JPS6279452A - Silver halide color photographic sensitive material - Google Patents

Abstract

PURPOSE:To improve the sensitivity and color developability without deteriorating other photographic characteristics by incorporating a specified pyrazoloazole type coupler and a specified compound into a silver halide photographic layer. CONSTITUTION:A pyrazoloazole type coupler represented by general formula I and a compound represented by general formula A are incorporated into a silver halide color photographic layer. In the formula I, R<1> is H or a substituent, X is H or a group eliminable by a coupling reaction with the oxidized product of an aromatic primary amine developing agent, each of Za, Zb and Zc is methine, substituted methine, =N- or -NH-, one of the Za-Zb and Zb-Zc bonds is a double bond and the other is a single bond. In the formula A, Y is aryl, alkyl, a heterocyclic group, -P(=O, side chain' -R5, side chain)-R4 or -C(=O, side chain)-R4, R' is alkyl, arylene or aralkylene, R is alkyl or aryl, Y and R are not simultaneously alkyl and R5 is alkyl, aryl, amino, alkoxy or aryloxy.

Description

Detailed Description of the Invention (Field of Industrial Application) The present invention relates to a pyrazoloazole magenta coupler, and the color image formation rate and ultra-high absorption density of this coupler. This invention relates to a silver halide color photographic light-sensitive material which can be combined with a compound effective for improving the quality of the photographic material.

(Prior art) When a silver halide color photographic light-sensitive material is color developed, the acid-ratio aromatic/class amine color developing main mulberry reacts with the coupler to produce indophenol, indoaniline, indamine, It is well known that azomethine, phenoxazine, phenazine, and similar dyes are produced to form color images. Of these, to form a magenta image! - Pyrazolone/anoacetophenone and pyrazoloazole couplers are used.

These magenta colors! Among the 1i (3! forming couplers, the dye formed from the pyrazoloazole coupler has no unnecessary absorption of the yellow component near 4A3Onm, has no tail breakage on the long wavelength side, and has excellent spectral absorption as a magenta color image. These pyrazoloazole coupler skeletons have long been known as British patents.
/ pyrazolobenzimidazole skeleton described in No. 2,
US patent 3.72! .

/H-pyrazolo[j, /-c] (described in No. 067)
/, 2, ≠] triazole skeleton, recently proposed in JP-A No. 12-12-12, /H-imidazoC/, 2-b] pyrazole skeleton, especially /H-pyrazolo (/, j-b) [/, 2. ≠〕triazole skeleton,
Tokukai Shoto-3Jj! /H-pyrazoloC/ described in No. F2.

! -d]tetrazole skeleton, /H-pyrazolo[/,j-b]pyrazole skeleton described in JP-A No. 1, No. 36, is known.

However, such pyrazoloazole-based magenta couplers have relatively low photographic sensitivity, and their color development is not yet sufficient.
I couldn't.

(Objective of the invention) Therefore, the object of the present invention is to improve the above-mentioned drawbacks of the pyrazoloazole magenta coupler without deteriorating all other photographic properties, and to improve the sensitivity and color development of the halogenated coupler. The purpose of the present invention is to provide a silver color photographic material.

(Structure of the Invention) An object of the present invention is to contain a pyrazoloazole coupler represented by the following general formula (I) and a compound represented by the general formula (A) in the same photographic layer. This was achieved using silver halide color photographic materials.

In the above formula, R1 represents a hydrogen atom or a substituent, and X represents a hydrogen atom or Mf which can be separated by a coupling reaction with an oxidized aromatic primary amine developer. Za, Zb and Zc are methine, substituted methine, =N- or -NH-
One of the Za-Zb bonds and Zb-Zc bonds is a double bond, and the other is a single bond. When Zb - Zc is a carbon-carbon double bond, it is a part of an aromatic ring.

When R1 or X forms a dimer or more multimer, and when Za, Zb or Zc is a substituted methine, it also includes the case where the substituted methine forms a dimer or more multimer.

