JPH0616163B2 - Silver halide color photographic light-sensitive material - Google Patents

Description

TECHNICAL FIELD The present invention relates to a silver halide color photographic light-sensitive material, and more specifically, it has excellent color reproducibility and environmental conditions (temperature conditions, etc.) during photography. The present invention relates to a silver halide color photographic light-sensitive material having little dependence.

(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 to reproduce a color image. Therefore, 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 having more excellent spectral absorption characteristics than ureido type and acylamino type (Japanese Patent Laid-Open Nos. 49-74027 and 49-1116).
No. 31, etc.) was developed. Furthermore, a pyrazoloazole-type magenta coupler with less unwanted side absorption (US Pat. No. 3,
725,067) have been developed. This latter coupler has less unnecessary absorption in the blue light region and the red light region as compared with the color image obtained from the 5-pyrazolone type magenta coupler, and is not only advantageous in terms of color difference, but the coupler itself does not emit light or heat. It has the following advantages: it is stable against temperature, it is difficult to decompose, and there is little yellowing of the resulting image over time.

(Problems to be Solved by the Invention) However, this pyrazoloazole-based magenta coupler causes unnecessary desensitization and produces unnecessary desensitization (or printing) as compared with a generally used 5-pyrazolone-type magenta coupler. It has a drawback that the color balance is lost depending on the environment (especially the temperature condition). For example, when the temperature at the time of shooting is high, the image appears as a whole green, and when the temperature is low such as winter, it appears as a reddish color. Not good for

Regarding such a change in photographic property depending on the environment at the time of shooting, for example, The Theory of the Photofraffic Process 4th Edition T.I. H. TH James, Chapter 4, Section 2, Chapter 5, Section 2, Photographic ·
Science Engineering (photogr.Sci.Eng.,) 1
7, 325 (1973) and the like. However, the environmental dependence of the pyrazoloazole-based magenta coupler during photographing is not known.

Therefore, an object of the present invention is to provide a silver halide color photographic light-sensitive material that takes advantage of the advantages of the pyrazoloazole-based magenta coupler and has the drawbacks of reduced sensitivity and less environmental dependence during photography.

More specifically, a first object is to provide a color photographic sensitizer having a more excellent color reproducibility by using a magenta color image having a good spectral absorption characteristic. The second object is to provide a color photographic light-sensitive material which has a strong color image and has improved white background contamination with age. A third object is to provide a photographic light-sensitive material that is less dependent on environmental conditions during photography.

(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. This can be achieved by containing silver halide to which a specific metal compound is added together with the coupler. It has been found that a sensitizer that is not easily affected by the temperature conditions during shooting can be obtained. The present invention has been accomplished based on this finding.

That is, an object of the present invention is to provide a silver halide having a layer containing at least one kind of magenta coupler represented by the following general formula [1] and adding 10 ^-9 to 10 ^-3 mol of iridium salt to at least one layer. Achieved by containing a silver halide color photographic light-sensitive material.

General formula (I) (In the formula, Za and Zb are Or = 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, at least one of R ₁ or R _2, represents a group bonded to the pyrazoloazole nucleus through a secondary or tertiary carbon, and, R ₁ or R ₂ is at least one -NH
It includes groups - SO _2. ) Preferred iridium salts to be added to the silver halide emulsion in the present invention are shown below.

(II-1) K ₃ IrCl ₆ (II-2) K ₂ IrCl ₆ (II-3) K ₃ IrBr ₆ (II-4) K ₂ IrBr ₆ (II-5) IrCl ₃ (II-6) IrBr ₄ It is already known that these iridium salts are added to a silver halide photographic emulsion and used. British Patent No. 60
No. 2,158 describes the stabilizing effect of photographic emulsions, and U.S. Pat. No. 2,448,060 describes the sensitizing effect. On the other hand, Japanese Patent Publication No.
No. 4, Japanese Patent Publication No. 45-32738, Japanese Patent Publication No. 49-3378
1, JP-A-52-65432, and JP-A-52-769.
23, JP-A-52-88340, JP-A-56-14.
No. 7142 describes the reciprocity law characteristic improving effect, latent image stability improving effect, slope characteristic improving effect, and pressure characteristic improving effect of these compounds.

However, it was first discovered in the present invention that the iridium salt as described above exhibits excellent temperature dependence prevention and desensitization prevention effects on certain pyrazoloazole-based magenta couplers described in detail later. It is a thing.

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-containing monomer, hereinafter referred to as a vinyl monomer) may be used, or a non-coupling agent 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 ones are those represented by the following general formula (III),
It is represented by (IV), (V), (VI) and (VII).

