JPS6292944A - Silver halide color photographic sensitive material - Google Patents

Abstract

PURPOSE:To obtain the title material capable of reducing sharply an absorption of a light at a long wavelength range and forming a colored image having a good hue and having a good stability on standing by incorporating a specific magenta coupler and a sensitizing coloring matter to an emulsion layer contg. silver chloride, silver chlorobromide or silver bromide. CONSTITUTION:The silver halide such as silver chloride, silver chlorobromide or silver bromide is incorporated to the emulsion layer provided on the substrate. The title material contains the magenta coupler shown by formula I (wherein R1 and R2 are each a hydrogen atom or a substituent, said substituent may form a dimer, X is hydro gen or a group capable of releasing by coupling it with an oxidant of an aromatic primary amine developing agent), and one or more of the sensitizing coloring matters shown by formulas II-IV (wherein W1 and W2 are each a hydrogen atom or an alkyl group, V1-V4 are each a hydrogen or a halogen atom or an alkylaryl group, etc., V5 and V6 are each the same meaning to the groups V1-V4 except an aryl group, V1 and V2 and V3 and V4 together with each other may form a condensed benzene ring respectively, R3-R11 are each an alkyl or an aralkyl group, etc., Y is O or S, X1-X3 is each an acidic anion, (l), (m) and (n) is each 0 or 1). Thus, the title material having the excellent stability on standing and having the excellent reproductivity of the hue is obtd.

Description

Detailed Description of the Invention (Industrial Application Field) The present invention relates to a silver halide color photographic light-sensitive material, and more particularly to a silver halide color photographic material with improved color reproducibility and oral stability. It relates to photographic materials.

(Prior Art) In silver halide color photographic 1μ optical materials, so-called dye-forming couplers (2) which form dyes by reacting with oxidized products of monochromatic silver halide emulsions and aromatic-grade amine developers (
A method using a coupler (hereinafter simply referred to as a coupler) is often used.

Among them, a combination of a yellow coupler, an uncoupler and a magenta coupler is usually used for color photographic materials.

Among these, pyrazoloazole couplers have recently been developed as magenta couplers.

Unlike conventional 5-pyrazolone magenta couplers, pyrazoloazole couplers do not have sub-absorption near 430 nm, and the absorption at longer wavelengths sharply decreases to zero, producing magenta color images with high color purity. It has favorable characteristics such as easy formation and excellent light fastness of the dye.

(Problem to be solved by the invention) However, when this pyrazoloazole type magenta coupler with excellent hue is used in combination with a silver halide emulsion and a silver chlorobromide emulsion, the coating solution and color light-sensitive material become desensitized over time. It was found that it causes Therefore, the present invention was achieved after various studies were conducted on measures to obtain a color photographic material with excellent stability over time using such a magenta coupler.

Therefore, an object of the present invention is to provide a silver halide color photograph with improved stability over time using a pyrazoloazole magenta coupler that sharply reduces absorption on the long wavelength side and can form a color image with excellent hue. Our purpose is to provide photosensitive materials.

In particular, it is an object of the present invention to provide a silver halide photographic material having improved stability over time by using the above-mentioned pyrazoloazole type magenta coupler in a silver chlorobromide emulsion.

[Means for solving problems]

As a result of repeated research in order to achieve the above object, the present inventors used a magenta coupler represented by the following general formula (Il) as a pyrazole azole type magenta coupler.
By using this in combination with a spectral sensitizing dye represented by the following general formulas (N to (C)), a color photographic material with excellent stability over time could be obtained without desensitization over time.

That is, the present invention has at least one silver halide emulsion layer on a support, and the silver halide of the emulsion layer is silver chloride,
silver chlorobromide or silver bromide, and at least one magenta coupler represented by the following general formula (I) and a sensitizing dye represented by the following general formula (A), (B) or (C) in the emulsion layer. A silver halide color photographic light-sensitive material characterized by containing at least one of the following.

General formula (wherein R□ and R2 represent a hydrogen atom or a substituent,
X represents a hydrogen atom or a group that can be separated by a coupling reaction with an oxidized aromatic primary amine developer, and R1
Alternatively, when R2 is a group other than a hydrogen atom, this includes the case where the group forms a dimer or more multimer. In addition, R and R
It is preferable that 2 is branched or has an -NH8○2- group.

In the above formula, Wl and W2 represent a hydrogen atom or an alkyl group.

V, VV and (4) represent a hydrogen atom, a halogen atom, an alkyl group, an aryl group, an alkoxy group, an amide group, an alkoxycarbonyl group, or a cyan group. (1) and v2 and (3) and (4) may be the same or different, and may be fused benzene rings.

■ and V6 may be the same or different, hydrogen atom,
halogen atom, alkyl group, alkoxy group, amide group,
Represents an alkoxycarbonyl group or a cyan group.

Two or more substituents represented by V□ to V6 may be contained in the same molecule. R3, R4, R5, R6, R7, RR
R and R1□ represent an alkyl group or an 8%9-10 aralkyl group. However, R3, R4 and R5
At least one of R6, R7, R8, R9, Rlo, and R11 represents a sulfo group, a carboxyl group, or a salt thereof, or an alkyl group or an aralkyl group containing a hydroxyl group.

Y represents an oxygen atom or a sulfur atom, and Xl, X2 and X3 represent acid anions. 1% m% and n represent O or 1, and when each compound is an inner salt, represent 0).

The present invention will be explained in detail below.

In the general formula (I), the multimer refers to a polymer having two or more groups represented by the general formula (1) in one molecule, and includes bis forms and polymer couplers. 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), or an aromatic primary amine A copolymer may be used with a non-color-forming ethylene-like monomer that does not couple with the oxidized developer.

R1 and R2 may be the same or different and each represents a hydrogen atom, a halogen atom, an alkyl group, an aryl, a heterocyclic group, a cyan group, an alkoxy group, an acyloquine group, a heterocyclicoxy group, an acyloxy group, a carbamoylamino group, and an lyloxy group. group, sulfonylox7 group, acylamino method, nilino group, ureido group, imido group, sulfamoylamino), eagle, carbamoylamino group, alkylthio group, arylthio group, heterocyclic thio group, alkoxycarbonylamino group, aryloxy /Represents a carbonylamino group, sulfonamide group, carbamoyl group, acyl group, sulfamoyl scrap, sulfonyl group, sulfinyl group, alkoxycarbonyl group, aryloxycarbonyl group, and X is a hydrogen atom, a halogen atom, a carboxy group, or an oxygen atom. A group that bonds to the carbon at the coupling position through an atom, a nitrogen atom, or a sulfur atom, and does not represent a group that separates from coupling. R1, R2 or X may be a divalent group to form a bis body. It may also be in the form of a polymer coupler in which the coupler residue is present in the main chain or side chain of the polymer, and in particular a polymer derived from a vinyl monomer having a moiety represented by the general formula is preferred, in which case R1, R2
Or X represents a vinyl group or a linking group.

