample thereafter.

Sample Nos. 102 to 111 are obtained by replacing or adding the magenta coupler (* 11) and the additives of the fifth and sixth layers of Sample No. 101. After the stepwise exposure for sensitometry of these samples, development measurement was performed by the following processing steps, and measurement was performed with FAD (Fuji Photo Film Co., Ltd. automatic measuring machine). The results are shown in Table 1 below.

[Treatment process]

First development (black and white development) 38 ℃ 1 minute 15 seconds Water wash 38 ℃ 1 minute 30 seconds Reverse exposure 100Lux or more 1 second or more Color development 38 ℃ 2 minutes 15 seconds Water wash 38 ℃ 45 seconds Bleach fixing 38 ℃ 2 minutes 00 seconds Washing with water 38 ° C 2 min 15 sec [Treatment liquid composition] First developer Nitrilo-N, N, N-trimethylene phosphonic acid pentasodium salt 0.6 g Diethylenetriamine pentaacetic acid pentasodium salt 4.0 g Potassium sulfite 30.0 g Potassium thiocyanate 1.2g Potassium carbonate 35.0g Hydroquinone monosulfonate / potassium salt 25.0g Diethylene glycol 15.0ml 1-Phenyl-4-hydroxy-methyl-4-methyl-3-pyrazolidone 2.0g Potassium bromide 0.5g Potassium iodide 5.0mg Add water 1 (pH9.70) Color developer Benzyl alcohol 15.0 ml Diethylene glycol 12.0 ml 3,6-Dithia-1,8-octanediol 0.2 g Nitrilo-N, N, N-trimethylene phos Phosonic acid / pentasodium salt 0.5 g Diethylenetriaminepentaacetic acid / pentasodium salt 2.0 g Sodium sulfite 2.0 g Potassium carbonate 25.0 g Hydroxylamine sulfate 3.0 g N-ethyl-N- (β-methanesulfonamidoethyl) -3-methyl- 4-Aminoaniline Sulfate 5.0g Potassium bromide 0.5g Potassium iodide 1.0mg Add water 1 (pH 10.0) Bleach-fix solution 2-Mercapto-1,3,4-triazole 1.0g Ethylenediaminetetraacetic acid disodium・ Dihydrate 5.0g Ethylenediaminetetraacetate iron (III) ammonium-hydrate 80.0g Sodium sulfite 15.0g Sodium thiosulfate (700g / l liquid) 160.0ml Glacial acetic acid 5.0ml Add water 1 (pH6.50) Color purity in this table means magenta filter CC200M
The sum of cyan and yellow densities (D _R and D _B , respectively) at the point where the magenta density (D _G ) measured with the Macbeth densitometer Status AA filter is 1.0 when (Fuji Film Co., Ltd.) is added to perform stepwise exposure. Represents the ratio (D _G / D _R + D _B ) to That is, it is a scale showing the amounts of extra cyan and yellow components in the magenta color, and generally, the smaller this value, the higher the color purity.

The increase in stain due to thermal fading indicates the value of the change in the density of yellowing of the white background after 15 days of the treated print using a constant temperature and humidity chamber of 80 to 70% with a B filter.

From the results of Table 1, sample numbers 107 and 109 according to the present invention
It can be seen that 111 has a high color purity and suppresses unnecessary color stains with almost no decrease in relative sensitivity.

Example 2 A color photosensitive material was prepared by coating the following photosensitive layers consisting of the first to third layers on a paper support laminated on both sides with polyethylene. The polyethylene coated with the first layer contains a titanium dioxide white pigment and a trace amount of ultramarine blue as a white pigment.

(Photosensitive Layer Composition) The numbers corresponding to the respective components indicate the coating amount expressed in g / m ² unit, and for silver halide, the coating amount in terms of silver.

1st layer (green-sensitive layer) Silver chlorobromide emulsifier (70 mol% silver bromide sensitizing dye * 31) ...... Silver 0.30 Magenta coupler (* 32) ...... 0.25 Magenta coupler solvent (* 34) ...... 0.30 Fading Inhibitor (* 9 / * 10) …… 0.05 / 0.10 Gelatin …… 1.00 Second layer (UV absorbing intermediate layer) UV absorber (* 33) …… 0.50 UV absorbing solvent (DBP) …… 0.20 Gelatin …… 0.15 Third layer (protective layer) Gelatin ... 1.50 Here, DBP represents dibutyl phthalate, and the chemical structures of * 31 to * 34 are shown below.