General formula (A) Y-0+R'-〇±R In the above formula, Y is a substituted or unsubstituted aryl group, a substituted or unsubstituted alkyl group, a substituted or 145
Represents U. R' is a substituted or unsubstituted alkylene group,
It represents a substituted or unsubstituted arylene group, or a substituted or unsubstituted aralkylene group, and R represents a substituted or unsubstituted alkyl group or an unsubstituted aryl group. However, Y and R are never an alkyl group at the same time. R4 and R5 represent a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted amine group, a substituted or unsubstituted alkoxy group, or a substituted or unsubstituted aryloxy group.

n is/~! represents an integer.

The chemical compound used in the present invention will be explained in more detail below.

In the general formula (I), the term "multimer" means one having two or more groups represented by the general formula (I) in the 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 prepared with a non-color-forming ethylene-like monomer that does not compile with the oxidized developer.

Among the pyrazoloazole magenta couplers represented by monofunctional formula (I), preferred ones are those represented by the following general formula (II):
, (Ill), (IV)-(V), (Vl), (■) and (■).

(■) (■) (1'/ ) (V) (Ml) (■) (■) Among the couplers represented by the general formulas (11) to (■), those preferred for the purpose of the present invention are the general formula (U ), (V) and (Ml), and more preferable ones are those of the general formula (Vl
).

In general formulas (I[) to (■), 几11. R, 12 and 几 may be the same or different and each represents a hydrogen atom, a halogen atom, an alkyl group, an aryl group, a heterocyclic group, a cyano group, an alkoxy group, an aryloxy group, a heterocyclic group, an acyloxy group, or a carbamoyl group. Oxy group, cisoloxy group, sulfonyloxy group, alleramino group, anilino group, ureido group, imido group, sulfamoylamino group, carbamoylamino group, alkylthio group, arylthio group, heterocyclic thio group, alkoxycarbonylamino group, aryl represents an oxysulfonylamino group, a sulfonamide group, a carbamoyl group, an acyl group, a sulfamoyl group, a sulfonyl group, a sulfinyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, and X is a hydrogen atom, a halogen atom, a carboxy group, or an oxygen atom, Represents a group that bonds to a carbon at a coupling position via a nitrogen atom or a sulfur atom, and is a group that is decoupled.几 , 几 , R or X may serve as a covalent group to form a bis form.

Furthermore, the coupler residues represented by the general formulas (■) to (■) may be in the form of polymer couplers in the main chain or side chain of the polymer (in particular, they are derived from vinyl monomers having the moieties represented by the general formulas). Preferred are polymers in which R, R, J or X represents a vinyl group or a linking group.

More specifically, 1(, ``-It12 and 1mo13 are hydrogen atoms, halogen atoms (e.g., chlorine atom, bromine atom, etc.), alkyl groups (e.g., methyl group, propyl group, [-butyl group, trifluoromethyl group), respectively. Base.