More specifically, R1 and R2 are a hydrogen atom, a chlorine 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, a tridecyl group, a -(24-ji-t
-amylphenoxy)propyl group, 2-t"decyloxyethyl group, 3-phenoxypropyl group, 2-hexylsulfonyl-ethyl group, cyclobennal group, befuryl group, etc.), alkenyl group (for example, allyl group) , octadecenyl group, etc.), aryl group (e.g. phenyl group, 4-
t-butylphenyl group, 24-di-1-amylphenyl group, 4-tetradecanamidophenyl group, etc.), heterocyclic group (e.g., 2-furyl group, 2-naenyl group, 2-pyrimidinyl group, 2-benzothiazolyl group) , etc.), cyano group, alkoxy group (e.g., methoxy group, ethoxy group,
2-methoxyethoxy group, 2-bidecyloxyethoxy group, 2-methanesulfonylethoxy7 group, etc.), aryluo=+73 (e.g., phenoxy group, 2-methylphenoxy group, 4-t-butylphenoxy group, etc.) , peterocyclic oxy group (e.g., 2-benzimidazolyloxy group,
), acyloxy groups (e.g., eva, acetoxy, hexadecanoyloxy, etc.), carbamoyloxy groups (e.g., N-phenylcarbamoyloxy, N-ethylcarbamoyloxy, etc.), silyloxy groups (e.g., trimethylsilyl), oxy group, etc.), sulfonyloxy group (e.g., eva, dodecylsulfonyloxy group, etc.), acylamino group (e.g., acetoxy group, penzamibi group,
Tetradecanamibi group, α-(24-di-t-amylphenoxy)butyramide group, r-(3-t-7'thyl-
4-human 90xyphenoxy)butyramide group, α-+
4-(4-hydroxyphenylsulfonyl)phenoxy)decaneamide group, etc.), anilino group (e.g., phenylamino group, 2-chloroanilino group, 2-chloro-5-
Tetradecanamide anilino group, 2-chloro-5-to9
Decyloxycarbonylanilino group, N-acetylani+)/group, 2-chloro-5-(α-(3-1-butyl-
(4-human 90xyphenoxy)toticanamide anilino group, etc.), ureido group (e.g., phenylureido group, metherureibi group, N,I''J-dibutylureido group, etc.), imide group (e.g., N-succinimide group, 3
-penzylhydantoinyl group, 1 group of 4-(2-ethylhexanoylamino)phthalimide, etc.), sulfamoylamino group (e.g., N,N-dipropylsulfamoylamino group, N-methyl-N- decylsulfamoylamino group, etc.), alkyltheo group (e.g. meternao group, octylthio group, tetradecylthio group, 2-phenoxyetherthio group, 3-phenoxypropyl group, 3-
(4-t-bunalphenogisi)propylnao group, etc.),
Arylthio groups (e.g., phenylthio group, 2-butoxy-5-7-octylphenylthio group, 3-ntadecylphenylthio group, 2-carboxyphenylthio group, 4
-tetradecanamide 1 phenylthio group, etc.), peterocyclic thio group (e.g. 2-benzothiazolylthio group, etc.)
, alkoxycarbonylamino group (e.g., methoxycarbonylamino group, tetrazofluoroxycarbonylamino group, etc.), aryloxycarbonylamino group (e.g., phenoxycarbonylamino group, 2,4-di-ta)
rt-bunalphenonoΦ dicarbonylamino group, etc.), sulfonamide group (e.g., methanesulfonamide 9 group,
hexadecanesulfonamide group, 0 benzenesulfonamide groups, 9 p-)luenesulfonamide groups, octadecanesulfonamide group, 2-methyloxy-5-t-bunalbenzenesulfonamide group, etc.), carbamoyl group (
For example, N-ethelcarbamoyl group, N,N-dipylcarbamoyl group, N-(2-t9decyloxyethyl)
Carbamoyl group, N-methyl-N-Fdecyl group, N-(3-(2,4-di-tθrt-amylphenoxy)propyl)carbamoyl group, etc.), acyl group (e.g., acetyl group, ( 2,4-ditθrt-amylphenoxy)acetyl group, benzoyl group%, etc.)% sulfamoyl group (e.g., +-, N-ethylsulfamoyl group, N,N-dipropylsulfamoyl i, N-(2-
7'siloxine ether)sulfamoyl group, N-ethyl-N-)''-y'silsulfamoyl group, N,
N-) Ethylsulfamoyl! , etc.), sulfonyl 7i
(for example, methanesulfonyl group, octanesulfonyl group, benzenesulfonyl group, toluenesulfonyl group, etc.), sulfinyl group (for example, octanesulfinyl group, hytecylsulfinyl group, phenylsulfinyl group,
), alkoxycarbonyl groups (e.g., methoxycarbonyl group, butyloxycarbonyl group, dodecylcarbonyl group, octadecylcarbonyl, !, etc.), aryloxycarbonyl groups (e.g., phenyloxycarbonyl group, 3-pentadecyloxycarbonyl group) , etc.);
Propanoyloxy group, benzoyloxy & 24-dichlorobenzoyloxy group, ethoxyoxaroylmanquin group, pyruvinyloxy group, cinnamoyloxy group, phenoxy group, 4-noanophenokyl group, 4-methanesulfonamidophenoxy group , 4-methanesulfonylphenoxy group, α-naphthoki 7 groups, 3-1-tadecylphenoxy group, benzyloxycarbonyloxy group, ethoxy group, 2-anoethoxy 7 groups, benzyloxy group, 2-7
enethyloxy group, 2-phenoxyethoxy group, 5-7
(enyltetrazolyloxy group, 2-pencinazolyloxy group, etc.), groups linked via nitrogen atoms (e.g., benzenesulfonyl group, N-ethyltoluenesulfonamide group, butafluoroptanamide group, :LLE),
6-bentafluoropenzamibi group, 9 octane sulfonamide groups, p-cyanophenylureido group, N, N-
diethylsulfamoylamino group, 1-piperidyl group,
5-di)f-24-dioxo-3-oxazolidinyl group, 1-benzyl-ethoxy-3-hydantoynyl group, 2N-Ll-dioxo-3(2H)-okine-L2-
benzisothiazolyl group, 2-oxo-R2-dihydro-1-pyridinyl group, imidazolyl group, pyrazolyl group,
λ5-diethyl-12,4-triazol-1-yl,
5-ma or 6-promobenzotriazol-1-yl, 5-methyl-R2,3,4-triazol-1-yl group, benzimidazolyl group, 3-benzyl-1-hydantoinyl, 4.1-benzyl- 5-hexadecyloxy-3-hydantoynyl group, 5-methyl-1-tetrazolyl group, etc.), arylazo group (e.g., 4-methoxyphenylazo group, 4-pivaloylaminophenylazo group,
2-naphthylazo group, 3-methyl-4-hydroxyphenylazo group, etc.), groups linked by a sulfur atom (e.g.
Phenylthio group, 2-calhoki/phenylthio group, 2-
Methoxy-5-t-octylphenylthio group, 4-methanesulfonylphenylthio group, 4-octanesulfonamidophenylthio group, 2-butoxyphenylthio group, 2
-(2-hexanesulfonylethyl) -5-tart
-octylphenylthio group, benzylthio group, 2-cyanoethylthio group, 1-ethoxy7carponyltritethylthio group, 5-phenyl-'2. λ45-tetrazolylthio group, 2-benzothiazolylthio group, 2-dodecylthio-
5-thiophenylthio group, 2-phenyl-3-doa'sil-L 2.4-) 1) 7 Solylu-5-thio group, etc.) ~ Those represented by general formula (1) are vinyl monomers. The linking group represented by R21, R22, R23 or
substituted alkylene groups, for example, menale/group, ena L/7
group, 1,10-decylene group, -cH2CH20CH2C
II2-1 etc.), phenylene group (substituted or unsubstituted phenylene group Y::, e.g. +L R4-phenylene g,
L3-phenylene group, -NHCO-, -CONH-, -〇-1-〇CO-O6
and aralkylene (e.g., groups that form the combination ℃).