Among the couplers represented by the general formulas (III) to (VII), preferred ones for the purpose of the present invention are the general formulas (III), (V) and
(VI), and more preferred is one represented by the general formula (VI).

The present invention preferably comprises at least one pyrazolotriazole coupler represented by the general formula (V) or (VI), and a halogen containing 10 ^-9 to 10 ^-3 mol of a water-soluble iridium salt per mol of silver. A silver halide color photographic light-sensitive material having a silver halide emulsion layer containing silver halide grains.

Formula (V) Formula (VI) (In the formula, R ¹¹ and R ¹² 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 developer.
R ¹¹ and R ¹² may be X and form a dimer or higher multimer. However, at least one of R ¹¹ or R ¹² represents a group that bonds to the pyrazoloazole nucleus through a secondary or tertiary carbon atom, and R ¹¹ or R ¹² represents at least one —NHSO ₂ — group. including. In the general formulas (III) to (VII), R ¹¹ , R ¹² and R ¹³ may be the same or different from each other, for example, a hydrogen atom, a halogen atom, an alkyl group, an aryl group, a heterocyclic group, a cyano group. , An alkoxy group, an 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 Group, alkoxycarbonylamino group, aryloxycarbonylamino group,
Represents a sulfonamide group, a carbamoyl group, an acyl group, a sulfamoyl group, a sulfonyl group, a sulfinyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, and X represents a hydrogen atom, a halogen atom, a carboxy group or an oxygen atom, a nitrogen atom or a sulfur atom. A group which is coupled to the carbon at the coupling position via the coupling-off group. R ¹¹ , R ¹² , R ¹³ or X may be a divalent group to form a bis form.

It may also 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 case 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.),
Alkyl group (for example, methyl group, propyl group, isopropyl group, t-butyl group, trifluoromethyl 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, cyclopentyl group, benzyl group Etc.), an aryl group (eg, a phenyl group, 4-t-
Butylphenyl group, 2,4-di-t-amylphenyl group, 4-tetradecanamidophenyl group, etc.), heterocyclic 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-dodecyloxyethoxy group,
2-methanesulfonylethoxy group, etc.), aryloxy group (for example, phenoxy group, 2-methylphenoxy group,
4-t-butylphenoxy group etc.), heterocyclic oxy group (eg 2-benzimidazolyloxy group etc.), acyloxy group (eg acetoxy group, hexadecanoyloxy group etc.), carbamoyloxy group (eg N-phenyl) Carbamoyloxy group, N-ethylcarbamoyloxy group etc.), silyloxy group (eg trimethylsilyloxy group etc.), sulfonyloxy group (eg dodecylflufonyloxy group etc.), acylamino group (eg acetamide group, benzoamide 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 (eg, , Phenylamino group, 2-chloroanilino group, 2-chloro-5-tetradecaneamido anilino group, 2-chloro-5-dodecyloxycarbonylphenyl anilino group, N- acetyl anilino 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 (for example, N-succinimide group, 3-benzylhydantoinyl group, 4-
(2-ethylhexanoylamino) phthalimide group, etc.), sulfamoylamino group (eg, N, N-dipropylsulfamoylamino group, N-methyl-decylflufamoylamino 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 (for example, 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), alkoxycarbonylamino group (eg, methoxycarbonylamino group, tetradecyloxycarbonylamino group, etc.), aryloxycarbonylamino group (eg, phenoxycarbonylamino group) , 2,4-di-t
ert-butylphenoxycarbonylamino group, etc., flufonamide group (eg, methanesulfonamide group, hexadecanesulfonamide group, benzenesulfonamide group, p-toluenesulfonamide group, octadecanesulfonamide group, 2-methyloxy-5-) t-butylbenzenesulfonamide group, etc.), carbamoyl group (eg,
N-ethylcarbamoyl group, N, N-dibutylcarbamoyl group, N- (2-dodecyloxyethyl) carbamoyl group, N-methyl-N-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-dodecyl group. Sulfamoyl group, N, N-diethylsulfamoyl group, etc., Sulfonyl group (eg, methanesulfonyl group, octanesulfonyl group, benzenesulfonyl group, toluenesulfonyl group, etc.) Sulfinyl group (eg, octansulfinyl group, dodecyl) Sulfinyl group, phenylfurfinyl group, etc.), alkoxycarbonyl group (eg, methoxycarbonyl group, butyloxycarbonyl group, dodecylcarbonyl group, octadecylcarbonyl group, etc.), aryloxycarbonyl group (eg, phenyloxycarbonyl group, 3- Penta Acyloxy - represents a carbonyl group, etc.), X is a hydrogen atom, a halogen atom (e.g.,
Chlorine atom, bromine atom, iodine atom, etc.), carboxy group,
Or a group linked by an oxygen atom (for example, an 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-benzothiazolyloxo group, etc.), groups linked by nitrogen atoms (for example, benzenesulfonamide group, N-ethyltoluenesulfonamide group, peptafluorobutanamide group, 2,3 , 4,
5,6-pentafluorobenzamide group, octanesulfonamide group, p-cyanophenylureido group, N, N
-Diethylsulfamoylamino group, 1-biperidyl 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 etc.), arylazo group (for example, 4-methoxyphenylazo group, 4-pivaloylaminophenylazo group, 2-naphthylazo group, 3-methyl-4-hydroxyphenylazo group etc.), sulfur Groups linked by atoms (for example, phenylthio group, 2-carboxyphenylthio group, 2-methoxy-5-t-octylphenylthio group, 4-methanesulfonylphenylthio group, 4-
Octanesulfonamide phenylthio 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).

