JPS61223742A - Silver halide color photographic sensitive material - Google Patents

Abstract

PURPOSE:To enhance color reproducibility and storage stability of an image and to improve color development performance by forming a layer contg. fine silver halide grain emulsion in a silver halide photographic sensitive material contg. a specified pyrazoloazole type magenta coupler. CONSTITUTION:The layer contg. silver halide fine grain emultion is formed in the silver halide color photographic sensitive material contg. a pyrazoloazole type magenta coupler represented by the formula shown on the right in which R<1> is H or a substituent; X is H or a group to be released by the coupling reaction with the oxidation product of an aromatic primary amine color developing agent; Za, Zb, and Zc are each optionally substd. methine, =N-, or -NH-, and of Za adn Zb bond, Zb and Zc bond is a double bond and the other is a single bond, and when Zb and Zc bond is a C=C bond, it may form a part of aromatic ring; R<1> or X may form a dimer or an oligomer, and when Za, Zb, or Zc is optionally substd. methine, this substituent may form a dimer or an oligomer. The formation of the fine grain emusion layer permits storage stability of an image to be enhanced and sufficient color development density to be obtained without lowering sensitivity at the time of development.

Description

Detailed Description of the Invention (Industrial Field of Application) The present invention relates to a silver halide color photographic light-sensitive material, and more specifically, it relates to a silver halide color photographic material that has improved color reproducibility and image storage stability, and has good color development. This invention relates to silver color photographic materials.

(Background Art) In order to form a color photographic image, photographic couplers of three colors, yellow, magenta, and cyan, are contained in a photosensitive layer, and the layer is processed with a color developing solution containing a color developing agent after being exposed to light. . In this process, the oxidized form of the aromatic primary amine undergoes a coupling reaction with the coupler, resulting in a coloring dye. However, in this case, it is preferable that the coupling rate is as high as possible and that the coloring property is good enough to give a high coloring density within a limited working time. Furthermore, the coloring pigments are bright cyan and magenta with little side absorption.

It is required to be a yellow dye and provide color photographic images with good color reproducibility.

On the other hand, the color photographic images formed are required to have good preservation under vegetative conditions. These storage conditions include, for example, storage conditions in a dark place where the image is exposed to the shadow of humidity and heat, and exposure conditions such as sunlight and indoor lights.Not only discoloration and fading of a one-color image, but also yellowing of the white background is extremely important. This is a serious problem.

In order to meet the above-mentioned requirements for color photographic materials, couplers play a major role as one-color image forming agents.
Conventionally, many improvements have been made by changing the coupler structure6. Conventionally, pyrazolone derivatives have been mainly used as magenta couplers, which are important from the viewpoint of visibility, but the color image formed from this is Not only in the green light range.

It also has unnecessary absorption in the blue and red light regions, and cannot be said to have sufficient performance. Furthermore, j-pyrazolone derivatives tend to decompose and turn yellow under light irradiation or high humidity, making them unsatisfactory in terms of image storage stability.

The color image obtained from the magenta coupler represented by the general formula (I) has less unnecessary absorption in the T light region and the red light region, and is not only advantageous in terms of color reproduction, but also when stored under light irradiation at high humidity F. However, although it is an extremely excellent coupler with little yellowing, it has major practical drawbacks such as decreased sensitivity during development and insufficient color density.

(Object of the present invention) An object of the present invention is to provide a photosensitive material that simultaneously satisfies the above-mentioned properties required of a color 4 true photosensitive material. More specifically, the first object of the present invention is to provide a color photographic material with excellent color reproducibility due to magenta color images with good light absorption characteristics. A second object of the present invention is to provide a color photographic material which has a solid color image under both dark and sunlight conditions and has improved white background staining.

A third object of the present invention is to provide a color photographic material that exhibits good color development with little fogging or decrease in sensitivity during development. Other objects of the invention will become clear from the description below.

(Structure of the Invention) An object of the present invention is to provide a silver halide color photographic light-sensitive material containing a pyrazoloazole magenta coupler represented by the following general formula (I), which has at least one layer containing a silver halide fine grain emulsion. This was achieved using a silver halide color photographic light-sensitive material characterized by the following characteristics.

General Formula (I) In the general formula (I), R represents a hydrogen atom or a substituent, and X represents a hydrogen atom or a group that can be separated by a coupling reaction with an oxidized aromatic primary amine developer. Z
a, Zb and Zc represent methine, substituted methine, =N- or -NH-, and the Za-Zb bond and zb -Zc M
One of the bonds is a double bond and the other is a single bond. Z
The case where b-Zc is a carbon-carbon double bond includes the case where it is part of an aromatic ring. When R or X forms a multimer or more, Za, Zb or Z
When c is a substituted methine, the case where the substituted methine forms a monomer or more is also included.

Invention 6: The compounds used will be explained in more detail below.

In 2 of the general formula (I), the multiplex means one having one or more f; 1 will be. Here, the polymer coupler may be a homopolymer consisting only of a monomer having a moiety represented by general formula (I) (preferably one having a vinyl group, hereinafter referred to as vinyl monomer).

A copolymer may be prepared with a non-color-forming ethylene-like monomer that does not couple with the aromatic primary amine OIIim compound.Among the pyrazoloazole magenta couplers represented by the general formula CI), preferred ones is the following general formula (II)
, (III), (I, (V), (VI).

They are represented by (■) and (■).

(If) (III) (IV) (V) (■) (■) (■) Among the couplers represented by general formulas (II) to (■), preferred for the purpose of the present invention are general formula (I), Among (V) and (■), the more preferred one is represented by the general formula (Vl).

In general formulas (I) to (■), B11.312 and B 2 may be the same or different and are each a hydrogen atom, a halogen atom, an alkyl group, an aryl group, a heterocyclic group, a cyano group, or an alkoxy group.

Aryloxy group, heterocyclic oxygen group, acyloxy group, carbamoyloxy group, silyloxy group, sulfonyloxy group, acylamino group, anilino group, ureido group,
Imide group, sulfamoylamino group, carbamoylamino group, alkyl luteo group, arylthio group, heterocyclic thio group, alkoxycarbonylamino group, arylo-flaticarbonylamino group, sulfonamide group, carbamoyl group, acyl group, sulfamoyl group, sulfonyl group, sulfinyl group, alkohodicarbonyl group, or aryloxycarbonyl group, and X is a hydrogen atom, a halogen atom, a carboxy group, t, or is bonded to the carbon at the coupling position via an oxygen atom, nitrogen atom, or sulfur atom. represents a group that undergoes coupling and decoupling. R, R, Rt or X is a
It may serve as a base of valence and form a bis body.