fj7 Preferred linking groups include the following.

-NHCO-, -CH2CH2-1 -CHCHO-CH2CH2゜-Nl(CO-1) The vinyl group may have substituents other than those represented by general formula (I) (preferable substituents are hydrogen atom, chlorine atom ,
Alternatively, it represents a lower alkyl group having 1 to 4 carbon atoms (eg, methyl group, ethyl group).

Monomers including those of general formula (I) may be copolymerized with non-chromogenic ethylene-like monomers that do not couple with the oxidation products of aromatic-grade amine developers.

Acrylic acid, α
- Chloroacrylic acid, α-alkylacrylic acid (e.g. methacrylic acid, etc.) and esters or amides derived from these acrylic acids (e.g. acrylamide, n-butylacrylamide, t-butylacrylamide, diacetone acrylamide, methacrylamide) 1, methyl acrylate, ethyl acrylate, n
-propyl acrylate, n-bunal acrylate, t
-butyl acrylate, 1so-butyl acrylate,
2-ethylhexyl acrylate, n-octyl acrylate, lauryl acrylate, methyl methacrylate, ethyl methacrylate, n-butyl methacrylate and β-hydroxy methacrylate), methylenebisacrylamide, vinyl esters (e.g. ethyl acetate, vinyl propionate) and vinyl laurate)
, acrylonitrile, methacrylonitrile, aromatic hinyl compounds (e.g. styrene and its derivatives, vinyltoluene, cyhinylbenzene, vinylacetophenone and sulphostyrene), itaconic acid, citraconic acid, crotonic acid, vinylidene chloride, vinyl alkyl ethers (reportedly vinyl ethyl ether), maleic acid, maleic anhydride, maleic esters, N-vinyl-2-pyrrolidone, N-vinylpyridine, and 2- and 4
-Vinylpyridine, etc. Two or more of the non-color-forming ethylenically unsaturated monomers used herein may 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. The solubility, compatibility of the photographic colloid composition with binders such as gelatin, its flexibility, thermal stability, etc. can be selected to be favorably influenced.

The polymer coupler used in the present invention may be water-soluble or water-insoluble, but polymer coupler latex is particularly preferred.

Particularly preferred pyrazoloazole yarn magenta couplers of the present invention are compounds in which at least one of Ro or R2 has a branched alkyl group at a position directly connected to the skeleton, and at least one -NH8 in R1 or R2. ○2
-It is a compound containing a substituent.

Particularly preferred among these are compounds represented by general formula (1-d) that satisfy the above conditions.

A detailed explanation of the branched alkyl group includes isopropyl group, °C-hexyl group, nclohexyl group, adamantyl group, 1-ethoxyisopropyl group, 1-phenoxy-
Ll-:) Methyl ethyl group, α, α-dimethylbenzyl group, α, α-dimethylphenyl enal group, α-ethylbenzyl group, l-ethyl-1-C4-(2-butoxy-5
-tart-octylbenzenesulfonamido') phenylcomethyl group, 1-methyl-2-(4-(4-dodezoloxybenzenesulfonamibi)phenyl)ethyl group, 1-methyl-2-(2-octyl Oxy-5-tar
t-octylbenzenesulfonamide 9) Ethyl group, L
l-dimethyl-2-(2-octyloxy-5-tar
t-octylbenzenesulfonamido)ethyl group, 1-
Methyl-2-C2-octyloxy-5-(2-octyloxy-5-tθrt=octylbenzenesulfonamide 1)benzenesulfonamide 9] ethyl group, 1-ethyl-2-(2-todecyloxy'/5 -tart
-octylbenzenesulfonamido)ethyl group, 1-(
2-hybiloxyethyl)-2-(α-(3-(2-octeroquine-5-tart-octerbenzenesulfonamibi)phenogysi]t1decaneamide1) ethyl group,
etc.

The pyrazoloazole magenta coupler represented by the general formula [■] used in the present invention is
2548, 59-171956, 60-33552
, 60-43659, US (Q Patents A06L432, 436α897, 3.72A067, etc.).

Specific examples of adult magenta couplers according to the present invention are shown below, but the invention is not limited thereto.

(M-1)
(H3 8: CM-3) (M Crystal 3 7(t) 6H' (M 21) CH3 (M-22) (M-24) (~l-27) (CH3 ■ Shi8"17 (tl ~ CM-33) (M-34) Next, the sensitizing dyes represented by the general formulas [A], CB) and [C] used in the present invention will be explained in more detail.

W and W2 are hydrogen atoms or alkyl groups (1 to 6 carbon atoms, such as methyl, ethyl, propyl,
butyl group, etc.).

Wl is preferably an ethyl group or a propyl group, and W and W3 are preferably hydrogen atoms.

vl, v2, v3, and v4 are hydrogen atoms, halogen atoms (e.g., chlorine atom, 1 bromine atom, etc.), alkyl groups (1 to 8 carbon atoms, e.g., methyl group, ether group, propyl group, butyl group, etc.) ), aryl group (for example, phenyl group, etc.), alkoxy group (1 to 8 carbon atoms, e.g. methoxy group, ethoxy group, propoxy group, etc.), amide group (
2-8 carbon atoms, e.g. acetamibi group, propionamide group, benzamide 9 group, etc.), alkoxycarbonyl group (2-8 carbon atoms, e.g. methoxycarbonyl group,
(etogyne carbonyl group, etc.) or a cyano group. V□ and v2 and ■3 and v4 may be the same or different, and may be a fused benzene ring.

v5 and ■6 may be the same or different, and
, ■3, and v4, it represents a group other than an aryl group and a condensed benzene ring.

Two or more substituents represented by v1 to v6 may be contained in the same molecule.

Next, preferable cases of (1) and ~v6 will be listed.