A gelatin hardener 2,4-dichloro-6-hydroxy-1,3,5-triazine sodium salt was added to the first to third layers in equal portions.

This photosensitive material was used as Sample 201.

Next, seven kinds of photosensitive samples of Samples 202 to 208 were prepared in exactly the same manner except that the changes were made as shown in Table 2. These samples were subjected to gradation exposure for sensitometry with a stretcher (Fuji Color Head 609 manufactured by Fuji Photo Film Co., Ltd.) and then developed by the following processing steps.

Processing process Temperature Time Image solution 33 ℃ 3.5 minutes Bleach-fix solution 33 ℃ 1.5 minutes Water wash 28-35 ℃ 3.0 minutes Developer Nitrilotriacetic acid ・ 3Na 2.0g Benzyl alcohol 15ml Diethylene glycol 10ml Na ₂ SO ₃ 2.0g KBr 0.5g Hydroxyl Amine sulfate 3.0 g 4-amino-3-methyl-N-ethyl-N- [β- (methanesulfonamido) ethyl] -p-phenylenediamine / sulfate 5.0 g Na ₂ CO ₃ (monohydrate) 30 g water Add pH to 1 liter (pH10.1) Bleach and fixer Ammonium thiosulfate (70%) 150.0 ml Na ₂ SO ₃ 15 g NH ₄ [Fe (EDTA)] 55 g EDTA 2.2 Na 4.0 g Add water to make 1 liter (PH 6.9) After the above-mentioned treatment, a characteristic curve (D-logE curve) was obtained with a self-recording densitometer using blue, green and yellow filters. The results are shown in Table 3.

Color purity in Table 3 of magenta color at the time of white exposure D _G =
It is a value calculated by the formula (D _B + D _R / D _R ) from the values of D _B and D _R at 1.0, and the meaning is the same as in Example 1. Also △
The _{Dmin (D G) 50 ℃ -80} % prior to exposure of the sample - show increased values of Dmin when allowed to stand under humidity 7 days high temperature and high.

As can be seen from Table 3, the pyrazoloazole-based coupler is very excellent in color purity as compared with the 5-pyrazolone-type coupler, but Dmin is high, which is not desirable. On the other hand, it can be seen that the combination of the specific pyrazoloazole coupler within the scope of the present invention and the additive can reduce the Dmin and obtain the desired photographic properties with almost no reduction in the sensitivity.

Example 3 On a subbed cellulose triacetate film support,
A multilayer color light-sensitive material having the following composition was prepared and used as Sample 301.