It may be in the form of a poly W-coupler in which the coupler residues represented by general formulas (!I) to (■) are present in the main chain or side chain of the polymer, and in particular vinyl monomers having a moiety represented by the general formula Preferred are polymers derived from B11. B12. B13 or X represents a vinyl group or a linking group. -For more details R
, R and R each represent a hydrogen atom, a halogen atom (for example, a chlorine atom, a bromine atom, etc.), an alkyl group (for example, a methyl group, a propyl group, a t-butyl group, a trifluoromethyl group).

Tridecyl group, 3-(co, di-t-amyl-7-eboxy)propyl group, allyl group, J-dodecyloxyethyl group, 3-phenol sulfonyl group, cyclopentyl group, cyclopentyl group , benzyl group 1, etc.),
Aryl group (for example.

phenyl group, e-t-butylphenyl group, co-, q-di-amylphenyl group, hiro-tetradecanamidophenyl group 1, etc.), heterocyclic group (e.g.

- monofuryl group, -theenyl group, coffeerimidinyl group,
-penzothiazolyl group, etc.), cyano group, alkoxy group (e.g., methoxy group, etho group, -methoxyethoxy group, codedecyl group, jetoxy group, comethanesulfonyl group, etc.), aryloxy group Group (
For example, phenoxy group, -1methylphenoxy group, 1-
i-butylphenol group, etc.), heterocyclic group (e.g., cobenzimidazolyloxy group, etc.), acyloxy group (e.g., acetyloxy group, hemodecanoyl group, etc.), carbamoyl Oxy groups (e.g., h-phenylcarpamoyloxy group, N-ethylcarbamoyloxy group, etc.), silyloxy groups (e.g., trimethylsilyloxy group, etc.), sulfonyloxy groups (e.g.,
dodecylsulfonyloxy group, etc.), acylamino group (
For example, an acetamide group, a benzamide group, a tetradecanamide group, an α-(co,lizy-t-amylphenoxy)butylamide) group, a γ-(,7-t-7”chiluhiro-hydro-diphenoxy)butyramide group, an α −(α
-(terhydroxyphenylsulfonyl)phenoxy)
(decaneamide group, etc.), Ayu9no group (e.g., phenylamino group, cochloroanilino group, -oneroro!-tetradecanamideanilino group, -oneroroS-dodecyloxycarbonylanilino group, N -acetylanilino group, cochloro!-(α-(s-t-methyl-hiro-hydroxyphenoxy)dodecanamido)anilino group, etc.), ureido group (e.g., phenylureido group, methylureido group, N, N- dibutylfreido group, etc.), imide group (e.g., N-x succinimide group, 3-penzylhydantoinyl L4=-(-monoethylhexanoylamino)phthalimide group, etc.), sulfamoylamino group (e.g., N, N-dipropylsulfamoylamino group, N
-methyl-hedecylsul7 amoylamino group, etc.),
Alkylthio groups (e.g. methylthio group, octylthio group, tetradecylthio group, cophenogyethylthio group, dipropylthio group in 3-phenol 1.7-(4'-t
-butylphenoxy)propylthio group, etc.>, arylthio group (e.g. phenylthio group,
t-octylphenylthio group, 3-pentadecylphenylthio group, cocarphodiphenylthio group, tetradecaneamidophenylthio group, etc.), heterofractionated thio group (
For example, -1penzothiazolylthio group, etc.), alkoxycarbonylamino group (for example, methoxycarbonylamino group, tetradecyloxycarbonylamino group, etc.)
, aryloxycarbonylamino group (for example, phenoxycarbonylamino 1irs 2 e 4'-')
-tert-butylphenoxycarbonylamino group, etc.), sulfonamide group (e.g. methanesulfonamide group, hexadecanesulfonamide group, benzenesulfonamide group, p-)luenesulfonamide group, octadecanesulfonamide group, -monomethyl oxy-z-ti methylbenzenesulfonamide group, etc.), carbamoyl group (
For example, N-ethylcarbamoyl i, N, N--)
-f-thylcarbamoyl group, he-(codedecyloxyethyl)carbazoyl group, N-methyl-N-dodecylcarbamoyl group, N-(y-(J, g-di-tert-amylphenoxy)propyl)carbamoyl group, etc.), acyl groups (e.g. acetyl group, (co, q-tert-
amylphenoxy)acetyl group, benzoyl group, etc.),
Sulfamoyl group (e.g., N-ethylsulfamoyl group, N,N-dipropylsulfamoyl group, N-(codedecyloxyethyl)sulfamoyl group, N-ethyl-N-dodecylsulfamoyl group, N,N- diethylsulfonyl group, etc.), sulfonyl group (e.g., methanesulfonyl group, octanesulfonyl group, benzenesulfonyl group, toluenesulfonyl group, etc.), sulfinyl group (e.g., octanesulfinyl group, dodecylsulfinyl group, phenylsulfinyl group, etc.) ), alkoxycarbonyl groups (e.g., methoxycarbonyl group, butyloxycarbonyl group, dobutylcarminyl group, octadecylcarminyl group, etc.), aryloxycarbonyl group (e.g., phenyloxycarbonyl group, j <ntadecylobase dicarbonyl group) , etc.), X represents a hydrogen atom, a halogen atom (e.g. chlorine atom, bromine atom, iodine atom, etc.), a carboxy group, noyloxy group,
benzoyloxy group, co, dichloropenzoyloxy 7 group, ethomudio, zaroyloxy group, pyruvinyloxy group, cinnamoyloxy group, phenoxy group, lycyanophenoginyl group, q-methanesulfonamidophenoxy group, Hiro- Methanesulfonylphenoxy group, α-naphthoxy &, 7--': ntadecylphenoxy group, benzyloxycarbonyloxy group, ethoxy group, cocyanoethyloxy group, penzylphenoxy group, cophenetyloxy group, cophenoxy Ethoxy group! -phenyltetrazolyloxy group, -penzothiazolyloxy group, etc.), groups linked via a nitrogen atom (e.g., benzenesulfonamide group, N-ethyltoluenesulfonamide group, bebutafluorobutanamide group, Ko, 3. Hiro, !, 6-bentafluorobenzamide group, octane sulfonamide group, p-cyanophenylureido group, N.

N-diethylsulfamoylamino group, l-biyridyl group,! -dimethyl-co, 41-dioxo-3-oxazolidinyl group, l-benzyl-ethoxy-3-hydantoinyl M, JN-i*t-dioxo-3(coH)-oxo-l, J-benzisothiazolyl group, 2 -Oxo-
/, Cokehydro-l-pyridinyl group, imidazolyl group, pyrazolyl group, 3,3-diethyl-7,co,l-triazol-7-yl, S- or 6-promobenzotriazol-l-yl, yo-methyl-1 ．． -0.7.4
'-) lyazol-7-yl group, indiimidazolyl group, 3-benzyl-l-hydantoynyl group, l-benzyl-! -basedecyloxy-J-hydantoinyl group, j
-methyl-7-tetrazolyl group, etc.), arylazo group (e.g., μmmethΦdiphenylazo group, a-piparoylaminophenylazo group, -1-naphthylazo group, 3-methyl-<1-hydroxyphenylazo group, etc.) ), groups linked via a sulfur atom (e.g., phenylthio group, cocarpoxyphenylthio group, comethoxy!-1-octylphenylthio group, dermethanesulfony A/phenylthio group, teroctanesulfonamidophenylthio group, copoxy7 engineering diruthio group, !-(cohegisansulfonylethyl)-j-tert-octylphenylthio group, benzylthio group, cocyanoethyltheo group, cycarbonyltritecylthio group in l-eth, -!t-phenylruco.