When Y represents an oxygen atom, vl is preferably a phenyl group or a condensed benzene ring, and (2) is preferably a phenyl group, a condensed benzene ring, a chlorine atom, or an alkoxy group.

When Y represents a sulfur atom, v2 is preferably
This applies to hydrogen atoms, halogen atoms, alkyl groups, phenyl groups, alkoxy groups, and amide groups.

(1) and v5 preferably represent a phenyl group or a chlorine atom, or are a fused benzene ring, and (2) and (6) preferably represent a trifluoromethyl group, a chlorine atom, an alkoxycarbonyl group, and a noano group. be. It is also preferable to use formula [C] in which one chlorine atom is present in both of the two benzotriazolyl groups, or two chlorine atoms are present in one of the two benzotriazolyl groups.

R21・R22・R23・R24・R25・R26・R
27・R28 and R29 are alkyl groups (carbon number 8
Hereinafter, for example, methyl group, ethyl group, propyl group, butyl group, etc. It may be branched or cyclic and represents, for example, an isopropyl group, a cyclohexyl group, etc.), or an aralkyl group (for example, a benzyl group, a phenethyl group, etc.).

Preferably, an alkyl group having 1 to 5 carbon atoms or 7 carbon atoms
~1o aralkyl group.

There are two or more of these groups in any of the general formulas [A], [B], and [C], but at least one of the groups present in the same molecule is a sulfo group, a carboxyl group, or a salt thereof. Alternatively, it represents an alkyl group or an aralkyl group containing a hydroxyl group.

X□, X2 and X3 represent acid anions (eg, chloride ion, bromide ion, iodide ion, p-toluenesulfonate ion, perchlorate ion, etc.).

11, m and n represent O or 1, and when each compound is an inner salt, they represent O).

General formulas [A), CB, l, and [
The sensitizing dye represented by C] is a known compound, and F
, M. Hamer (F', M. Hamer), ■
Heterocyclic Compounds/Dice and Relay Compounds (Hetero
cyclic compounds -Cyanlne
Dyes and Related Compound
s)”, Chapter 5, pp. 116-147, John
John Wiley and Sons
nd 5ons) Publishing (1964).

D, M, Cynitr-r-(D, M, Stur
mer), 1 Heterocyclic Compounds - Special Topics in Heterocyclic Compounds
Chemistry (Heterocyclic Compo)
unds -5special Topics in He
terocyclic chemistry)”,
Chapter 8, Volume 5, pp. 482-515, published by John Wiley & Sons (1977), Special Publication 1977-
13823, 44-16589, 48-9966,
It can be easily synthesized by referring to the methods described in JP-A No. 43-4936, JP-A No. 52-82416, and the like.

The following general formulas [A] and [B] are used in the present invention.

Specific examples of sensitizing dyes represented by and [C] are shown below,
The present invention is not limited thereto.

(A-1) (A-7) (A-8) (A-9) (A-10) (A-15) (A-17) °B-〇. 2.5 General formulas [A], [B), and [C
] The sensitizing dye represented by...1×10 mol to 5×10 mol, preferably 1×1 mol per mol of silver halide.
0 mol to Z5X10 mol, particularly preferably 4x1
It is contained in the silver halide emulsion layer in a proportion of 0 mol to 1 x 10 mol.

Two or more sensitizing dyes represented by the general formulas [A], [B], and [C] can be used in the same silver halide emulsion layer, or the same sensitizing dye can be used in different silver halide emulsion layers. It can also be used in emulsion layers.

The magenta coupler represented by the general formula [2] according to the present invention can be dispersed and contained in at least one hydrophilic organic colloid layer constituting the photographic light-sensitive layer together with a high-potency organic solvent. The preferred ratio of the magenta coupler to silver nitrate in the magenta coloring layer is 0.0.
5 to 5 moles.

As a method for introducing a coupler into a silver halide emulsion layer, a known method such as that described in US Pat. No. 2,322,027 is generally used.

The ratio of the high boiling point solvent to the pyrazoloazole magenta coupler is preferably O to 6.0. If the high boiling point organic solvent is insufficient to dissolve the coupler, a coupler solvent such as a phosphate ester coupler solvent may be used in combination. Also, in the present invention, before dissolving the coupler in the coupler solvent, the boiling point is about 30 to 150.
C. organic solvents such as lower alkyl acetates such as ethyl acetate and butyl acetate, ethyl propionate, secondary butyl alcohol, methylinobutyl ketone, β-ethoxyethyl acetate, methyl cellosol noacetate, etc. may be coexisting. .

Even when a coupler dissolved in a coupler solvent is introduced into a silver halide emulsion layer by these methods,
For example, Japanese Patent Publication No. 51-39853, Japanese Patent Publication No. 51-59
The dispersion method using a polymer described in No. 943 can also be used in combination.

When the coupler has an acid group such as carboxylic acid or sulfonic acid, it can also be introduced into the hydrophilic colloid as an alkaline aqueous solution.

In the present invention, various color couplers can be used in addition to the magenta coupler described above. Here, the term "color coupler" refers to a compound that generates a dye through a coupling reaction with an oxidized product of an aromatic primary amine developer. Typical examples of useful color couplers include naphthol or phenolic compounds, pyrazolones or pyrazoloazole compounds, and open chain or heterocyclic ketomethylene compounds. Specific examples of these cyan, magenta and yellow couplers that can be used in the present invention Serte Disclosure (RD) 17643 (December 1978)
It is described in Section 1-D and the patent cited in 18717 (November 1979).

It is preferable that the color coupler incorporated in the light-sensitive material has a pallast group or is made into a p' IJ polymer so that it has diffusion resistance. A divalent coupler substituted with a coupling-off group is preferable to a divalent coupler in which the coupling active position is a hydrogen atom because it can be coated in a low amount of silver. Furthermore, couplers in which the coloring dye has appropriate diffusivity, colorless couplers, DIR couplers that release a development inhibitor upon coupling reaction, or couplers that release a development accelerator can also be used.

Yellow couplers that can be used in the present invention include:

Oil-protected acylacetamide 5 couplers are a typical example. Specific examples thereof are described in U.S. Pat. No. 2.407.210, U.S. Pat. The use of two-equivalent yellow couplers is preferred for the present invention; U.S. Pat.
Oxygen atom separation type yellow couplers described in Japanese Patent Publication No. 393a501 and No. 4,022,620, Japanese Patent Publication No. 58-10739, and U.S. Patent No. 4.40
No. 1752.

4.32 to 024, RD18053 (April 1979), British Patent No. L42 to 020, West German Application No. 2.213917, 2261.361, 2
．． Typical examples thereof include the nitrogen atom separation type yellow couplers described in 32'J587 and 2.433812. α-pivaloylacetanilide couplers have excellent color fastness, especially light fastness, and -10,000-penzoylacetanilibi couplers provide high color density.