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

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

R ¹¹ , R in the case where the vinyl monomer contains the compounds represented by the general formulas (III), (IV), (V), (VI), and (VII)
^The linking group represented by ¹² , R ¹³ or X is an alkylene group (a substituted or unsubstituted alkylene group, for example, a methylene group, an ethylene group, a 1,10-decylene group, —CH ₂
CH ₂ OCH ₂ CH ₂ — and the like), phenylene group (substituted or unsubstituted phenylene group, for example, 1,4-phenylene group, 1,3-phenylene group, Etc.), —NHCO—, CONH—, —O—, —OCO— and aralkylene groups (eg, Etc.) and groups that are established by combining those selected from the above.

Preferred linking groups include:

_{-NHCO -, - CH 2 CH 2} -, -CH ₂ CH ₂ NHCO-, _{-CONH-CH 2 CH 2 NHCO-,} -CH 2 CH 2 O-CH 2 CH 2 -NHCO-, The vinyl group may have a substituent other than those represented by the general formulas (III), (IV), (V), (VI) and (VII), and a preferable substituent is a hydrogen atom, a chlorine atom or a carbon atom. It represents a lower alkyl group of 1 to 4 (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 compounds that do not couple with oxidation products of aromatic primary amino developing agents. You may make a copolymer with a monomer.

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-alkyl acrylic acid (eg methacrylic acid) and esters or amides derived from these acrylic acids (eg acrylamide, n-butyl acrylamide, t-butyl acrylamide diacetone acrylamide, 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, etc.) 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, non-color forming ethylenically unsaturated monomers for copolymerization with solid water-insoluble monomer 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 synthesis method are described in Japanese Patent Application Nos. 58-23434 and 58-151354.
58-45512, 59-27745, 58-1
42801 and U.S. Pat. No. 3,061,432.

Specific examples of typical magenta couplers among the couplers represented by formula (I) are shown below, but the invention is not limited thereto.

I-1. I-2. I-3. I-4. I-5. I-6. I-7. I-8. I-9. I-10. I-11. I-12. I-13. I-14. I-15. I-16. I-17. I-18. I-19. I-20. I-21. I-22. I-23. I-24. I-25. I-26. I-27. I-28. I-29. I-30. I-31. I-32. I-33. I-34. I-35. Preferred embodiments of the present invention will be described below.

The preferable ratio of the magenta coupler to silver halide in the magenta color forming layer is 0.05 to 5 mol, more preferably 0.1 to 0.5 mol.

The weight ratio of the high boiling point solvent to the pyrazoloazole magenta coupler is preferably 0 to 6.0. More preferably, it is 0.3 to 2.0. The silver halide emulsion containing an iridium compound is preferably used as a silver halide emulsion having a plurality of layers.

The amount of the iridium compound added is 10 ^-9 to 10 ^-3 mol, preferably 10 ^-8 to 10 ^-6 mol, based on 1 mol of the silver halide. The iridium compound can be added to the silver halide grains during grain formation, after grain formation, during chemical ripening, or during coating. Desirably during particle formation or
It can be added by the time of chemical aging.

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 described in Research Disclosure (RD) 17643 (December 1978) Section VII-D and the patent cited in 18717 (November 1979). Has been done.

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. It is also possible to use a coupler in which the color-forming dye has an appropriate diffusibility, a non-color-forming coupler, or a DIR coupler which releases a development inhibitor upon coupling reaction or a coupler which releases a development accelerator.