3.'t! -tetrazolylthio group, cobenzoteazolylthio group, codedecylthio-3-thiophenylthio group, copheny-3-dodecyl-7゜co+''-triazolyl-yo-thio group, etc.).

In couplers of general formulas (I) and [111),
几 and R may be combined to form a j-negative member ring.

When R11, B12, B, 13 or X becomes a divalent group to form a bis body, preferably 几, B12,
B is a substituted or unsubstituted alkylene group (for example,
Methylene group, ethylene group, 1,10-decylene group, -C
H2CH2-0-CH2CH2-1, etc.), substituted or unsubstituted phenylene groups (e.g., i, u-phenylene JL
/l, 7-phenylene group, -NHC(J-R”4-CU
NH- group (R14 represents a substituted or unsubstituted alkylene group or phenylene group, for example -NHCOC) (2
C82CUNH-1C)(3-NHCOCHC-CH2C(JNH-CH3-8-14-8- group (14 is a substituted or unsubstituted alkylene group, for example, -8-CHCH2-8-1 CH3-8 -CH2C-CH2-8-1, etc.)'4e, C
H3X represents the above monovalent group converted into a monovalent group at an appropriate position.

General formula (lI), (El), (IV), (V), (■)
, (■) and (■) are included in the vinyl monomer, the linking group represented by R1, R or X is an alkylene group (substituted or unsubstituted alkylene group). , for example, methylene group, ethylene group, /, 10
-decylene group, -CH2CH20CH2CH2-1, etc.)
, a phenylene group (substituted or unsubstituted) unicine group,
Example Lld, / t u-phenylene fi%/1. ? -phenylene group, -NHCO-1-CONH-1-〇-1-OCO-, and aralkylene group (for example, includes a group formed by combining α).

Preferred linking groups include the following.

NHCU-1-CH2CH2-1 -CONH-CHCH2CH2υ-1 -CHCH(J-CH2CH2- to HCU-1 The vinyl group has the general formula (I), (l[), (ff), (V), (
Substituents other than those represented by Vl), (■)t or (■) may be used. Preferred substituents are hydrogen atoms, chlorine atoms, or lower alkyl groups having 1-3 carbon atoms (for example, methyl groups, ether group).

General formula (I), (II), (IY), (V), (Vl)
, (■) and (■) may be copolymerized with non-chromogenic ethylene-like monomers that do not couple with the oxidation products of aromatic-grade amine developers. good. “ Non-chromogenic ethylene-like monomers that do not couple with the oxidation products of aromatic-grade amine developers include acrylic acid, α
- Chloroacrylic acid, α-alkylacrylic acid (such as methacrylic acid) and esters or amides derived from these acrylic acids (such as acrylamide, n-butylacrylamide, t-butylacrylamide, diacetone acrylamide, methacrylamide,
Methyl acrylate, ethyl acrylate, n-propyl acrylate, n-butyl acrylate, t-butyl acrylate), 1so-butyl acrylate, 2-
Ethyl ester acrylate, n-octerolylate, lauryl acrylate, methyl methacrylate, ethyl methacrylate, n-butyl methacrylate and β-hydroxy methacrylate), methylene dibisacrylamide, vinyl esters (e.g. vinyl acetate, vinyl propionate and vinyl laurate), acrylonitrile, methacrylaterile, aromatic vinyl compounds (e.g. styrene and its conductors, beer toluene, cyhinylbenzene, vinyl acetophenone and sulphostyrene), itaconic acid, citraconic acid, crotonic acid, vinylidene chloride, vinyl alkyl ethers (
(vinyl ethyl ether), maleic flL, m-hydric maleic acid, maleic esters, N-vinyl-1-pyrrolidone, N-vinylpyridine, and co- and l-
Examples include vinylpyridine. One or more of the non-color-forming ethylenically unsaturated monomers used here can also be used together. Examples include n-butyl acrylate and methyl acrylate, styrene and methacrylic acid, methacrylic acid and acrylamide, methyl acrylate and diacetone acrylamide, and the like.

As is well known in the polymeric color coupler art, non-chromogenic ethylenically unsaturated monomers for copolymerization with solid water-insoluble monomeric couplers depend on the physical and/or chemical properties of the copolymer formed, e.g. solubility, compatibility of the photographic colloidal composition with binders such as gelatin, its flexibility,
It can be selected so that thermal stability etc. are favorably influenced.

The polymer coupler used in the present invention may be water-soluble or water-insoluble, but among them, polymer coupler latex is particularly preferred. Examples are given, but the invention is not limited to these.

(M-/) (M-ko) (M-J) (M-10) (M-//) (M-tko) (M-/,?) (M-tu) (M-zr) ( M-JA) (M-241) CM-J! ? ) CM-JA) (M-17) (M-ichiza) (M-koq) (M-3o) (M-j/) (M-32) (M-,7j) (M-341) ( M-J,?) (M-j 4) (M-37) (M-at) (M-eO) (M-1/) (M-4t4) (M-daJ) (M-child (M -417) (M-!I> (M-7?) (M-+</) (M-42) (M-bu4t) (M-at) (M-4,<) (M-6ri ) (M-70) (M-7/) (M-72) (M-73) (M-77) (M-r) (M-/J) (/4n (l) General formula of the present invention The coupler represented by [1] can be synthesized according to the method described in the following literature.

The compound of general formula (I11 and [■]) is
6.2! The compound of the general formula [1113 is applied to the patent application Shoj♂-/j131 da, etc., and the compound of the general formula 1''V) is applied to the general formula [■] The compound is disclosed in Japanese Patent Application Publication No. 2003-120003 and 79-27.
74t! etc., the compound of the general formula [■] is
74t2rO/ etc., and the compound of general formula [■] is
It is written in ffJ in the United States, θOtsu7゜4t32, etc., respectively.

The coupler of the present invention represented by the general formula (I) can be used per mole of silver halide present in the same layer.
1 mole, good'LL, <hat X/o mole~!
x10-1 mole. Moreover, two or more types of couplers of the present invention can be added to the same layer.