Cyan couplers that can be used in the present invention include oil-protected naphthol couplers and phenolic couplers, such as the naphthol couplers described in U.S. Pat. No. 2,474,293 and preferably U.S. Pat. No. 4,05
No. 2,212, No. 4,146,396, WJ71
．． Typical examples include the oxygen atom elimination type two-equivalent naphthol couplers described in No. 22a233 and No. 4.29fi200. Specific examples of phenolic couplers include U.S. Pat. No. 236a929 and U.S. Pat.
No. 01,171, No. 2772162, No. 2895
．． It is described in No. 826, etc. Cyan couplers that are stable against humidity and temperature are preferably used in the present invention, and a typical example thereof is a phenolic coupler having an alkyl group equal to or higher than ethyl group at the meta-position of the phenol nucleus described in U.S. Pat. No. 3,772,002. Cyan coupler, U.S. Pat. No. 2,772.162, U.S. Pat. No. 3,758,308
No. 412 No. 396, No. 4334011, No. 1 No. 327173, West German Patent Publication No. 432 to 729
Z described in No. 12L365 and European Patent No. 12L365, etc.
5-diacylamino substituted phenolic couplers and those having a phenylureido group at the 2-position described in U.S. Pat. and a phenolic coupler having an acinoamide group at the 5-position.

In order to correct unnecessary absorption in the short wavelength range of dyes generated from magenta and cyan couplers, it is preferable to use a color coupler in combination with a color negative sensitive material for photographing. U.S. Patent No. 4.16a670 and Japanese Patent Publication No. 1987-
Yellow colored magenta couplers described in US Pat. No. 39413, etc. or US Pat.
．． 3 & 258 and British Patent No. 1.146,36
Typical examples include the magenta-colored cyan coupler described in No. 8.

It is possible to improve the graininess by using a coupler in which the coloring dye has an appropriate diffusivity. Such a coupler is
US Patent No. 4,366.237 and British Patent No. 21
A specific example of a magenta coupler is given in No. 2a570, and also in European Patent No. 9 to No. 570 and West German Application No. λ23.t5.
No. 33 describes specific examples of yellow magenta or cyan couplers.

Dye-forming couplers and special couplers listed above.

A dimer or higher polymer may also be formed. Typical examples of polymerized dye-forming couplers are described in U.S. Pat.
No. 1,820 and No. 7LO80211. Specific examples of polymerized magenta couplers are given in British Patent No. 2.102173 and U.S. Patent No. F, 1.3.
No. 67.282.

The various couplers used in the present invention can be used in combination in the same layer of the photosensitive layer in order to satisfy the characteristics required for the photosensitive material, or the same compound can be used in two or more different layers. You can also introduce more than that.

As the binder or protective colloid 9 that can be used in the emulsion 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. .

In the present invention, the gelatin may be either lime-treated or acid-treated. For more information on how to make gelatin, see Arthur Vuis, The Macromolecular Chemistry on Gelatin (Academic Press).

(published in 1964).

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

Particularly preferred is silver chlorobromide containing from 20 mole percent to 100 mole percent silver bromide.

Average grain size of silver halide grains in a photographic emulsion (grain diameter in the case of spherical or approximately spherical grains).

In the case of cubic grains, the grain size is taken as a long grain size and is expressed as an average based on the projected area. ) is not particularly limited, but is preferably 2μ or less.

The particle size may be narrow (or wide).

The silver halide grains in the photographic emulsion layer may have a regular crystal structure such as a cube or a hexagonal, or may have an irregular crystal structure such as a ring or a plate. Alternatively, it may be a composite form of these crystal forms. It may also consist of a mixture of particles of various crystalline forms.

Further, an emulsion may be used in which ultratabular silver halide grains having a grain diameter of 5 times or more the grain thickness occupy 50% or more of the total projected area.

Silver halide grains may have different phases inside and on the surface.Also, they may be grains in which the latent image is mainly formed on the tiger face. , may be done.

The photographic emulsion used in the present invention is the one described in "Chemistry and Physics of Photography" by P. Grafquite (#? - published by Le Montel, 1967).
1 Photographic Emulsion Chemistry” by G. F. Daaffin (Focal Press, 1966).

"Manufacture and Coating of Photographic Emulsions" by V. L. Zelikman et al. (Focal Press, 1964) (P.

Glafkides, ” Chimie et
Ph,ysique Photograph-1
que” (Paul Hontel, (1967
) ), G, F'.

Duffin, “Photographic
! ;mulsion Chemistry” (F'o
cal Press, (1966)), V.
L., Zellkmane et al., ”Hak
ing and coating photograp
hicEmulsion” (FocaIPress
(1964)). In other words, any of the acidic method, neutral method, ammonia method, etc. may be used (and the method for reacting the soluble silver salt with the soluble halogen salt may be a one-sided mixing method, a simultaneous mixing method, a combination thereof, etc.). Good too.

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, it is also possible to use a method in which the pAg in the liquid phase in which silver halide is produced is kept constant, that is, the so-called Chondrold 9 double jet method.

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

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

In the process of silver halide grain formation or physical ripening,
A cadmium salt, a zinc salt, a lead salt, a thallium salt, an iridium salt or a complex salt thereof, a rhodium salt or a complex salt thereof, an iron salt or an iron complex salt, etc. may be present.

Silver halide emulsions are usually chemically sensitized.

For chemical sensitization, see "Basic Silver Halide Photographic Processing", edited by H. Freezer, Akademitsche Farark, 1.
(Published in 968) (H, Fr1eser.

Die Grundlagender Photogr
aphischenProzeesemit 5il
ber-halogenidsn” (Akad
emische Verlagsge8ellshaf
675-734 of J. T., 1968) can be obtained by using the method described in J.

That is, a sulfur sensitization method using a compound containing sulfur that can react with active gelatin or silver (for example, thiosulfur tvxc, thioureas, mercapto compounds, rhodanine); reduction sensitization method using noble metal compounds (e.g. gold complex 14λ
In addition to Pt, Engr.

A noble metal sensitization method using a complex salt of a metal of group (I) of the periodic table such as Pa can be used alone or in combination.

The photographic emulsion used in the present invention may 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. That is, thiazoles, such as pencinazolium salts, nitroimidazoles, nitrobenzimidazoles, chlorobenzimitazoles, bromobenzimidazoles, mercapdonazoles,
Mercaptobenzothiazoles, mercaptobenzimidazoles, mercaptothiadiazoles, aminotriazoles, benzotriazoles, nitrobenzotriazoles, mercaptotetrazoles (especially 1-phenyl-5-mercabutodetrazole, etc.), mercaptopyrimidines, mercaptotriazines, etc.; thioketo compounds, such as oxadorinthione; azaindenes, such as triazaindenes, tetraazaindenes (particularly 4-hydroxy-substituted (Lλ3a,7)tetraazaindene), monotaazaindenes, etc.; benzene Compounds known as anti-capri agents or stabilizers can be added, such as thiosulfonic acid, benzenesulfinic acid, benzenesulfonic acid amide, etc.