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 US Pat. No. 2,40.
No. 7,210, No. 22,875,057 and No. 3,265,506. In the present invention, it is preferable to use a two-equivalent yellow coupler, and US Pat. Nos. 3,408,194 and 3,447,928 are preferred.
No. 3,933,501 and No. 4,022.
No. 620 and other yellow couplers of oxygen atom elimination type or Japanese Patent Publication No. 58-10739, U.S. Pat. Nos. 4,401,752, 4,326,024, R
D18053 (April 1979), British Patent No. 1,42
No. 5,020, West German Application Publication No. 2,219,917,
Typical examples thereof include nitrogen atom elimination type yellow couplers described in Nos. 2,261,361 and 2,329,587 and 2,433,812. The α-pivaloyl acetanilide type couplers are excellent in the fastness of color forming dyes, especially the light fastness, while the α-benzoyl acetanilide type couplers can obtain a high color density.

Cyan couplers that can be used in the present invention include oil-protection type naphthol type and phenol type couplers. The naphthol type couplers described in US Pat. No. 2,474,293, preferably US Pat. No. 4,05.
2,212, 44,146,396, 4,
Representative examples thereof include oxygen atom desorption type two-equivalent naphthol couplers described in U.S. Pat. Nos. 228,233 and 4,296,299. Specific examples of the phenol-based coupler are described in US Pat. Nos. 2,369,929 and 2
No. 2,801,171, No. 2,772,162, No. 2,895,826. Cyan couplers that are fast to humidity and temperature are preferably used in the present invention, and typical examples thereof include US Pat.
No. 2,772,162, U.S. Pat. No. 3,772,162, U.S. Pat. No. 3,758,308, and U.S. Pat. 126, 396,
No. 4,334,011, No. 24,327,173
2, West German Patent Publication No. 23,329,729 and Japanese Patent Application No. 58-42671, and 2,5-diacylamino-substituted phenol couplers and US Pat. Nos. 3,446,622 and 4,4. 333, 999, 4,451,559 and 4,427,767.
And the like, which have 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, after dissolving in either a single liquid of a high boiling organic solvent having a boiling point of 175 ° C. or higher and a so-called auxiliary solvent having a low boiling point or a mixed liquid of both, 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 US Pat. No. 2,32
2, 027 and the like.

The standard amount of 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.

The silver halide emulsion used in the present invention usually comprises a water-soluble silver salt (for example, silver nitrate) solution and a water-soluble halogen salt (for example, potassium bromide, sodium 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 (the grain diameter is the grain size for spherical or near-sphere grains, and the ridge length is the grain size for cubic grains) is 2μ or less. 0.1μ or more is preferable,
Particularly preferred is 1 μ or less and 0.15 μ or more. 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 a 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 in an emulsion layer having substantially the same color sensitivity are mixed in the same layer or different layers. 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 shape of the silver halide grains used in the present invention may be one having a regular crystal such as a cube, octahedron, dodecahedron and tetradecahedron, and may be irregular such as spherical.
It may have an (irregular) crystal form, or may have a composite form of these crystal forms. Also, tabular grains may be used, and particularly, the value of length / thickness ratio is 5 or more, especially 8
An emulsion in which the above tabular grains account for 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 P. Graf Kiddes "Chemie and Physique Photograph"
ique) (published by Paul Montell, 1967), G.I.
F. Duffin's "Photograhic Emulsio"
Chemistry) (Focal Press, 1966)
Year), V. L. It can be adjusted by the method described in "Making and Coating Photographic Emulsion" by Zelikuman et al. (Foral Press, 1964). That is, the acidic method,
A neutral method, an ammonia method, or the like may be used, and a method of reacting the soluble silver salt and the soluble halogen salt may be a one-sided mixing method, a simultaneous mixing method, or a combination thereof. 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, silver halide forms pA in the liquid phase.
It is also possible to use a method of keeping g constant, that is, a so-called controlled table 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, Rhodan potassium or U.S. Pat. No. 3,271,157;
No. 1-12360, JP-A No. 53-82408, JP-A No. 53-144319, JP-A No. 54-100717, or JP-A No. 54-155828. It can be used in 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 production process of the light-sensitive material, during storage or during 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 1764
3 (December 1978) and ibid 18716 (197).
(November 9).

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 also relates to Research Disclosure 17123 (July 1978).
It is also applicable to a black and white light-sensitive material using a mixture of three-color couplers described in (Mon.).

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-toluenesulfonates and the like can be mentioned.