Tridecyl group 1. ．． 7-(,2,tl-di-1-amylphenoxy)propyl group, allyl group, codedecyloxyether group, 3-7 enoquinbrobyl group, cohexylsulfonyl-ethyl group - cyclopentyl group, benzyl group, etc.), aryl group (For example, phenyl group, u-t
-7” tylphenyl group, y, q-di-t-amylphenyl group + leechtradecanamidophenyl group, etc.),
Heterocyclic groups (e.g. -furyl group, cortienyl group +
(copyrimidinyl group, nibenzothiazolyl group, etc.)
, cyano group, alkoxy group (e.g., methoxy group, ethoxy group, comethoxyethoxy group, codedecyloxyethoxy group, niemethanesulfonylethoxy group, etc.),
Aryloxy group (e.g., phenoxy group, nimethylphenoxy group-1@-j-butylphenoxy group, etc.),
Heterocyclic oxy groups (e.g., nibenzimidazolyloxy groups, etc.), acyloxy groups (e.g., acetoxy groups, hexadecanoyloxy groups, etc.), carbamoyloxy groups (e.g., N-phenylcarbamoyloxy groups, N
-ethylcarbamoyloxy group, etc.), silyloxy group (e.g., trimethylsilyloxy group, etc.), sulfonyloquine group; Tetradecanamide group, α-(2,U-
Di(-amylphenoxy)butyramide group, γ-(,
, 7-t-butyl-q-hydroxyphenoxy)butyramide group, α-(p-(U-hydroxyphenylsulfonyl)phenoxy)decaneamide group, etc.), anilino group (e.g., phenylamino group, λ-chloroanilino group,
2-chloro-5-tetradecanamide anilino group, no 10-row 5-dodecyloxycarbonylanilino group, N
-acetylanilino group, NichloroS-(α-(3-
t-butyl-q-hydroxyphenoxy/)dodecanamido)anilino group, etc.), ureido group (e.g., phenylureido group, methylureido group, N,N-dibutylureido group, etc.), imide group (e.g., N- succinimide group, 3-penzylhydantoinyl group, U-<nee ethylhexanoylamine) phthalimide group, etc.), sulfamoylamino group (e.g., N,N-dipropylsulfamoylamino group, N-methyl- N-f silsulfamoylamino group, etc.), alkylthio group (e.g., methylthio group, octylthio group, tetradecylthio group, cofdinoxyshetertheo group, 3-phenoxypropylthio group, 3-(&-t-butylphenoxy) propylthio group,
etc.), arylthio groups (e.g., phenylthio group, copoxy 1-1-octylphenylthio group, 3-pentadecylphenylthio group, dicarboxyphenylthio group, Hiro-tetradecanamidophenylthio group, etc.),
Heterocyclic thio groups (e.g., nibenzothiazolylthio, etc.), alkoxycarbonylamino groups (e.g., methoxycarbonylamino, tetradecyloxycarbonylamino, etc.), aryloxycarbonylamino groups (e.g., phenoxycarbonylamino), group, r, u-tert-bunalphenoki7carbonylamino group, etc.), sulfonamide group (e.g., methanesulfonamide group, hexadecanesulfonamide group, benzenesulfonamide group, p-)luenesulfonamide group, octadecanesulfonamide group group, comethyloxy s -t -
i-thylbenzenesulfonamide group, etc.), carbamoyl group (e.g., N-ethylcarbamoyl L N I N-
';'-j thylcarbamoyl group, N-<codecyloxyethyl)carbamoyl group, N-methyl-N-dodecylcarbamoyl group, N-(,7-(co,q-diter
t-amylphenoxy)propyl)carbamoyl group, etc.), acyl group (e.g., acetyl group%(2#”-di-t
ert-amylphenoxy)acetyl group, benzoyl group, etc.), sulfamoyl group (e.g., N-ethylsulfamoyl group, NlN-diylopylsulfamoyl group,
N-(J-dodecyloxyx f /l/ )sulfamoyl group, N-ethyl-he-dodecylsulfamoyl M
, NlN-diethylsulfamoyl group, etc.), sulfonyl group (sidelight, methanesulfonyl group, octanesulfonyl group, Hensensulfonyl group, toluenesulfonyl group,
etc.), sulfinyl M (e.g., octane sulfinyl group, decylsulfinyl group, phenylsulfinyl group, etc.), alkoxycarbonyl M (e.g., methoxycarbonyl group, butyloxycarbonyl group, dotesylcarbonyl group, octadecylcarbonyl group, etc.), aryloxycarbonyl group (eg.
(e.g., chlorine atom, bromine atom, iodine atom, etc.), carboxy group, or group linked with an oxygen atom (e.g., acetoxy group, propanoyloxy group, benzoyloxy group, co-, tI-dichlorobenzoyloxy group, ethoxyoxaloxy group) yloxy group, pyruvinyloxy group, cinnamoyloxy group, phenoxy group, guccianophenoxyl group, q-methanesulfonamidophenoxy group, q-methanesulfonylphenoxy group, α-naphthoxy group, J-pentadecylphenoxy group, benzyloxycarbonyloxy group, ethoxy group, cocyanoethoxy group, penzyloxycarbonyloxy group, cophenethyloxy group, cophenoxyethoxy group, S-phenyltetrazolyloxy group, cobenzoteazolyloxy group, etc.) , a group connected by a nitrogen atom (
For example, benzenesulfonamide group, N-ethyltoluenesulfonamide group, butafluorobutanamide group,
J, J r g r j + A' tafluorobenzamide group, octanesulfonamide group, p-cyanophenylureido group % N IN-diethylsulfamoylamino group, l-pi is lysyl group, yo, tadimethyl-co, dioxo- ,? -oxasolicinyl group, l-benzyl-ethoxy-3-hydantoynyl group, coNt, t
-dioxo-J(2H)-oxo-/, cobenzointheazoryl group, co-oquine/, 2-dihydro-7-pyridinyl group, imidazolyl group, pyrazolyl group, J, S-
Diethyl-/, 2. It-) riazol-/-yl, r
-4dada6-bromo-benzotriazol-/-yl,
! -Methyl-7+2゜3, ψ-triazol-/-yl group, benzimidazo! J Lug...? --<Njiru l-
Hydantoinil! , /--S-hexadecyloxy-J-hydantoinyl group, S-methyl-/-tetrazolyl group, etc.), arylazo group (e.g., ψ-methoxyphenylazo group, goupivaloylaminophenylazo group, conaphthylazo group, 3-methyl-<1-hydroxyphenylazo group, etc.), groups linked via a sulfur atom (
For example, phenylthio group, λ-carboxyphenylthio group, λ-methoxy5-1-octylphenylthio group,
q-methanesulfony/L, phenylthio group, q-octanesulfonamidophenylthio group, copetoxyphenylthio group, -1(cohegisansulfonylethyl)-5
-tert-octylphenyl luteo group, benzylthio group, cocyanoethyl theo group, 1-ethoxycarbonyltritecylthio group, 5-phenylruco group.