The photographic emulsion layer or other hydrophilic colloid layer of the light-sensitive material of the present invention includes coating aids, antistatic properties, smoothness improvement, emulsification dispersion, adhesion prevention, and improvement of photographic properties (e.g., development acceleration, high contrast, sensitization). Various surfactants may be included for various purposes.

The photographic emulsion layer of the photographic light-sensitive material of the present invention contains, for example, polyalkylene oxide or its derivatives such as ethers, esters, and amines, thioether compounds, thiomorpholines, quaternary ammonium salt compounds, urethane derivatives,
It may also contain urea conductors, imidazole derivatives, 3-pyrazolidones, and the like.

The photographic light-sensitive material used in the present invention may contain a dispersion of a water-insoluble or sparingly soluble synthetic polymer in the photographic emulsion layer and other hydrophilic colloid layers for the purpose of improving dimensional stability. .

The photographic emulsions used in the present invention may be spectrally enhanced with methine dyes and the like. Dyes that may be used include cyanine dyes, merocyanine dyes, complex cyanine dyes, combined merocyanine dyes, holopolar-cyanine and hemicyanine dyes, styryl dyes, and hemioxyturic 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. That is, e-loline nucleus, oxazoline nucleus, thiazoline nucleus, pyrrole nucleus, oxazole nucleus, thiazole nucleus, selenazole nucleus, imidazole nucleus, tetrazole nucleus, pyridine nucleus, etc.; a nucleus in which an alicyclic hydrocarbon is fused to these nuclei; and A nucleus in which an aromatic hydrocarbon ring is fused to these nuclei.

T r, r b H, inbirenin nucleus, penzintrunine nucleus, indole nucleus, benzoquinato9-ol nucleus, naphthoxazole nucleus, pensinaazole nucleus, naphthonaazole nucleus, benzoselenazole nucleus, benzimidazole nucleus, quinoline nucleus, etc. is applicable. These nuclei may be substituted on carbon atoms.

Merocyanine dye or composite melonanine color 2 contains a pyrazolin-5-one nucleus, a thiohydantoin nucleus, and a 2-thioxazolidine-Z nucleus as a nucleus having a ketomethylene structure.
A 5- to 6-membered heterocyclic nucleus such as a 4-dione nucleus, a naazolidine-Z4-dione nucleus, a rhodanine nucleus, a thiobarbituric acid nucleus, etc. can be applied.

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 sensitizing dyes, there are also dyes that do not have a spectral sensitizing effect or substances that do not substantially absorb visible light,
A substance exhibiting supersensitization may also be included in the emulsion. for example,
Aminosteryl compounds substituted with nitrogen-containing heterocyclic groups (e.g., U.S. Pat. No. 2.933390, U.S. Pat. No. 3,635,7)
21), aromatic organic formaldehyde condensates (such as those described in US Pat. No. 3,743,510), cadmium salts, azaindene compounds, and the like. The present invention can also be applied to multilayer, multicolor photographic materials having two different spectral sensitivities on a support. Multilayer natural color photographic materials are usually used.

The support has at least one red-sensitive emulsion layer, at least one green-sensitive emulsion layer, and at least one blue-sensitive emulsion layer. The order of these layers can be arbitrarily selected as required. 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.

Different combinations may be used depending on the case.

In the same or other photographic emulsion layer or non-light-sensitive layer of the photographic light-sensitive material of the present invention, in addition to the coupler represented by the general formula [I], other dye-forming couplers, that is, aromatic-grade A compound that can develop color by oxidative coupling with an amine developer (for example, a phenylene diamine derivative or an aminophenol derivative) may be used. For example, as a magenta coupler, 5-pyrazolone coupler, pyrazolone benzimidazole coupler, pyrazolo [! 'xt-C) [tz4) There are triazole couplers, pyrazolopyrazole couplers, pyrazolotetrazole couplers, open chain acylacetonitrile couplers, etc. Yellow couplers include a/lylacetamito couplers (for example, penzoylacetonitrile couplers,
cyan couplers include naphthol couplers and phenol couplers. These couplers are non-diffusible ones that have a hydrophobic group called a melasto group in the molecule, or 4 I
Preferably one with a J mom. The coupler may be either 4-equivalent or 2-equivalent to silver ion. Further, a colored 9 coupler having a color correction effect or a coupler that releases a development inhibitor during development (so-called DIR coupler) may be used.

In addition to DIR and couplers, the coupling reaction product is colorless and may contain a colorless DIR coupling compound that releases a development inhibitor. In addition to the DIR coupler, the light-sensitive material may contain a compound that releases a development inhibitor during development. Further, the light-sensitive material may contain a coupler or a compound that releases a development accelerator upon development.

The coupler of the present invention and the couplers described above can be used in combination of two or more types in the same layer in order to satisfy the characteristics required of a photosensitive material, or the same compound can be added to two or more different layers. Of course it doesn't matter.

In the photographic light-sensitive material of the present invention, the photographic emulsion layer and other hydrophilic colloid layers may contain an inorganic or organic hardening agent. For example, chromium salts (chromium acetate, chromium acetate, etc.), aldehydes (formaldehyde, glyoxal, geltaraldehyde 1, etc.), N-methylol compounds (dimethylol urea, methylol dimethylhydantoin, etc.).

Dioxane derivatives (23-dihydroxydioxane, etc.), active vinyl compounds (L a 5- ) IJ acryloyl hexahyha o-8-triazine, L3-
active halogen compound (2,4-dichloro-6-hydroxy-
〇-triazine), mucohalogenic acid-ffj (mucochloric acid, mucophenoxychlorate)%, etc. can be used alone or in combination.

In the photosensitive material of the present invention: 1. When the hydrophilic colloid layer contains dyes, ultraviolet absorbers, etc., they may be mordanted with a canonical polymer or the like.

The light-sensitive material of the present invention may contain a hydroquinone derivative, an aminophenol derivative, a gallic acid derivative, an ascorbic acid derivative, etc. as a color antifoggant.

The photosensitive material of the present invention may contain an ultraviolet absorber in the hydrophilic colloid layer. For example, benzo) IJ azole compounds substituted with aryl groups (e.g., U.S. Pat. No. 353
3794), 4-thiazolidone compound (
For example, U.S. Patent No. 314794, U.S. Patent No. 3,352,68
1), benzophenone compounds (for example, those described in JP-A No. 46-2784), cinnamic acid ester compounds (for example, those described in U.S. Pat.
707; those described in No. 375), butadiene compounds (
4045.229) or benzoxidol compounds (e.g., those described in U.S. Pat. No. 4,045.229);
70Q455) can be used.

An ultraviolet-absorbing coupler (eg, an eva-α-naphthol-based cyan dye-forming coupler) or an ultraviolet-absorbing polymer may be used. These ultraviolet absorbers may be mordanted in specific layers.