1st layer: Antihalation layer Black colloidal silver 0.25g / m ² UV absorber U-1 0.24g / m ² High boiling point organic solvent O-1 Gelatin layer containing 0.1cc / m ² (dry film thickness 2μ) 2nd Layer: intermediate layer Gelatin layer containing compound H-1 0.05 g / m ² high boiling point organic solvent O-2 0.05 cc / m ² (dry film thickness 1 μ) Third layer: first red-sensitive emulsion layer Sensitizing dye S- 1 and S-2 spectrally sensitized silver iodobromide emulsion Silver amount: 0.5 g / m ² (iodine content 4 mol%, average particle size 0.3 μ) Coupler C-1 0.25 g / m ² High boiling organic Solvent O-2 Gelatin layer containing 0.12 cc / m ² (dry film thickness 1 μm) Fourth layer: second red-sensitive emulsion layer Silver iodobromide emulsion spectrally sensitized with sensitizing dyes S-1 and S-2 Silver amount: 0.8 g / m ² (iodine content 2.5 mol%, average particle size 0.55 μ) Coupler C-1 0.70 g / m ² Gelatin layer containing high boiling organic solvent O-2 0.33 cc / m ² (dry film Thickness 2.5μ) Fifth layer: Middle layer Compound H-1 0.1 g / m ² High boiling organic solvent O-2 Gelatin layer containing 0.1 cc / m ² (dry film thickness 1 μm) Sixth layer: first green sensitive emulsion layer Sensitizing dyes S-3 and S- Silver iodobromide emulsion spectrally sensitized in No. 4 Silver amount 0.7g / m ² (iodine content 3 mol%, average particle size 0.3μ) Coupler C-2 0.35g / m ² High boiling organic solvent O-2 Gelatin layer containing 0.26 cc / m ² (dry film thickness 1 μm) Seventh layer: second green emulsion layer Silver iodobromide emulsion spectrally sensitized with sensitizing dyes S-3 and S-4 Silver amount ... 0.7 g / m ² (iodine content 2.5 mol%, average particle size 0.8 μ) Coupler C-2 0.25 g / m ² High boiling organic solvent O-2 Gelatin layer containing 0.05 cc / m ² (dry film thickness 2.5 μ) eighth layer: gelatin layer containing an intermediate layer compound H-1 0.05g / m ² high-boiling organic solvent ^O-2 0.1g / m 2 (dry film thickness 1 [mu]) ninth layer: yellow filter layer yellow colloidal silver 0.1 g / m ² compound H-2 0.05g / m ² high boiling point Gelatin layer containing organic solvent O-2 0.04 cc / m ² (dry film thickness 1 μm) 10th layer: first blue-sensitive emulsion layer Silver iodobromide emulsion spectrally sensitized with sensitizing dye S-5 Silver amount ... ... 0.6 g / m ² (iodine content 2.5 mol%, average particle size 0.7 μ) Coupler C-3 0.5 g / m ² High boiling organic solvent O-2 Gelatin layer containing 0.1 cc / m ² (dry film thickness 1.5 μ ) Eleventh layer: Second blue-sensitive emulsion layer Silver iodobromide emulsion spectrally sensitized with sensitizing dye S-5 Silver amount ... 1.1 g / m ² (iodine content 2.5 mol%, average grain size 1.2 μ) Coupler C-3 1.2g / m ² High boiling organic solvent O-2 Gelatin layer containing 0.23cc / m ² (dry film thickness 3μ) 12th layer: 1st protective layer UV absorber U-1 0.11g / m ² UV absorber U-2 0.29 g / m ² High boiling point organic solvent O-1 Gelatin layer containing 0.28 cc / m ² (dry film thickness 2 μm) 13th layer: 2nd protective layer Fine-grained iodobromide on the surface silver emulsion silver amount ...... 0.1g / m ² (iodine content of 1 mol , Average particle size 0.06μ) Gelatin layer containing polymethylmethacrylate particles (average particle size 1.5μ) (dry film thickness 0.8μ) In addition to the above composition, each layer contains gelatin hardener H-3 and surfactant. H-4 and H-5 were added.

The compounds used to make the samples are shown below.

H-4 Alkylbenzenesulfonic acid Na salt The sample produced as described above was designated as sample number 301, and was used as a comparative control sample hereinafter. Next, as shown in Table 4, Samples 302 and 303 were prepared so that the seventh layer coupler C-2 and the coating silver amount were changed to obtain almost the same gradation.

These samples were exposed to white wedge and developed according to the following steps. Fuji type concentration measurement FAD
The results measured with the mold are shown in Table 4.

Processing time Process temperature First development 6 minutes 38 ℃ Water wash 2 minutes "Reverse 2 minutes" Color development 6 minutes "Adjustment 2 minutes" Bleach 6 minutes "Settling 4 minutes" Water washing 4 minutes "Stability 1 The composition of the normal temperature drying treatment solution is as follows.