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. As the bleaching agent, for example, compounds of polyvalent metals such as iron (III), cobalt (III), chromium (VI), copper (II), peracids, quinones, nitroso compounds and the like are used. Representative bleaching agents are ferricyanide compounds; dichromates; organic complex salts of iron (III) or cobalt (III), such as ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, nitrilotriacetic acid, 1,3-diamino-2-provanoltetraacetic acid. Aminopolycarboxylic acids such as or complex salts of organic acids such as citric acid, tartaric acid and malic acid; persulfates; manganates; nitrosophenol and the like can be used. Of these, ethylenediaminetetraacetic acid iron (I
II) 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 an independent 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, L. E. West "Water Quality Criteria", "Science and Engineering of Photography" (Photo.Sci.Eng.), Volume 6, 344-3
You may add the compound as described in page 59 (1965) etc. 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 / 57
You may implement the multistage countercurrent stabilization treatment process as described in -8543. Various compounds are added to the stabilizing bath for the purpose of stabilizing the image. For example, various buffers (eg borate, metaborate, borax, phosphate, carbonate, potassium hydroxide, sodium hydroxide, aqueous ammonia) for adjusting the membrane pH (eg pH 3 to 8) , A monocarboxylic acid, a dicarboxylic acid, a polycarboxylic acid and the like are used in combination) and formalin. In addition, water softener (inorganic phosphoric acid,
Aminopolycarboxylic acid, organic phosphoric acid, aminopolyphosphonic acid, phosphonocarboxylic acid, etc.), bactericide (benzoisothiazolinone, irithiazolone, 4-thiazoline benzimidazole, halogenated phenol, etc.), surfactant, fluorescent brightening Various additives such as agents and hardeners may be used, 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,
57-144547, 57-2111147, 58-50532, 58-50536, 58-.
No. 50533, No. 58-50534, No. 58-505.
35 and 58-115438.

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. In addition, West German Patent No. 2, for saving silver in the light-sensitive material
226,770 or US Pat. No. 3,674,499
You may perform the treatment using the cobalt intensification or the hydrogen peroxide trapping force described in No.

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.

(Effects of the Invention) The silver halide color photographic light-sensitive material of the present invention is characterized by excellent sensitivity, color reproducibility and image storability, and low dependence on environmental conditions at the time of photographing or development. Further, the image obtained by this silver halide color photographic light-sensitive material has an excellent effect that the yellowing of the white background during storage is significantly reduced.

(Example) Hereinafter, the present invention will be described in detail based on specific examples.
The present invention is not limited to these.

Example 1 The emulsion of the present invention and the comparative emulsion were prepared as follows.

Solution I Solution II Solution III Solution IV Solution V While keeping Solution I at 65 ° C. with stirring, Solutions II and IV were added at a silver potential of +10 mV over 40 minutes, followed by Solution II.
The same potential as I was added over 40 minutes. After washing with water three times by the sedimentation method, the pH was adjusted to 6.5 and ordinary gold and sulfur sensitization was performed. The emulsion thus obtained was (E-
1).

In the preparation of the emulsion (E-1), an emulsion prepared by adding an aqueous solution of the iridium compound (II-1) 20 minutes after the start of the addition of the solutions III and V was added so as to be 10 ⁻⁷ mol with ^respect to 1 mol of silver. (E
-2), and similarly the iridium compound (II-1) was added to 10
Emulsions added at ^-2 mol and 10 ^-10 mol respectively (E-
3) and (E-4). On the other hand, iridium compounds (II
-1) was added 20 minutes after the start of addition of solutions II and IV (E-5), and emulsion immediately after addition of solutions III and IV (E-6) was sensitized with gold and sulfur. The previously added one was designated as (E-7).

Therefore, the emulsions included in the present invention are (E-2), (E
-5), (E-6), (E-7), and (E-1),
(E-3) and (E-4) are not included.

Using these emulsions, the first to third layers were coated on a triacetate film base in the following order to prepare samples 101 to 107, respectively.

1st layer: Green-sensitive layer Spectral-sensitized to green with a green sensitizer (* 1) Emulsion (E-1) Silver 1.5 g / m ² Magenta coupler (* 2) (* 5) or (* 6) ) 0.35 g Coupler solvent (* 3) 0.10 g Gelatin 4.00 g Second layer: Yellow filter layer Yellow colloidal silver 0.04 g Gelatin 1.00 g Third layer: Protective layer Gelatin 2.00 g The above composition for each layer Besides, a gelatin hardening agent (* 4) and a surfactant were added.

The compounds used to make the samples are shown below.