The photosensitive material of the present invention may contain a water-soluble 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,
Included are steryl dyes, merocyanine dyes, cyanine dyes and azo dyes. Among them, oxynol 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 antifading agents include hydroquinone derivatives, gallic derivatives, p-alkoxyphenols, p-oxyphenol derivatives, and bisphenols.

For the photographic processing of the layer consisting of the photographic emulsion used in the present invention, for example, Research Disclosure No. 176 No. 28-
Any of the known methods and known treatment liquids as described on page 30 can be applied. The treatment temperature is usually chosen between 18°C and 50°C, but it may also be lower than 18°C or higher than 50°C.

As the fixer, one having a commonly used composition can be used. As the fixing agent, in addition to thiosulfates and thiocyanates, organic sulfur compounds known to be effective as fixing agents can be used. The fixing solution may contain a water-soluble aluminum salt as a hardening agent.

Color developers generally consist of an alkaline aqueous solution containing a color developing agent. The color developing agent is a known general aromatic amine developer, such as phenylenediamines (e.g. 4-
Amino-N, N-diethylaniline, 3-methyl-4-
Amino-N, N-diethylaniline, 4-amino-N-
Ether-N-β-human 10xyethylaniline, 3-methyl-4-amino-N-ethyl/L-N-β-hyFJ o
xyetheraniline, 3-methyl-4-amino-N-ethyl-N-β-meta/sulfoamidoethylaniline, 4
-amino-3-methyl-N-ethyl-N-β-methoxy7
enalaniline, etc.) can be used.

In addition, F', A. Mason, Photo Processing Chemistry (Focal Press, 1966) (L.

F', A, Hason' Photography
hic Processing Chemi-stry
(F'ocal Press) (1966))
, pp. 220-229, U.S. Pat. No. 2.19&015, U.S. Pat.

Color developers may also contain pH buffering agents such as alkali metal sulfites, carbonates, borates, and phosphates, development inhibitors or anticapri agents such as bromides, iodides, and organic anticapri agents. It can contain. Further, if necessary, a water softener, a preservative such as chlorine droxylamine, an organic solvent such as benzyl alcohol or diethylene glycol, polyenalene glycol, or a quaternary ammonium salt.

Development accelerators such as amines, dye-forming couplers, competitive couplers, fogging agents such as sodium boron hydride 9-libi, auxiliary developers such as 1-phenyl-3-pyrazolidone, viscosity-imparting agents, polycarboxylic acid chelating agents, It may also contain antioxidants and the like.

The photographic emulsion layer of the color developer is usually bleached.

The bleaching process may be performed simultaneously with the fixing process, or may be performed separately. Examples of bleaching agents include iron (■),
Compounds of polyvalent metals such as cobalt (I), chromium (■), and copper (II), peracids, quinones, nitrone compounds, and the like are used.

For example, 7-functional ricyanide 1 dichromate, organic complex salts of iron(1) or cobalt(III), such as ethylenediaminetetraacetic acid, nitrilotriacetic acid, L3-diamino-2
-Aminopolycarbo/acids such as propatooltetraacetic acid or complex salts of organic acids such as quench/acid, tartaric acid, malic acid; persulfates, permanganates; nitrosophenols, etc. can be used. Of these, potassium ferricyanide, sodium iron(III) ethylenediaminetetraacetate, and ammonium iron(1) ethylenediaminetetraacetate are particularly useful. Iron(III) ethylenediaminetetraacetate
Complex salts are useful both in stand-alone bleach solutions and in -bath bleach-fix solutions.

The color photographic emulsion layer forming the strawberry dye image layer of the present invention is coated on a flexible support such as plastic film, paper, or cloth commonly used in photographic light-sensitive materials. Useful as flexible supports are films of semi-synthetic or synthetic polymers such as cellulose acetate, cellulose acetate butyrate, polystyrene, polyethylene terephthalate, polycarbonate, baryta layers or alpha-olefin polymers (e.g. polyethane/, polypropylene). It is paper coated or laminated with etc. The support may be colored using dyes or pigments. It may be made black for the purpose of blocking light.

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 bent lead oxide, bent lead sulfide, calcium carbonate, antimony trioxide, white silica, white alumina, and natanium phosphate, among which 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 as reflective materials, 9 layers of hydrophilic colloid containing white pigment at high density are further provided between the support and the emulsion layer to improve the whiteness and sharpness of photographic images. 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 method is particularly preferable because photographic images with particularly excellent detection and depiction of dark areas can be obtained. In this case, the synthetic resin film raw material is
As white pigments, barium sulfate and titanium oxide are particularly useful.

After development and drying, the photographic material of the present invention can be laminated with a plastic film on the front and back sides. Plastic films for lamination include polyolefin,
Examples include polyester, polyacrylic acid ester, polyvinyl acetate, polystyrene, butadiene-styrene copolymer, polycarbonate, etc., and polyethylene terephthalate, copolymer of vinyl alcohol and ethylene, polyethylene, etc. are particularly useful.

The present invention will be explained below by way of examples.

Example 1 To 9.8 g of Exemplified Compound (M-25), 211 Ll of tri-octyl phosphoric acid ester (TOP) and 2 liters of ethyl acetate were added.
Add 0ml and dissolve, and add this solution to 5% alkanol B.
(Alkylnaphtherene sulfonate manufactured by Tubon) Lo
The mixture was emulsified and dispersed in 80 rrdl of a 10% gelanan aqueous solution containing nl. This is referred to as emulsion (a).

Next, an emulsion (b) was prepared in exactly the same manner as above except that 4 g of Exemplified Compound) J-270 was used instead of CM-11).

On the other hand, silver chlorobromide emulsion (Br80 mol, Ag66,0
g/kl? (containing) as a green-sensitive sensitizing dye of the present invention (A
-7) was added in an amount of 2.5 x 10-' mol per mol of silver chlorobromide, and the entire amount of the above-mentioned emulsions (a) and (b) was added to 135 g each of the green-sensitive emulsion and the soybean emulsion. These are (A), (B
).

Yet another using the silver chlorobromide emulsion described above.

The same amount of the following green-sensitive sensitizing dye for comparison was added, and the entire amounts of the emulsions (a) and (b) above were added to the same amount of the green-sensitive emulsion.

Let these be (C) and (q).

These (A) to (D) were dissolved in a constant temperature bath at 40°C for 4 hours while stirring for 5 hours. After that, L was used as a hardening agent.
2-bis(vinylsulfonyl)ethane was added and the coating amount was 200 μ/rr in each case on a paper support laminated with polyethylene. A gelatin solution containing the same hardening agent was applied as a protective layer on top of the sample (N~
(I created q.

Each film sample was passed through a continuous wedge, exposed to green light, and processed as described below.