The silver halide fine grain emulsion used in the present invention suitably has an average grain size θ, 07 to 0, θμ, and the smaller the grain size, the more preferable it is. Also, silver chloride, silver chlorobromide, and silver bromide are all used as emulsions! Emulsions containing silver bromide of θ molti or more are preferred.

Although both light-sensitive and non-photosensitive fine grain emulsions can be used, low-sensitivity silver halide grains that are not substantially developed are more advantageous for the purpose of the present invention. The amount added is θ, θθ!
~θ, /f/m2 is appropriate and 0.0/~θ
,0. tf/m is preferred.

Incidentally, such low-sensitivity silver halide grains can be prepared in the same manner as in preparing ordinary non-light-sensitive silver halide emulsions.
Alternatively, it can be prepared in a similar manner to the preparation of ordinary photosensitive silver halide emulsions. In this case, the silver halide grain surfaces do not need to be chemically sensitized or spectral sensitized.

For the purpose of the present invention, it is effective to add such a silver halide fine grain emulsion to an emulsion layer containing a pyrazoloazole magenta coupler represented by the general formula CI). Furthermore, it is effective to add it to an emulsion layer containing other couplers that are far away from each other, or to an intermediate layer or a protective layer. It may also be added to two or more layers at the same time.

Before adding silver halide fine grain emulsions to the coating solution, known stabilizers such as triazole compounds, azaindene compounds, penzothiazolicum compounds, and mercapto compounds should be added in advance. is preferred.

Examples of the silver halide color photographic light-sensitive material to be used in the present invention include color paper, color reversal film, color negative film, color positive film, etc., but in particular, color paper, color reversal film, color positive film, and color reversal film may be used. is preferred.

The magenta coupler of the present invention and the combination couplers described below can be introduced into the light-sensitive material by various known dispersion methods, such as solid dispersion method, alkaline dispersion method, preferably latex dispersion method, and more preferably oil-in-water dispersion method. This can be cited as an example.

In the oil-in-water dispersion method, a high-boiling organic solvent with a boiling point of /J'C or more and a so-called auxiliary solvent with a low boiling point are dissolved either alone or in a mixture of the two, and then dissolved in the presence of a surfactant. Finely dispersed in an aqueous medium such as water or an aqueous gelatin solution. Examples of high boiling point organic solvents are U.S. Pat.
, No. 027, and other representative examples are described in later sections. Dispersion may be accompanied by phase inversion, and if necessary, the auxiliary solvent may be removed or reduced by distillation, noodle washing, ultrafiltration, or the like before use for coating.

Specific examples of high-boiling organic solvents include phthalic acid esters (e.g., dibutyl phthalate, dimethyloctyl phthalate, dicyclohexyl phthalate, di-J-ethyl cylphthalate, didodecyl phthalate, etc.), phosphorus F11 or Phosphonic acid esters (triphenyl phosphate), ) licresyl phosphate, -
monoethyl hexyl phosphate, tricyclohexyl phosphate, ) ethyl hexyl phosphate, tridodecyl phosphate, tributoxyethyl phosphate, trichloropropyl phosphate,
λ-ethylhexylphenylphosphonate, etc.),
Benzoic acid esters (coethylhexylbenzoate, dodecylbenzoate, coethylhexyl-p-hydroxybenzoate, etc.), amides (diethyldodecanamide, N-tetradecylpyrrolidone, etc.), alcohols or phenols (instearyl alcohol, 2, 4t-di-tert-aminyl, etc.), aliphatic carboxylic acid esters (dioctyl azelate, glycerol tributyrate, isostearyl lactate, trioctyl citrate, etc.), anilines (N, N-dibutyl phtate
octylaniline, etc.), hydrocarbons ()q roughin,
(dodecylbenzene, diisopropylnaphthalene, etc.), and as an auxiliary solvent, solvents with a boiling point of about 300
An organic solvent having a temperature of from about /600C to about /600C can be used, and typical examples thereof include ethyl acetate, butyl acetate, ethyl propionate, methyl ethyl ketone, cyclohexanone coethoxyethyl acetate, dimethylformamide, and the like.

The process and effects of latex dispersion methods and specific examples of latex for impregnation are disclosed in U.S. Pat. No. 1, Tata.

No. 343, West German Patent Application No. 2. j≠1. Core No. 3 and No. 2. ! Reference I, No. 230, etc.

In addition to the magenta coupler of the present invention, conventional color couplers can be used in combination with the color photosensitive material of the present invention. Typical examples of useful color couplers include naphthol or Fi mizenol compounds and open chain or heterocyclic ketomethylene compounds.

Specific examples of cyan, magenta, and yellow couplers that can be used in the present invention are provided in Research Disclosure (Re5).
search Disclo@ure, abbreviated as RD)
/74≠J (/7 in 1 month of the year) ■-D section, cited in 1iyl no'17/7 (/7 in 2 months of the year) and described in the following patent.

Preferably, these couplers have ballast groups or are polymerized and diffusion resistant. It is preferable that the coupling position is substituted with a leaving group rather than a hydrogen atom. Couplers in which the chromophoric dye has suitable diffusivity, colorless couplers, or couplers which release a development inhibitor or accelerator upon coupling reaction can also be used.

A representative example of the yellow coupler that can be used in the present invention is an oil-protected acylacetamide coupler. A specific example is US Patent No. 2.4t
07, Core No. 0, Core No. 2. /7j, 0?7 and 3. - is written in j, jObu issues, etc. A 2-equivalent yellow coupler is preferably used in the present invention, US Pat. No. 3,4t01, /? No. Z, No. 3.4t 2.
De 2/No. 3. 33. jθ / No. and same g, 4t
Oxygen atom separation type yellow coupler or Tokkosho described in θ/lrjλ issue etc. ? -/θri No. 3, U.S. Patent No. 1, 0.2, 520, U.S. Patent No. 3, 3.2, 0
No. 241, RD//θ! 3 (2013), British Patent No. 1,1 is No. 020, West German Application Publication Tube 2. -/ri,
RI/RI No.-, Ko 4/, 367, 2nd and 3rd Kota, 127 and λ.

33. Typical examples include the nitrogen atom separation type yellow couplers described in r/co. The α-piparoylacetanilide couplers are characterized by the fastness of color-forming dyes, and the -10,000-α-benzoylacetanilide couplers are characterized by good color-forming properties.

The magenta coupler that can be used in combination with the present invention is preferably an oil-protected indacylon or cyanoacetyl coupler! - Examples include pyrazolone couplers. ! The -pyrazolone coupler is preferably one in which the 3-position is substituted with an arylamino group or an acylamino group from the viewpoint of the hue of the chromophore and the speed of color development.A representative example thereof is U.S. Patent No. , same No. 2.
j4tJ, No. 703, same No. 2. ≦Oθ, No. 7//, No. λ, No. 01, No. 3, No. J, 042.63
-3, same No. 3. /j co, t? No. 6 and No. 3 of the same. ? 3
Go.