* 1 * 2 * 5 * 6 I-23 * 3 Tricresyl phosphate * 4 These samples 101 to 107 were subjected to white wedge exposure under the conditions of 10 ° C., 25 ° C. and 35 ° C., and subsequently subjected to the development processing described below. Treatment process Process time Temperature First development 6 minutes 38 ° C Water wash 2 minutes 〃 Reversal 2 minutes 〃 Color development 6 minutes 〃 Adjustment 2 minutes 〃 Bleach 6 minutes 〃 Soaking 4 minutes 〃 Water washing 4 minutes 〃 Safe The composition of the 1-minute normal-temperature drying treatment liquid is as follows. First developer water 700 m Nitrilo-N, N, N-trimethylene phosphonic acid pentasodium salt 2 g Sodium sulfite 20 g Hydroquinone monosulfonate 30 g Sodium carbonate (monohydrate) 30 g 1-Phenyl-4methyl-4-hydroxy Methyl-3 pyrazolidone 2 g Potassium bromide 2.5 g Potassium thiocyanate 1.2 g Potassium iodide (0.1% solution) 2 m Water was added 1000 m Inversion liquid water 700 m Nitrilo-N, N, N-trimethylene phosphonic acid-5 Sodium salt 3 g Stannous chloride (dihydrate) 1 g p-Aminophenol 0.1 g Sodium hydroxide 8 g Glacial acetic acid 15 m Water was added to 1000 m Color developer water 700 m Nitrilo-N, N, N-trimethylene phosphonic acid-5 Sodium salt 3g Sodium sulfite 7g Third phosphorus Sodium (12-hydrate) 36 g Potassium bromide 1 g Potassium iodide (0.1% solution) 90 m Sodium hydroxide 3 g Citrazic acid 1.5 g N-Ethyl-N- (β-methanesulfonamiadethyl) -3-methyl -4-aminoaniline / sulfate 11 g 3,6-dithiaoctane-1,8-diol 1 g Water was added to 1000 m adjusted liquid water 700 m sodium sulfite 12 g ethylenediaminetetraacetic acid sodium salt (dihydrate) 8 g thioglycerin 0.4 m glacial acetic acid 3m Water added 1000m Bleached water 800m Ethylenediaminetetraacetic acid sodium (dihydrate) 2g Ethylenediaminetetraacetic acid iron (III) ammonium (dihydrate) 120g Potassium bromide 100g Water added 1000m Fixer water 800m Sodium thiosulfate 80g sodium sulfite 5g Sodium bisulfite 5g Water added 1000m Stable water 800m Formalin (37% by weight) 5.0m Fuji Drywell (Fuji Film Co., Ltd. surfactant) 5.0m Water added 1000m Measurement was carried out with a G filter of a self-recording densitometer (FAD) to obtain a relative sensitivity of 1.0.

The color purity in the above table is the value of D _B and D _R at the point of D _G = 2.0, where D _B , D _G and D _R are the magenta color density measured with B, G and R filters, respectively. It is a value obtained by the formula: degree of colored paper = (D _B + D _R / D _G ).
Therefore, as the magenta color paper degree, the smaller the value, the more pure the color is magenta.

From the results shown in Table 1, pyrazoloazole couplers generally have higher color purity than 5-pyrazolone couplers, but they are susceptible to sensitivity deterioration and sensitivity change due to photographing temperature. However, the combination of the specific pyrazoloazole-based magenta coupler according to the present invention and the iridium-containing emulsion can solve these problems, and can provide a light-sensitive material having high color purity, reduced sensitivity, and extremely low temperature dependence. Recognize.

Example 2 A paper support laminated on both sides with polyethylene was multilayer-coated with the following first to eleventh layers to prepare a color photographic light-sensitive material. 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.

(Composition of Photosensitive Layer) 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.