First developer Water 700 ml Nitrilo-N, N, N-trimethylenephosphonic acid pentasodium salt 2 g Sodium sulfite 20 g Hydroquinone monosulfonate 30 g Sodium carbonate (monohydrate) 30 g 1-phenyl-4-methyl-4- Hydroxymethyl-3 pyrazolidone 2 g Potassium bromide 2.5 g Potassium thiocyanate 1.2 g Potassium iodide (0.1% solution) 2 ml Water added 1000 ml Inversion solution water 700 ml Nitrilo-N, N, N-trimethylenephosphonic acid pentasodium salt 3g Stannous chloride (dihydrate) 1g p-Aminophenol 0.1g Sodium hydroxide 8g Glacial acetic acid 15ml Water added 1000ml Color developer water 700ml Nitrilo-N, N, N-trimethylenephosphonic acid pentasodium salt 3g Sodium sulfite 7g Tribasic sodium phosphate (12-hydrate) 36g Potassium bromide 1g Potassium iodide (0.1% solution) 90ml Sodium hydroxide 3g Citrazine 1.5g N-Ethyl-N- (β-methanesulphonamidoethyl) -3-methyl-4-aminoaniline ・ sulfate 11g 3,6-dithiaoctane-1,8-diol 1g Water is added 1000ml Adjustment liquid water 700ml Sodium sulfite 12g Sodium ethylenediaminetetraacetate (dihydrate) 8g Thioglycerin 0.4ml Glacial acetic acid 3ml Add water 1000ml Bleach 800g Ethylenediaminetetraacetic acid sodium (dihydrate) 2g Ethylenediaminetetraacetic acid iron (III) ammonium (dihydrate) Salt) 120g Potassium bromide 100g Add water 1000ml Fixer water 800ml Sodium thiosulfate 80.0g Sodium sulfite 5.0g Sodium bisulfite 5.0g Add water 1000ml Stabilizer water 800ml Formalin (37wt%) 5.0ml Fuji Drywell (Fuji Film Co., Ltd. surfactant) 5.0 ml Add 1000 ml of water The definition of magenta color purity (D _R + D _B ) / D _G in Table 4 is slightly different from that in Example 1. The Macbeth Color Checker Color Rendition Chart
Color Cheker Color Rendition Chart) The density of "magenta" color obtained by standard photography of Macbeth Co., Ltd. is calculated using the values of D _R , D _B , and D _G measured using a Macbeth densitometer. . In the case of reversal processing, the 7th layer fog generated in the first developing bath is D _G
Reduction of Dmax with Dmax (D _G) as a measure of fog for appearing in the image as (reduced coloring level). Also showed the degree of first image development fogging when left for 3 days under 45 ° C. -80% RH coated finished film (3d) with the value of ΔDmax (D _G). Wet heat (60 ℃ 70%) of the bare part of the processed film
The increase in stain over time due to 6 weeks) is shown by the value of ΔDmin (D _B ).

As can be seen from Table 4, the samples of the present invention do not impair the color purity and the low-stain characteristics due to the treated wet heat, do not adversely affect the sensitivity and the first development fog, and preserve the raw film with time. It turns out that can be improved.

Example 4 A silver halide color photographic light-sensitive material was prepared by coating a light-sensitive layer consisting of the following first to seventh layers on a paper support laminated on both sides with polyethylene. The polyethylene coated with the first layer contains titanium dioxide and a trace amount of ultramarine.

(Structure of Photosensitive Layer) The numbers corresponding to the respective components represent the coating amount expressed in the unit of g / m ² , and the silver halide coating amount represents the coating amount in terms of silver.

1st layer (blue sensitive emulsion layer) Silver chlorobromide emulsion (80 mol% silver bromide) ...... Silver 0.30 Yellow coupler (* 15) ...... 0.70 Same as above Solvent (TNP) ...... 0.15 Gelatin ...... 1.20 Second layer (Intermediate layer) Gelatin: 0.90 Di-t-octylhydroquinone: 0.05 Same as above Solvent (DBP): 0.10 Third layer (green sensitive emulsion layer) Silver chlorobromide emulsion (70 mol% of silver bromide): Silver 0.45 Magenta coupler (* 11) ...... 0.35 Same solvent (TOP) ...... 0.44 Anti-fading agent (* 9 / * 10) ...... 0.05 / 0.10 Gelatin ...... 1.00 4th layer (UV absorbing intermediate layer) UV absorber (* 41 / * 42 / * 2) …… 0.06 / 0.25 / 0.25 Same solvent (TNP) …… 0.20 Di-t-octylhydroquinone …… 0.05 Same solvent (DBP) …… 0.10 Gelatin …… 1.50 Fifth layer ( Red-sensitive emulsion layer) Silver chlorobromide emulsion (50 mol% of silver bromide) ...... Silver 0.20 Cyan coupler (* 43 / * 44) ...... 0.20 / 0.20 Same solvent (TN P / DBP) ...... 0.10 / 0.20 Gelatin ...... 0.90 6th layer (UV absorbing intermediate layer) UV absorber (* 41 / * 42 / * 2) ...... 0.06 / 0.25 / 0.25 Same solvent (DBP) ...... 0.20 Gelatin ...... 1.50 7th layer (protective layer) Gelatin ...... 1.50 where DBP is dibutyl phthalate and TOP is tri (n-).
Octyl) phosphate, TNP is tri (n-nonyl)
Represents phosphate.

The following dyes were used as the spectral sensitizer for each emulsion layer.

Blue sensitive emulsion layer; (2 × 10 ⁻⁴ mol was added per mol of silver halide.) Green-sensitive emulsion layer; (2.5 × 10 ⁻⁴ mol added per mol of silver halide.) Red-sensitive emulsion layer; (2.5 × 10 ⁻⁴ mol was added per mol of silver halide.) The following dyes were used as the anti-irradiation dye in each emulsion layer.