It is described in No. 071, etc. 2 equivalents! -Pyrazolone couplers are preferred, as the leaving group U.S. Pat. or the nitrogen atom leaving group described in US Patent No. 4t,! ! -／、? The arylthio group described in No. 97 is preferred. Further, the pyrazolone coupler having a palust group as described in European Patent No. 73.4jj has high color-forming reactivity.

Cyan couplers that can be used in the present invention include oil-protected naphthol-based and phenolic couplers, and US Patent Nos. λ, (t74t, 2?, ?
Preferably, the naphthol couplers described in U.S. Patent No. 9. θ! 2, 2/, No. 2, same No. 6.3, No. 6,
Same No. 4t, 22♂, 233 and same No. 2, -
Specific examples of roughenol couplers include the highly active 2-equivalent naphthol coupler of nine oxygen atom elimination type described in US Patent No. 00, US Pat. 69
, No. 929, No. 4t23.730, No. 2
．． No. 272.762 and No. 272.762. It is described in ♂rij, No. 726, etc.

Humidity and temperature robust cyan couplers are preferably used in the present invention, exemplified by the phenolic cyan couplers described in US Pat. No. 3,772.002, US Pat. No. J, 772.

/6-No. J, 7j1.702, Same No. G.

/26.326, Dow No. 33, No. 011, Dow No. 327.173, West German Patent Publication No. 3゜32, 72
9 and % Gansho J Jr-4t267/, etc., and U.S. Patent No. 3.4t≦, U.S. Patent No. 22, U.S. Pat.
33, Wata No. 9, same No. 9, 4t! / , No. 339 and the same No. G, 4t Co 2゜7 Co No. 7, etc. have a phenylureido group at the co-position and! These are phenolic couplers having an acylamino group in the - position.

Of course, two or more types of the coupler of the present invention and the couplers described above can be used in the same layer in order to satisfy the characteristics required of a photosensitive material, or the same compound can be added to one or more different layers. No problem.

The color coupler used in combination may also be entirely composed of polymers of No. 2 or higher. Typical examples of polymerized couplers are U.S. Pat.
It is described in the // issue. Specific examples of polymerized magenta couplers are given in British Patent No.

No. 102.173 and U.S. Patent No. 4t, 3b7゜2♂
It is listed in No.

As the binder or protective colloid that can be used in the emulsion layer or intermediate layer of the light-sensitive material of the present invention, it is advantageous to use gelatin, but other hydrophilic colloids can also be used alone or together with gelatin.

Any of silver bromide, silver iodobromide, silver iodochlorobromide, silver chlorobromide and silver chloride may be used as silver halide in the photographic emulsion layer of the photographic light-sensitive material used in the present invention.

The average grain size of the silver halide grains in the photographic emulsion (expressed as the grain diameter for spherical or approximately spherical grains, and the ridged grain size for cubic grains, expressed as an average based on the projected area) is particularly important. Although it is not, it is preferably 3μ or less.

The particle size distribution may be narrow or wide.

The silver halide grains in the photographic emulsion may have a regular crystalline structure such as a cube or a hexagonal, or may have a spherical or hexagonal shape.
It may have an irregular crystalline shape such as a plate shape, or it may be a composite of these crystalline shapes. The emulsion may be composed of a mixture of grains of various crystal forms.Also, an emulsion may be used in which ultratabular silver halide grains with a grain diameter of at least one times the grain thickness occupy 10% or more of the total projected area. It's okay.

The silver halide grains may have different phases inside and on the surface. Further, the particles may be particles in which the latent image is mainly formed on the surface, or may be particles in which the latent image is formed as a crown inside the particle.

The photographic emulsion used in the present invention includes P, graphide (P
, Grafkides), 1 Chimle etP.
hysique Photographique
)'', Paul Montel
) Published by the company (/1962), G, F, Dahuy (G, F
, Duffin), 1 Photographic Emulsion Chemistry (Photographic Emulsion Chemistry)
Emulsion Chemistry)”, published by FocalPress (1964), V, L, Zelikman (V, L, Zelikman)
)Other Domains, 1 Making and Coating Photographic-Effk John (Making an
d CoatingEmulsion), Focusa A/
- It is described in the press publication (/?6 da year) and can be adjusted using the nen method. That is, any of the acidic method, neutral method, ammonia method, etc. may be used, and the method for reacting the soluble silver salt and the soluble halide salt is the one-sided mixing method.

Either a simultaneous mixing method or a combination thereof may be used.

It is also possible to use a method in which particles are formed in an excess of silver ions (so-called back-mixing method).

As one type of simultaneous mixing method, a method in which the pAg in the liquid phase in which silver halide is produced can be kept constant, that is, a so-called Chondrald double jet method can also be used.

According to this method, a silver halide emulsion having a regular crystal shape and a nearly uniform grain size can be obtained.

Two or more types of silver halide emulsions formed separately may be mixed and used.

In the process of silver halide grain formation or physical ripening, cadmium salts, zinc salts, lead salts, thallium salts, iridium salts or complex salts thereof, rhodium salts or complex salts thereof, iron salts or iron complex salts, etc. may be allowed to coexist. .

Silver halide emulsions are usually chemically sensitized.

For chemical sensitization, for example, H, Freezer (H, Fr
1eser, ) ed., 'Die Grundlagender.
Die Grundlagende (DieGrundlagende)
rPhotographischenProzes
se mit Silberhalogeniden
)'', Akademi 5che Verlagsgeschaft (Akademi 5che Verlagsgese
llschaft), (/?bu 7th year) No.67j~rij
The method described on page 4 can be used.

That is, sulfur sensitization using sulfur-containing compounds that can react with active gelatin and silver (e.g., thiosulfates, thioureas, mercapto compounds, rhodanines); reducing substances (e.g., stannous salts, amines, hydrazine derivatives, formamidine sulfinic acid, silane compounds); noble metal compounds (e.g., total complex salts, Pt, I
A noble metal sensitization method using complex salts of metals of group (I) of the periodic table such as r%Pd can be used alone or in combination.

The photographic emulsion used in the present invention can contain various compounds for the purpose of preventing fog during the manufacturing process, storage, or photographic processing of the light-sensitive material, or for stabilizing photographic performance. Namely, azoles such as benzothiazolium salts, nitroimidazoles, nitrobenzimidazoles, chlorobenzimidazoles, bromobenzimidazoles, mercaptothiazoles, mercaptobenzothiazoles, mercaptobenzimidazoles, mercaptothiadiazoles, aminotriazoles. , benzotriazoles, nitrobenzotriazoles, mercaptotetrazoles, especially l-phenyl-! Mercaptopyrimidines: Mercabutotriazines: Thioketo compounds such as oxatrintheone Niazaindenes, such as doriazaindenes, tetraazaindenes (especially dihydroxy-substituted (/, !, ja, 7) ) Tetraazaindenes), pentaazaindenes; many compounds known as antifoggants or stabilizers can be added, such as henzenethiosulfonic acid, benzenesulfinic acid, benzenesulfonic acid amide, etc. can.