First layer (anti-halation layer) Black colloidal silver 0.10 Gelatin 0.20 Second layer (low-sensitivity red-sensitive layer) Silver iodobromide emulsion spectrally sensitized with red sensitizing dye (* 15 and * 14) (Silver iodide 3.5 mol%, average particle size 0.7 μ) Silver 0.15 Gelatin 1.00 Cyan coupler (* 13) 0.30 Color inhibitor (* 12) 0.15 Coupler solvent (* 28 And * 11) 0.06 Third layer (high-sensitivity red-sensitive layer) Silver iodobromide emulsion spectrally sensitized with a red sensitizing dye (* 15 and * 14) (8.5 mol% silver iodide, average) Grain size 0.7μ) Silver 0.10 Gelatin 0.50 Cyan coupler (* 13) 0.10 Anti-fading agent (* 12) 0.05 Coupler solvent (* 28 and * 11) 0.02 Fourth layer ( Intermediate layer) Yellow colloidal silver 0.02 Gelatin 1.00 Color mixing inhibitor (* 24 0.08 Color mixture inhibitor solvent (* 23) 0.16 Polymer latex (* 16) 0.40 Fifth layer (low sensitivity green sensitive layer) Iodobromide spectrally sensitized with green sensitizing dye (* 22) Silver emulsion (silver iodide 1.5 mol%, average grain size 0.4μ) Silver 0.02 Gelatin 0.70 Magenta coupler (* 21) 0.40 Anti-fading agent A (* 20) 0.05 Anti-fading agent B (* 19) 0.05 Anti-fading agent C (* 18) 0.02 Coupler solvent (* 17) 0.25 g 6th layer (high sensitivity green sensitive layer) Spectral sensitization with green sensitizing dye (* 22) Silver iodobromide emulsion (3.5 mol% silver iodide, average grain size 0.9 μ) silver 0.02 gelatin 0.70 magenta coupler (* 21) 0.40 anti-fading agent A (* 20) 0 .05 anti-fading agent B (* 19) 0.05 anti-fading agent C (* 18) 0.02 Coupler solvent (* 17) 0.25 7th layer (yellow filter layer) Yellow colloidal silver 0.20 Gelatin 1.00 Color mixing inhibitor (* 24) 0.06 Color mixing inhibitor solvent (* 23) 0.24 Eight layers (low-sensitivity blue-sensitive layer) Silver iodobromide emulsion spectrally sensitized with a blue sensitizing dye (* 26) (2.5 mol% silver iodide, average grain size 0.5 μ) Silver 0.15 gelatin 0.50 Yellow coupler (* 25) 0.20 Coupler solvent (* 28) 0.05 9th layer (high-sensitivity blue sensitive layer) Silver iodobromide emulsion spectrally sensitized with a blue sensitizing dye (* 26) (Silver iodide 2.5 mol%, average grain size 1.4 μ) Silver 0.20 Gelatin 0.50 Yellow coupler (* 25) 0.20 Coupler solvent (* 28) 0.05 10th layer (UV absorbing layer) ) Gelatin 1.50 UV absorber (* 29) 1 0.000 UV absorber solvent (* 28) 0.30 Color mixing inhibitor (* 27) 0.08 11th layer (protective layer) Gelatin 1.00 Hardener (* 30) 0.17 The compound used here is , As follows: * 11 dioctyl phthalate * 12 2- (2-hydroxy-3-sec-butyl-
5-t-butylphenyl) benzotriazole * 13 2- [α- (2,4-di-t-amylphenoxy) butanamide] -4,6-dichloro-5-ethylphenol * 14 5,5'-dichloro- 3,3'-Di (3-sulfobutyl) -9-ethylthiacarbonylcyanine Na salt * 15 Triethylammonium-3- [2- {2-
[3- (3-Sulfopropyl) naphtho (1,2-d) thiazoline-2-ylidenemethyl] -1-butenyl} -3
-Naphtho (1,2-d) thiazolino] propane sulfonate * 16 polyethyl acrylate * 17 trioctyl phosphate * 18 2,4-di-t-hexyl hydroquinone * 19 di- (2-hydroxy-3-t- Butyl-5-
Methylphenyl) methane * 20 3,3,3 ', 3'-tetramethyl-5,6,6
5 ', 6'-Tetrapropoxy-1,1'-bisspiroindane * 21 1- (2,4,6-trichlorophenyl) -3
-(2-chloro-5-tetradecanamido) anilino-
2-Pyrazolino-5-one * 22 5,5'-diphenyl-9-ethyl-3,3 '
-Disulfopropyloxacarbocyanine Na salt * 23 Phosphoric acid-o-cresyl ester * 24 2,4-Di-t-octylhydroquinone * 25 α-pivaloyl-α-[(2,4-dioxo-
1-benzyl-5-ethoxyhydantoin-3-yl)
-2-Chloro-5- (α-2,4-dioxo-t-amylphenoxy) butanamino] acetanilide * 26 Triethylammonium 3- [2- (3-benzylrhodanin-5-ylidene) -3-benzoxazoli Nyl] propane sulfonate * 27 2,4-di-sec-octylhydroquinone * 28 Trinonyl phosphoric acid ester * 29 5-Chloro-2- (2-hydroxy-3-t-)
Butyl-5-t-octyl) phenylbenztriazole * 30 1,4-bis (vinylsulfonylacetamido) ethane * 31 The sample manufactured as described above is referred to as sample number 201,
This was used as a comparative control sample thereafter.

Sample No. 201 of the second, third, fifth, sixth, eighth and ninth layers of silver halide emulsion or the fifth and sixth layers of magenta coupler (* 2
1) Samples 202 to 208 that were replaced as shown in Table 2 below were prepared.

Table 3 below shows the results of measuring these samples with a Fuji type self-recording densitometer, after performing stepwise exposure for sensitometry and developing treatment in the following processing steps.