3.'t! ;-tetrazolylthio group, cobenzoteazolylthio group, codedecylthio-5-thiophenylthio group, copheny-J-)"decyl-7゜j, tl-
)! J azolyl-5-thio group, etc.).

In the couplers of general formulas CII ml and [1■], R12 and R13 may be combined to form a 5- to 7-membered ring.

B+1. When B12, R13 or X becomes a covalent group to form a bis body, preferably
is a substituted or unsubstituted alkylene group (e.g., methylene group, ethylene group, /, 10-decylene group, -CH2C1
-12-0-CI-12CH2-1, etc.), substituted or unsubstituted phenylene groups (e.g. /, q-phenylene group,
1r3-) unilene group, -N I-I C(J-几”
-CONI-1- group (R14 represents a substituted or unsubstituted alkylene group or phenylene group, for example -Nl
-IC(JCH2C1-1゜C(,)NH-1H3 -N l-I CU CI-I C-CI-12C(
J N 1-1-CI-13 -8-R''-3- group (R14 represents a substituted or unsubstituted alkylene group, for example, -8-CHCI-1゜-8-1 CI-13 -8- CHC-CH2-3-1, etc.), and CH3

General formula (■), (II), (Iv), (V), (Vl
), (■) and (■) are included in the vinyl monomer, the linking group represented by Bll, B12, 几13 or X is an alkylene group (substituted or unsubstituted alkylene group). For example, methylene group, ethylene M, /, 10-decylene group, -CHCH2 (JCII
2C1-12-1, etc.), a phenylene group (substituted or unsubstituted) unilene group, for example, 1. Hiro-phenylene group,
l, 3-phenylene group, -Nl-ICO-1-CONH-1-0-1-(JCQ
- and aralkylene groups (for example, α).

Preferred linking groups include the following.

-NHCO-1-CH2CH2-1 ○ -C(JNH-CHCH2N1-IC(J-1-CH2
CH2(J-CH2CH2-Nl-ICU-1, the vinyl group has the general formula (II), (Ill), (l■), (
Substituents other than those represented by V), (■1), (■) or (Vlll) may be used. Preferred substituents are hydrogen atoms, chlorine atoms, or lower alkyl groups having 1 to q carbon atoms (e.g. methyl group, ethyl group).

General formula (Itton, (III), (1v), (V), (
'/I), (■1) and (■) are copolymerized with non-chromogenic ethylene-like monomers that do not couple with the oxidation products of aromatic-grade amine developers. You can also make polymers.