In the photographic emulsion layer of the photographic light-sensitive material of the present invention, for the purpose of increasing sensitivity, increasing contrast, or accelerating development, for example, polyalkylene esters or derivatives thereof such as ethers, esters, and amines, thioether compounds, thiomorpholines, etc. Quaternary ammonium salt compounds, urethane derivatives,
It may also contain urea derivatives, imidazole derivatives, 3-pyrazolidones, and the like.

In the photographic light-sensitive material used in the present invention, for the purpose of improving dimensional stability in the photographic emulsion layer and other hydrophilic colloid layers,
Dispersions of water-insoluble or sparingly soluble synthetic polymers can be included.

The photographic emulsions used in the present invention may be spectrally sensitized with methine dyes and others. The dyes used include cyanine dyes, merocyanine dyes, complex cyanine dyes, complex merocyanine dyes, holopolar cyanine dyes, hemicyanine dyes, styryl dyes and hemioxonol dyes. Particularly useful dyes are those belonging to the cyanine dyes, merocyanine dyes, and complex merocyanine dyes. Any of the nuclei commonly used for cyanine dyes can be used as the basic heterocyclic nucleus for these dyes.

These sensitizing dyes may be used alone or in combination, and combinations of sensitizing dyes are often used particularly for the purpose of supersensitization.

Along with the sensitizing dye, it is a dye that itself does not have a spectral sensitizing effect or a substance that does not substantially absorb visible light,
A substance exhibiting supersensitization may also be included in the emulsion. - For example, aminostyryl compounds substituted with nitrogen-containing heterologous groups (
For example, US patent λ.

933.320, J, tjj, No. 7.2/), aromatic organic acid formaldehyde condensates (for example, those described in U.S. Pat. No. 3,74tJ, 310), cadmium salts, azaindene compounds, etc. May include.

The invention is also applicable to multilayer, multicolor photographic materials having at least one different spectral sensitivity on the support. Multilayer natural color photographic materials usually consist of a red-sensitive emulsion layer, a green-sensitive emulsion layer, and a blue-sensitive emulsion layer on a support. Each has at least one.

You can choose any order of these shields depending on your needs.

Usually, the red-sensitive emulsion layer contains a cyan-forming coupler, the green-sensitive emulsion layer contains a magenta-forming coupler, and the blue-sensitive emulsion layer contains a yellow-forming coupler, but different combinations may be used depending on the case.

The photographic light-sensitive material of the present invention may contain an inorganic or M-organic hardener in the photographic emulsion layer and other hydrophilic colloid layers.

For example, activated vinyl compounds (/, j.

! -triacryloyl-hexahydro-5-triazine, /, 3-vinylsulfonyl-2-propatol, etc.)
, active halogen compound (Z, 4t-dichloro-3-hydroxy-5-triazine), mucohalogen e'l
A (mucochloric acid, mucophenoxychloric acid, etc.), etc. can be used alone or in combination.

The light-sensitive material produced using the present invention may contain a hyde non-derivative, an aminophenol derivative, a gallic acid derivative, an ascorbic acid conductor, and the like as a color antifogging agent.

The photosensitive material of the present invention may contain an ultraviolet absorber in the hydrophilic colloid layer. For example, U.S. Patent No. 3, t, 3
J, 7 free issue, same gu, 2j &, θ/3 issue, Tokko Akira! /
-634tO and European Patent No. 7.160, etc., benzotriazoles substituted with an oryl group; US Pat. /the law of nature! , butadines listed in the Tatata issue,
US patent 3,7θ! .

Cinnamic acid esters described in Rot No. 3.707.371, US Pat.
No. 0 and British Patent No. 1,! 2/,! Benzophenones described in No. jj, U.S. Patent No. 3.7-7.27
Polymer compounds having ultraviolet absorbing residues t such as those described in No. - and No. 4tj/, No. 724 of the same can be used. U.S. Patent Nos. J * 4t Tade, No. 26 and 3. ri0θ, 41j! Ultraviolet-absorbing fluorescent brighteners described in this issue may also be used. Typical examples of ultraviolet absorbers are described in 几D24T23DE (/ri? June 1999).

The photosensitive material produced using the present invention may contain a water bathing dye in the hydrophilic colloid layer as a filter dye or for various purposes such as preventing irradiation. Such dyes include oxonol dyes, hemioxonol dyes, styryl dyes, merocyanine dyes, cyanine dyes and azo dyes. Among them, oxonol dyes: hemioxonol dyes and merocyanine dyes are useful.

In carrying out the present invention, the following known anti-fading agents may be used in combination, and the color image stabilizers used in the present invention may be used alone or in combination of two or more. Known anti-fading agents include hydroquinone derivatives, gallic acid derivatives, p-fultugiciphenols, p-ox diphenol fermentation derivatives, and bisphenols.

The color photographic emulsion layer forming the dye image 1vI according to the present invention is coated on a flexible support such as a plastic film, paper, or cloth commonly used in photographic light-sensitive materials.

When these supports are used for reflective materials, it is preferable to add a white pigment to the support or laminate layer. White pigments include titanium dioxide, barium sulfate,
Examples include zinc oxide, zinc sulfide, calcium carbonate, antimony trioxide, silica white, alumina white, titanium phosphate, etc., and titanium dioxide, barium sulfate, and zinc oxide are particularly useful.

The surface of these supports is generally treated with an undercoat to improve adhesion with photographic emulsions and the like. The surface of the support may be subjected to corona discharge, ultraviolet irradiation, flame treatment, etc. before or after the undercoating treatment.

When these supports are used for reflective materials, a hydrophilic colloid layer containing a high density of white pigment is provided between the support and the emulsion layer to improve the whiteness and sharpness of the photographic image. I can do it.

In the reflective material having the magenta coupler of the present invention, a paper support laminated with a polymer is often used as the support, but if a synthetic resin film kneaded with a white pigment is used, smoothness, gloss, sharpness, In addition to improving the degree of
This is particularly preferable since it provides photographic images with particularly excellent saturation and depiction of dark areas. In this case, the synthetic resin film raw material is
Polyethylene terephthalate and cellulose acetate are particularly useful as white pigments, and barium sulfate and titanium oxide are particularly useful.

The color photographic light-sensitive material of the present invention (in addition to the above, various photographic additives known in this field, such as stabilizers, antifoggants, surfactants, antistatic agents, developing agents, etc.) may be added as necessary. can be added, examples of which are described in Research Disclosure/744tj.