[Treatment process]

First development (black and white development) 38 ° C 1 minute 15 seconds Water washing 38 ° C 1 minute 30 seconds Reverse exposure 100 Lux or more 1 second or more Color development 38 ° C 2 minutes 15 seconds Water washing 38 ° C 45 seconds Bleach fixing 38 ° C 2 minutes 00 Second water wash 38 ° C. 2 minutes 15 seconds [Treatment liquid composition] First developer nitrilo-N, N, N-trimethylenephosphonic acid pentasodium salt 0.6 g Diethylenetriaminepentaacetic acid pentasodium salt 4.0 g Potassium sulfite 30. 0 g potassium thiocyanate 1.2 g potassium carbonate 35.0 g hydroquinone monosulfonate / potassium salt 25.0 g diethylene glycol 15.0 m 1-phenyl-4-hydroxy-methyl-4-methyl-3-pyrazolidone 2.0 g potassium bromide 0. 5g Potassium iodide 5.0mg Add water 1 (pH 9.70) Color developer Benzyl alcohol 15.0 m diethylene glycol 12.0 m 3,6-dithia-1,8-octane diol 0.2 g nitrilo-N, N, N-trimethylene phosphonic acid pentasodium salt 0.5 g diethylenetriamine pentaacetic acid pentasodium salt 2.0 g Sodium sulfite 2.0 g Potassium carbonate 25.0 g Hydroxyamine sulfate 3.0 g N-Ethyl-N- (β-methanesulfonamidoethyl) -3-methyl-4-aminoaniline sulfate 5.0 g Potassium bromide 0. 5 g Potassium iodide 1.0 mg Water was added 1 (pH 10.40) Bleach-fixing solution 1-Mercapto-1,3,4-triazole 1.0 g Ethylenediaminetetraacetic acid dinatrium dihydrate 5.0 g Ethylenediamine tetra Iron (III) acetate ammonium-hydrate 80.0 g Sodium sulfite 15.0 g Thio Sodium acid (700 g / liquid) 160.0M glacial acetic 5.0m Water to make 1 (pH6.50) From the results shown in Table 3, the pyrazoloazole couplers having good color purity are less sensitive than the 5-pyrazolone couplers or have a large temperature dependency during printing, and the color balance changes depending on the temperature. Although not preferred, it can be understood that these disadvantages can be eliminated by the combination of the specific pyrazoloazole coupler contained in the present invention and the emulsion using iridium.

Example 3 On a paper support laminated on both sides with polyethylene, the following 1st layer (bottom layer) to 7th layer (top layer) were coated and multilayer silver halide color photographic light-sensitive materials A to H were coated. Table 4
Shows the contents of the sample.

Each layer contains gelatin hardener 2,4-dichloro-
6-Hydroxy-1,3-5-triazine sodium salt and surfactant were added.

For Sample 301, the emulsions of the first, third and fifth layers and the magenta coupler of the third layer were changed as shown in Table 5, and Samples 302 to
305 was created.

Table 6 shows the results of measurement with a Fuji type self-recording densitometer, after performing a stepwise exposure for sensitometry on each of these samples and then performing a development process by the following process steps.

Processing step 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 The components of each processing solution are as follows.

Color developer Water 800 m Sodium tetrapolyphosphate 2.0 g Benzyl alcohol 14.0 m Diethylene glycol 10.0 m Sodium sulfite 2.0 g Potassium bromide 0.5 g Sodium carbonate 30.0 g N-ethyl-N- (β-methanesulfonamidoethyl) -3-methyl-4-aminoanilinesulfonate 5.0 g Hydroxylamine sulfate 4.0 g Water was added to 1000 m pH (25 ° C) 10.00 Bleach-fixing solution Water 400 m Ammonium thiosulfate (70%) 150 m Sodium sulfite 18 g Ethylenediaminetetraacetic acid iron (III) ammonium 55 g Ethylenediamine acetic acid / di sodium 5 g Water was added to 1000 m pH (25 ° C.) 6.70 The color purity was measured in the same manner as in Example 2 by measuring the magenta density of the exposed portion of the G filter.

It can be seen from Table 6 that the examples according to the present invention provide samples with good color purity and no temperature dependence during exposure.

Claims (1)

[Claims] 1. A silver 1 and at least one pyrazolotriazole coupler represented by the following general formula (V) or (VI):
A silver halide color photographic light-sensitive material having a silver halide emulsion layer containing silver halide grains containing 10 ^-9 to 10 ^-3 mol of a water-soluble iridium salt per mol. Formula (V) Formula (VI) (In the formula, R ¹¹ and R ¹² 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 developer.
R ¹¹ , R ¹² or X may form a dimer or higher multimer. However, at least 1 of R ¹¹ or R ¹²
Represents a group attached to the pyrazoloazole nucleus via a secondary or tertiary carbon, and R ¹¹ or R ¹² contains at least one —NHSO ₂ — group. )