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, [-butyl acrylate, 1so-butyl acrylate, -monoethylhexyl acrylate, n-octyl acrylate, lauryl acrylate, methyl methacrylate, ethyl methacrylate, lobyl methacrylate and β
-hydroxy methacrylate), methylene dibis acrylamide, vinyl esters (e.g. vinyl acetate,
vinylpropionate and vinyllaurate), acrylonitrile, methacrylaterile, aromatic vinyl compounds (e.g. styrene and its derivatives, vinyltoluene, cyhinylbenzene, vinylacetophenone and sulfostyrene), itaconic acid, citraconic acid, crotonic acid, vinylidene Chloride, vinyl alkyl ether 1 liter
(LtH vinyl ethyl ether), maleic acid, maleic anhydride, maleic ester, N-vinyl-nypyrrolidone, N-vinylpyridine, and ny- and q-vinylpyridine. The non-color-forming ethylenically unsaturated monomers used here may be used in combination. For example, lobe tyl acrylate and methyl acrylate, styrene and methacrylic acid, methacrylic acid and acrylamide, methyl acrylate M-3 M-μ H3 H3 -10 M-/ / C2H5 M-/, 2 M-/3 M-/ ≠ -1j M -/7 H3 -it M-23 M-2 Hiro M-2! (CH2)3 (2) The coupler represented by the general formula (I) of the present invention can be synthesized according to the methods described in the following documents.

Compounds of general formulas (In) and (M) are
L co! ≠ etc., the compound of the general formula (III) is described in Japanese Patent Publication No. 2003-111003, etc., and the compound of the general formula (V) is described in the Japanese Patent Application Publication No. 7-27-27≠// etc., the compound of the general formula (III) is The compound W) is disclosed in Japanese Patent Application Publication No. 2003-120002 and 7/9. Tarλ77 Hiromu! Etc., the chemical compound of the general formula (■) is published in Japanese Patent Application Publication No. 60-1983! λ, etc., and the compound of general formula (■) is disclosed in U.S. Patent J, 0
6/, +132, etc., respectively.

Also, JP-A No. 31-≠20≠j, JP-A-Sho! / 7
7.133, Tokukai Sho! Tar/7 Hiromu, No. 136, Tokukai Sho! Tar/77.36≠ issue, Tokukai Sho! Tar/77.1
No. 17, Tokukai Shojter/77! The highly color-forming ballast groups described in J Otsu No. 77.111 and the like are also applicable to the b deviations of the compounds of the above general formulas (If) to (■).

General formula (A) Y-0+R'-0+rlR In the formula, Y represents an f-substituted or unsubstituted aryl group, a substituted or unsubstituted alkyl group, or a substituted or group. R
' represents a substituted or unsubstituted alkylene group, a substituted or unsubstituted arylene group, Otomo represents a substituted or unsubstituted aralkylene group, R represents a substituted or unsubstituted alkyl group, or a substituted or unsubstituted aryl group. represent. R4 and R5 represent a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted amine group, a substituted or unsubstituted alkoxy group, and in particular a substituted or unsubstituted aryloxy group.

n represents an integer of /-j.

The substituents of the above substituted alkyl group, substituted aryl group, substituted alkylene group, substituted arylene group, substituted aralkylene group, substituted alkoxy group or substituted aryloxy group include a halogen atom, an alkyl group, an aryl group, a heterocyclic group, a cyano group, Alkoxy group, aryloxy group, heterocyclic oxy group, acyloxy group, carbamoyloxy group, silyloxy group, sulfonyloxy group, acylamino group, anilino group, ureido group, imide group, sulfamoylamino group, carbamoylamino group, alkylthio group , arylthio group, heterocyclic thio group, alkoxycarbonylamino group, aryloxycarbonylamino group, sulfonamide group, carbamoyl group, acyl group, sulfamoyl group,
Represents sulfonyl group, sulfinyl group, alkoxycarbonyl group, aryloxycarbonyl group, and gold.

The compound of general formula (A) will be explained in more detail.

Y is an aryl group (e.g. phenyl group, /- or λ-
Naphthyl group, ≠-chlorophenyl group,! -(N-i thyl)sulfamoylphenyl group, Hiro-tert-octylphenyl group, 3-dodecyloxyphenyl group, 2. ≠
-di ter t --e methyl group, di(nee ethylhexane) amidophenyl group, etc.), alkyl group (
For example, methyl group, ethyl group, λ-ethylhexyl group,
Benzyl group, hexadecyl group, benzoylmethyl group, N
-(2, Hiroji-tert-antyl)carbamoylmethyl group, 2-chloroethyl group, niphenoxyethyl group, etc.), heterocyclic group (e.g., t-ba, λ-furyl group, nitenyl group, 29 μm di- Butoxy-A- [/, 3.j]
triazinyl group, l-pyrimidinyl group, p, +-Hiro-chlorobenzoyl group, ethoxycarbonyl group, (co, ≠-
acetyl group, 3
-[α-(2, Hiro-G-tert-amylphenoxy)
butylamide] represents a benzoyl group, an N-phenylcarbamoyl group, etc.).