The color developer that can be used in the present invention is preferably an alkaline aqueous solution containing an aromatic primary amine color developer as a main component. As a color developing agent, guamino-N, N-diethylaniline, 3-methyl-guamino-N, N-diethylaniline, y-aminoheethylhe β-hydroxyethylaniline, 3-methyluda-amino-ethylhe β -Hydroxyethylaniline, 3-methylderaminoheetherhe β-
Methanesulfamide ethylaniline, kuamino-3-
Typical examples include methyl-h-ethyl-N-β-methoxyethylaniline.

The color developer may contain pH buffering agents such as alkali metal sulfites, carbonates, borates, and phosphates, development inhibitors or antifoggants such as bromides, iodides, and organic antifoggants. can be included. If necessary, water softeners, preservatives such as hydroxylamine, organic solvents such as benzyl alcohol and diethylene glycol, development accelerators such as polyethylene glycol, quaternary ammonium salts, and amines, dye-forming couplers, competitive couplers,
Fogging agents such as sodium boron hydride, /-
Auxiliary developers, tackifying agents, such as phenyl-3-pyrazolidone, US Patent No. 3, Or3.

It may contain the polycarboxylic acid-based child sheet agent described in No. 723, the antioxidant described in West German Publication (JLS) Co., Otsu, 22, ?J-θ, and the like.

After color development, the photographic emulsion J- is usually subjected to a marking process.

The bleaching process may be performed simultaneously with the fixing process, or may be performed separately. Examples of bleaching agents include iron(I),
Compounds of polyvalent metals such as cobalt (I), chromium (■), and copper (II), peracids, quinones, nitroso compounds, and the like are used. For example, ferricyanide, dichromate, organic complex salts of iron(III) or subaru)(II[),
For example, ethylenediaminetetraacetic acid, nitrilotriic acid fl!
,/,! -Aminopolycarboxylic acids such as diamino-coprobanoltetraacetic acid or complex salts of organic acids such as citric acid, tartaric acid and malic acid; persulfates, manganates; nitrosophenols, etc. can be used.

Of these, potassium ferricyanide, sodium iron(It) ethylenediaminetetraacetate and iron(I[[)ammonium ethylenediaminetetraacetate] are particularly useful. Ethylenediaminetetraacetic acid iron (In) complex salts are useful in both stand-alone bleach solutions and -bath bleach-fix solutions.

It may be washed with water after color development or bleach-fixing treatment.

Color development can be carried out at any temperature between /10C and jroc.

The development time is preferably as short as about 3 minutes to about 7 minutes. For continuous development processing, liquid replenishment is preferable, with 33θCC to 40cc per square meter of processing area,
Preferably, a liquid of 10θCC or less is replenished.

Bleach fixing starts from /♂0C! Although it can be carried out at any temperature of 01C, it is preferably 3θ0C or higher. The time required for washing with water after color development or bleach-fixing is usually 3 minutes or less, and it is also possible to wash with water within 7 minutes using a stabilizing bath.

Colored pigments deteriorate and fade due to exposure to heat and temperature, but also due to mold during storage. Cyan images are particularly susceptible to severe deterioration due to mold, so it is preferable to use a fungicide. Specific examples of antifungal agents are disclosed in JP-A-37-/J724.
There are corchiazolylbenzimidazoles as described in t4t. The antifungal agent may be built into the photosensitive material, or may be added from the outside during the development process, or may be added at any process if it coexists with the processed photosensitive material.

(Example) The present invention will be described below with reference to Examples, but the present invention is not limited thereto.

(Example/) A multilayer color photographic paper having the layer structure shown in Table I was prepared on a paper support coated with polyethylene on both sides. The coating solution was prepared as follows.

First layer coating solution preparation: Yellow Kabra (a) 10? and color image stabilizer (b)2. 4 tmy of ethyl acetate/θ and solvent (c)/7 were added and dissolved, and this solution was emulsified and dispersed in 70% aqueous gelatin solution containing 10 ml of sodium dodecylbenzenesulfonate. On the other hand, silver chlorobromide emulsion (silver bromide 10% to A51'-70P/#
Contains) the following blue-sensitive dyes per mole of silver chlorobromide, 2! Add 4 moles of X/θ to make a blue-sensitive emulsion
I made it.

The emulsified dispersion and the emulsion were mixed and dissolved, and the concentration was adjusted with gelatin to give the composition shown in Table I to prepare a coating solution for the first layer.

The second layer to second layer coating solution were also prepared in the same manner as the seventh layer coating solution. As a gelatin hardening agent for each layer /-oxy-3
，! -Dichloros-triazine sodium salt was used.

The following spectral sensitizers were used in each emulsion.

The structural formulas of the compounds used in this example, such as couplers, are as follows.

(a) Yellow coupler (C) Solvent (C, Hl, O+VP=U (e) Solvent (f) UV absorber /:j:j mixture (molar ratio) α (b) Color image stabilizer (i ) Solvent P=U /:, a mixture of the two coating solutions for the first to second layers can be coated simultaneously after adjusting the balance of surface tension and viscosity to prepare a multilayer silver norogenide color photographic light-sensitive material. .

When preparing the third layer coating solution, the fine grain emulsion of the present invention (silver bromide 10
In addition, samples A to H were prepared in which only the third layer had a different structure, as shown in Table (1).

These silver halide color light-sensitive materials were wedge exposed in a conventional manner and processed according to the processing steps and processing solution formulations shown below.

Sensitometric evaluation was performed on the obtained sample. The results are shown in Table ■〉.

〔Processing method〕

Process Temperature Time Bleach fixing 33°C 7 minutes 30 seconds Washing 33°0 3 minutes [Processing solution composition] (Color developer) Water 100
rnl sodium tetrapolyphosphate 2.0? Benzyl alcohol lda, 01 diethylene glycol 10. oxl sodium sulfite λ, Ofpotassium bromide
0. jf sodium carbonate
30.0? Heethyl-(β-methanesulfonamidoethyl) -3-methyl-deraminoaniline sulfone) j, OfhydroΦ
Zylamine sulfur flR salt a, o y - add water
/θ00dpH(,ZJ”C)
100.20 (bleach-fix solution) Water 4t0
0 ammonium gothiosulfate (70%) /zθ
d Sodium sulfite / If ethylenediaminetetraacetic acid iron acetate t) Ammonium! j? Ethylenediaminetetraacetic acid Naj? add water
/θ00gopH(λj0c)
2. o.

As is clear from Table ■, the coexistence of fine grain emulsions increases relative sensitivity without worsening fog.
An increase in the maximum color density was observed, and a significant improvement in color development was observed.

(Example =) Samples No. - T were prepared in the same manner as in (Example/) by changing the layer to which the fine grain emulsion of the present invention (60 moles of silver bromide) was added.

Table ■〉 shows the sample contents.