Green-sensitive emulsion layer; Red-sensitive emulsion layer; This silver halide color photographic light-sensitive material was designated as Sample 401.

Next, as shown in Tables 5 and 6, Samples 402-409 were prepared in exactly the same manner except that the type and coating amount of the coupler, silver amount and additives of the third layer of the light-sensitive material were changed. These samples were subjected to gradation exposure for sensitometry with a stretcher (Fuji Color Head 609 manufactured by Fuji Photo Film Co., Ltd.) and then developed by the following processing steps. The results are shown in Tables 5 and 6.

Treatment process Temperature Time Color development 33 ° C 3 minutes 30 seconds Bleach-fixing 33 ° C 1 minute 30 seconds Water washing 24-34 ° C 3 minutes Drying 80 ° C 1 minute The components of each processing solution are as follows.

Color developer Water 800 ml Diethylenetriaminepentaacetic acid 3.0 g Benzyl alcohol 15 ml Diethylene glycol 10 ml Sodium sulfite 2.0 g Potassium bromide 0.5 g Potassium carbonate 30.0 g N-ethyl-N- (β-methanesulfonamidoethyl) -3-methyl-4-amino Aniline sulphate 5.0g Hydroxylamine sulphate 4.0g Fluorescent brightener (4,4'-distilbene type) 1.0g Add water 1000ml pH (25 ℃) 10.10 Bleach fixer water 400ml Ammonium thiosulfate (70% solution) 150ml Sodium sulfite 18g Ethylenediaminetetraacetic acid iron (III) ammonium 55g Ethylenediaminetetraacetic acid / 2Na 5g Water added 1000ml pH (25 ℃) 6.70 The definition of magenta color purity in Tables 5 and 6 is Example 1
Is the same as. Further, the yellow smear of the print due to ΔDmin (D _B ) warming showed a value in which the yellow stain on the white background portion of the print after the development treatment increased at 60 ° C.-70% -6 weeks.

As can be seen from Tables 5 and 6, the samples according to the present invention (Samples 404-409) have favorable photographic characteristics (color freshness, little fog increase over time, and yellow prints) without a relative decrease in sensitivity. It can be seen that (less bami) is obtained.

Claims (1)

[Claims] 1. Contain at least one pyrazoloazole-based coupler represented by the following general formula (V) or (VI) and at least one compound represented by the following general formula (IIa) or (IIb). A silver halide color photographic light-sensitive material characterized by: General formula (V) And general formula (VI) (In the formula, R ¹¹ and R ¹² may be the same or different from each other, and each is a hydrogen atom, a halogen atom, an alkyl group, an aryl group, a heterocyclic group, a cyano group, an alkoxy group, an aryloxy group, a heterocyclic oxy group, Acyloxy group, carbamoyloxy group, silyloxy group, sulfonyloxy group, acylamino group, anilino group, ureido group, imide group, sulfamoylamino group, carbamoylamino group, alkylthio group, arylthio group, heterocyclic thio group, alkoxycarbonylamino Group, an aryloxycarbonylamino group, a sulfonamide group, a carbamoyl group, an acyl group, a sulfamoyl group, a sulfonyl group, a sulfinyl group, an alkoxycarbonyl group or an aryloxycarbonyl group, and X represents a hydrogen atom, a halogen atom, a carboxy group or an acid. Atom via a nitrogen atom or a sulfur atom represents a coupling split-off to groups with a group bonded to the carbon of coupling position .R ¹¹ or R ¹² or X may form a bis-be divalent groups. It may also be in the form of a polymer coupler in which the coupler residue represented by the general formula (V) or (VI) is present in the main chain or side chain of the polymer, provided that at least one of R ¹¹ or R ¹² is secondary or Represents a group bonded to a pyrazoloazole nucleus via a tertiary carbon, and R ¹¹ or R ¹² contains at least one —NHSO ₂ — group.) General formula (IIa) And the general formula (IIb) (In the formula, Z ¹ and Z ² each independently represent an atomic group necessary for forming an imidazole ring, a pyridine ring, a thiazole ring or a selenazole ring, and these may be combined. R ³ and R ⁵ Each represents an optionally substituted alkyl group, an alkenyl group, an aralkyl group or an aryl group, R ⁴ represents a hydrogen atom or an optionally substituted alkyl group, and R ³ and R ⁴ form a ring. .X representing the good .L divalent linking group be ^- is .m representing the anion represents 0 or 1, n is 0, 1 or 2).