Treatment process temperature Time color development 33℃ 3 minutes 30 seconds Bleach fixing 33℃ 1 minute 30 seconds Washing with water
Dry for 3 minutes at 35-35℃
80°C Color developer composition Nitrilotriacetic acid/3Na 2.
09 Benzyl alcohol 15a+4
Dienalene glycol 10mA'sodium sulfite 2. Of! Potassium bromide 0.5.9 human 9
0xylamine sulfate 3.0.9
4-Amino-3-methyl-N-ethyl-N-(β-(methanesulfonamido'')ethyl)-p-phenylenediamine sulfate 5.0 g Sodium carbonate (monohydrate) 309 Add water
1000 ml (pH 10.1) Revealing fixer composition Ammonium thiosulfate (70wt4) 150a
t Sodium sulfite 15g (ED
TA) Iron ammonium salt 51 (EDT
Table 1 shows the results of measuring the relative sensitivity of the magenta color image obtained by adding A).disodium 4I water and processing for 1000 days.

From the results in Table 1, it can be seen that samples (A) and CB) of the present invention have sufficient sensitivity, but samples using comparative sensitizing dyes show a significant decrease in sensitivity.

Example 2 As shown in Table 2, Sample E was prepared by coating the first to seventh layers on a paper support laminated on both sides with polyethylene.

The coating solution for the first layer was prepared as follows. That is, the yellow coupler 100y shown in Table I is di(2-
ethylhexyl) phthalate 40M and ethyl acetate 20M
This solution was dissolved in a 10% gelatin aqueous solution containing 80 ml of a 5% aqueous solution of Alkanol B (alkylnaphthalene sulfonate, manufactured by DuPont).
00g was emulsified and dispersed. Next, the entire amount of this emulsified dispersion was mixed into 1450 g of blue-sensitive silver chlorobromide emulsion (Br 90 mol%) (
(containing 667 g of Ag) to prepare a coating solution. Coating solutions for the other layers were prepared in the same manner. 12-bis(vinylsulfonylethane) was used as the hardener for each layer.

The following materials were used as sensitizing dyes for each emulsion layer.

Blue-sensitive emulsion layer; a3'-di(-sulfopropyl)-selenacyanine sodium salt () Rogge/2X10-4 mol per mol of silver halide) Green-sensitive emulsion layer; A-7 (2 x 10-4 mol per mol of silver halide) .5X10-4 mol) Red-sensitive emulsion layer; S3'-G(-sulfopropyl)-9
-Methyl-theadicarbocyanine sodium salt (25X 10-4 mol per mol of silver halide) In addition, the comparative dye of Example 1 was used as the sensitizing dye in the green-sensitive emulsion layer (third layer). Sample F was prepared in the same manner as Sample E.

Also, replace the magenta coupler in the third layer with two of the couplers below.
70■/rr? Sample G was prepared in the same manner as Sample E except that

1 Comparative Magenta Coupler Samples E-G were stored one at 25° C. and 60% RH for 3 days and the other at 40° C. and 80% RH for 3 days. These samples were passed through a continuous wedge in the same manner as in Example 1,
1. Exposure to green light was applied and the same development process as in Example 1 was performed.
, a magenta image was obtained.

Table 3 shows the results of comparing the relative sensitivities of the magenta images thus obtained.

Similar to Sample E, excellent stability and one-color reproducibility were obtained in Sample E in which the magenta coupler in the third layer was changed to that of the present invention.

From the results in Table 3, Sample E using the magenta coupler and sensitizing dye of the present invention shows no decrease in sensitivity even under high temperature and high humidity storage conditions, whereas sample E using the sensitizing dye other than the present invention shows no decrease in sensitivity. It can be seen that the sample F used exhibits a slight decrease in sensitivity even at low temperatures and low humidity, and is significantly desensitized at high temperatures and high humidity.

Next, samples E-G were printed on a color printer through photographed and developed color negative film, and the color prints obtained by the same development process as above were compared. Prints obtained from samples E and F.

In particular, colors in the red to blue range with high saturation are extremely well reproduced between the groups, whereas the prints obtained from Sample G containing the comparison magenta coupler faithfully reproduce the primary colors in the red to blue range. It had not been done.

In addition, samples in which the magenta coupler in the third layer of Sample E was replaced with other couplers M-28, M-30° and M-34 of the present invention also exhibited excellent stability and color reproducibility similar to Sample E. It was done.

〔Effect of the invention〕

According to the present invention, it is possible to obtain a silver halogenide color light-sensitive material having excellent stability over time and hue reproducibility.

Procedural Amendment January 1985 // Mouth Patent Application No. 233865 of 1985 2, Name of the invention Silver halide color photographic light-sensitive material 3, Person making the amendment Relationship with the case 'Patent applicant name (520) Fuji Photo Film Co., Ltd. 7, "Detailed Description of the Invention" column 8 of the specification to be amended, contents of the amendment 1) Lines 1 to 4 of page 81 of the specification (typewritten) 2. Delete the sentence "Color reproducibility was obtained in sample E."

2) rM in the magenta canoler column in Table 3 on page 81
Correct -40J to rM-27J.

Procedural amendment January 7th, 1985 1985 Patent Application No. 256865 @2, Title of Invention ・・Silver logenide power 2-Photographic light-sensitive material 3. Person who makes corrections Relationship to the case゛Patent applicant Name (520) Fuji Photo Film Co., Ltd. Specification 8. Contents of amendment

Claims (1)

[Claims] (1) It has at least one silver halide emulsion layer on the support, the silver halide in the emulsion layer is silver chloride, silver chlorobromide or silver bromide, and the emulsion layer has the following general formula: (I)
at least one kind of magenta coupler and the following general formula (A)
, (B) or (C). General formula (I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (In the formula, R_1 and R_2 represent hydrogen atoms or substituents, and X is a hydrogen atom or Represents a group capable of leaving, R
When _1 or R_2 is a group other than a hydrogen atom, it also includes the case where the group forms a dimer. ) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [A] ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [B] ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [C] In the above formula, W_1 and W_2 are hydrogen atoms Or represents an alkyl group. V_1, V_2, V_3 and V_4 are a hydrogen atom, a halogen atom, an alkyl group, an aryl group, an alkoxy group,
Represents an amide group, an alkoxycarbonyl group, or a cyano group. V_1 and V_2 and V_3 and V_4 may be the same or different, and may be fused benzene rings. V_5 and V_6 may be the same or different and represent a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, an amide group, an alkoxycarbonyl group, or a cyano group. Substituents represented by V_1 to V_6 have 2 substituents in the same molecule.
or more may be included. R_3, R_4, R_5, R_6
, R_7, R_8, R_9, R_1_0 and R_1_
1 represents an alkyl group or an aralkyl group. However, at least one of R_3 and R_4 and R_5 and R_6 and R_7, and R_8 and R_9 and R_1_0 and R_1_1 represents an alkyl group or an aralkyl group containing a sulfo group, a carboxyl group, a salt thereof, or a hydroxyl group. . Y represents an oxygen atom or a sulfur atom, and X_1, X_2, and X_3 represent acid anions. l, m, and n represent 0 or 1, and when each compound is an inner salt, they represent 0).