After exposing each sample in the same manner as Sample 1-Tt- (!i!Example/), each sample was coated with Fujicolor Roll Brosetner FP-P-//j
' (manufactured by Fuji Photo Film Co., Ltd.) was used to perform continuous processing using the following processing steps.

〔Processing method〕

Process Time Temperature Tank capacity Color development 3 minutes 30 seconds 310C±0.3°c to
43 Bleach fixing 1 minute 30 seconds 33°C± /'C4tO
J3 water washing■ 7 minutes 33°C±3°C2o water washing■ 7
Minutes 33°C±3°C 20 minute wash ■ 7 minutes 33°C±
3°C sob The washing process was a three-stage countercurrent washing from washing (①) to washing (③).

In addition, the amount of processing liquid brought in from the various pre-tanks from the bleach-fixing step to washing with water is θrd/m2.

The conditions of the color development process are all constant, and the replenishment amount is photosensitive material/m
The solution used is as follows:

[Processing liquid composition]

(Coloring liquid) Tank liquid Replenisher water
tθθml J”00M
1 nitrilotriacetic acid-JNa 2.0ff-, 2,
Of Benzyl Alcohol /4 Punishment /rwJ
Diethylene glycol /θrrtl iow
l Sodium sulfite 2.0? =,! ? Hydroxylamine sulfate 3.0f 3. , tf Potassium bromide /, Off - Sodium carbonate 3θgL jjf Heteru N-(β
- Methanesulfonamidoethyl)-3-methyl-guaminoaniline sulfate! , Of fOf water added /θθortJ/θoompH10,/
, t 10. tnz The conditions of the bleach-fixing process are all constant, and the replenishment amount is 60 txl per m2 of sensitive material. The solution used has the following formulation.

(Bleach-fix solution) Tank solution Replenisher water
4t00- da θ0 friend 1 ammonium thiosulfate (70%) /JOd jθ
O-Sodium sulfite /I? 3≦? Iron (I) ethylenediaminetetraacetate ammonium sr) /10 f
Ethylenediaminetetraacetic acid・ , 2Na jf /θ? Add water to 10ooILlioθO-pH
6,706,! 0 The conditions of the water washing process are all constant, and the replenishment amount is sensitive material/ln”
One hit! θ-. The following six solutions are used.

/-Hydroxyethylidene- /, /-diphosphonic acid (60) Co, 0d Aluminum sulfate 1.0? Sulfanilamide 0.7? The pH was adjusted to 11 with water and adjusted to pH 7.0 with aqueous ammonia.

The results of sensitometry at the time when each sample was treated are shown in Table V.

As is clear from Table II and Table V, the effect of the fine grain emulsion is unique to the magenta coupler represented by the general formula (I) of the present invention, and is effective even if it is not necessarily in the same layer as the magenta coupler. This was confirmed.

(Example 3) Samples C%F, H, J%M, and U were processed as in Example 3 without being exposed. The obtained sample was placed in a λθ million-lux xenon bleacher for 2 days,
Store in %RIH under each condition for 1θ day and check the degree of yellowing of the white background.

Table ■〉 shows no increase in yellow density on a white background.

From Table ■〉 Table ■〉, it can be seen that the magenta coupler represented by the general formula (I) of the present invention has a significantly improved degree of yellowing of the white background compared to conventional magenta couplers under various storage conditions. Recognize.

Patent applicant Fuji Photo Film Co., Ltd. Procedural amendment (side 1, case description 1985 patent application No. 4/P7)
No. 2, Title of the invention Silver halide color photographic light-sensitive material 3, Relationship with the case of the person making the amendment Patent applicant 4, Date of the amendment order Showa! / year / month date (shipment date) & subject of amendment We will submit an engraving of Statement 6, the details of the amendment (no changes to the content).

Procedural amendment ■, Indication of case Showa tO patent application No. 44/77 2, Title of invention Silver halide color photographic light-sensitive material 3
, Relationship with the case of the person making the amendment List of patent applicants Subject of the amendment ``Detailed Description of the Invention'' column of the specification & Contents of the amendment The description of the ``Detailed Description of the Invention'' section of the specification shall be as follows: Correct.

l) The 70th member is rj in the row, 10X10 4,6/, 2"f"1.toxt
o 'moj/m2J.

2) Page 70, line io [t, ozxto 'wt/m'J'k'y, ozx
io 4m6)/m”J.

3) Page 70 // line "!, koxto-'pu/m"Jt Correct as "z, Joxto 'mat/m"J.

4c) Page 70, page 1 [/,! 0X10 “I!j/Atsushi 2” to “t, zox”
io”mol/mJ.

j) On page 70/line j, change "t,zoxto "d/rn"J to "/,!0X1
Correct as 0 “mol/rn”J.

6) Page 70 - Line 222 [ko, J j X / 0' d/z ” J
is corrected as [a, 5Jxio 'mol/m''J.

7) Page 70 - line 6 [7, ko2xzO’sj/m”Jt [7, Correct as x x to 'moJ/m''J.

l) Page 70, line 27 [t, 5rxto 'td/rn"Jk"1.3jx
1O-4mol/TrL2".

? ) The structural formula of the color image stabilizer on page 71 is ”　　　　　　− and correct it.

IO) On page 7, line 13 to line l, change "The numbers in the table are for fine grain emulsion" to "The numbers in the table are the amount of silver (r/m")? represent ” he corrected.

The year 1985 is Monday - 7th 1. Display of the case Showa tθ year patent application No. A4'15'
No. 7 No. 2, Title of the invention Silver halide color photographic light-sensitive material 3, Relationship with the case of the person making the amendment Patent applicant contact information 10
6 2-26-30 Nishi-Azabu, Minato-ku, Tokyo Subject of amendment: “Detailed Description of the Invention” column of the specification & Contents of amendment: Insert a separate sheet between page 3 of the specification and page 32 .

(M-r6) ・Se (M-rr) CH,=C-CH3 〉 ゝCaH1let)

Claims (1)

[Scope of Claims] A silver halide color photographic light-sensitive material containing a pyrazoloazole magenta coupler represented by the following general formula (I), characterized by having at least one layer containing a silver halide fine grain emulsion. Silver halide color photographic material. General formula (I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ In the general formula (I), R^1 represents a hydrogen atom or a substituent, and X represents a hydrogen atom or a combination with an oxidized aromatic primary amine developer. Represents a group that can be separated by a coupling reaction. Za, Zb, and Zc are methine, substituted methine,
=N- or -NH-, and the Za-Zb bond and Zb
One of the -Zc bonds is a double bond, and the other is a single bond. The case where Zb-Zc is a carbon-carbon double bond includes the case where it is part of an aromatic ring. When forming a dimer or more multimer with R^1 or X,
Furthermore, when Za, Zb or Zc is a substituted methine, it also includes the case where the substituted methine forms a dimer or more multimer.