R' is an alkylene group (e.g. %/1λ-ethylene group, l
, 3-propylene group, /+tt-i tyrene group, l, 3-
Butylene group λ, 2-dimethyl-/lλ-ethylene group, /
, /, 2.2-tetrafluoro-/, 2-ethylene group, λ-phenyl-/, 2-ethylene group, etc.), arylene group (for example, l.

Hiro-phenylene group, l,3-phenylene group 1.2゜3,
j, l, -tetrachloro-7, hiro-phenylene group, /,
≠−naphthylene group, λ,! -diacetyl/9μm phenylene M, 2.6-di-phenyl-/, ≠-phenylene group, etc.), aralkylene group (e.g. benzylylene group, alkyl group and aryl group of R4 and R5 are all explained by Y. Represents the same alkyl group or aryl group as in 9, R4
, R5 is an amino group (e.g., amino group, anilino group, ethylamino group, N,N-diethylamino group, N-methyl-N-phenylamino group, N-(2-chloro-yo-tetradecamphenyl)amino group, etc.), alkoxy groups (e.g., methoxy group, ethoxy group, benzyloxy group, methoxyethoxy group, butoxyethoxy group, ni(2°co,,2-)lifluoroethoxy)ethoxy group, etc.), aryloxy group ( For example, it represents a phenyloxy group, an α- or β-7tyloxy group, a 3.yo-dimethoxy7ethyloxy group, a ≠-phenylphenyloxy group, etc.).

When a plurality of R or R's exist in the same molecule, they may be the same or different from each other.

Among the compounds represented by the general formula (A), particularly preferred compounds are the following general formulas (A-/), (A-2) or (A-2).
−J). Among them, preferred compounds are represented by the general formula (A-/).

In general formulas (A-/), (A-2), and (A-3), R, R', R4, R5, R6, and n have the same meanings as described for general formula (A). Expression, mh
l independently represents an integer of 0-1. When there are multiple R's in the same molecule, they may be the same or different.

R6 is a halogen atom, alkyl group, aryl group, hetero group, cyano group, alkoxy group, aryloxy group, heterocyclic oxy group, acyloxy group, carbamoyloxy group, silyloxy group, sulfonyloxy group, acylamino group, anilino group, ureido group, imide group, sulfamoylamino group, carbamoylamino group, alkylthio group,
represents an arylthio group, a heterocyclic thio group, an alkoxycarbonylamine group, an aryloxycarbonylamino group, a sulfonamide group, a carbamoyl group, an acyl group, a sulfamoyl group, a sulfonyl group, a sulfinyl group, an alkoxycarbonyl group, an aryloxycarbonyl group,
Among R6, particularly preferred are an acylamino group, a sulfamoylamino group, a carbamoylamino group, a sulfonamide group, a carbamoyl group, or a sulfamoyl group.

The compound represented by general formula (A) is, for example, Y-OH
It can be easily synthesized by a reaction such as +Z(-R'-0-mother-in-law-R-=17nu → (A) (here, Z represents a halogen atom, such as a chlorine atom, a bromine atom, etc.) .

Specific examples of the compound represented by the general formula (A) used in the present invention are shown below, but the invention is not limited thereto.

/j a /l.

(C4H90CH2CH20)yPlriQ ko 2 ko 3 ko j j 3 The photographic layer in the present invention refers to the silver halide emulsion layer and its adjacent layer.

The pyrazoloazole coupler represented by the general formula (I) of the present invention is preferably added to the silver halide photographic light-sensitive layer, but depending on the purpose, it may be added to a non-light-sensitive field adjacent to the light-sensitive layer. The amount added is per mole of silver halide present in the same layer or adjacent layer/×IQ -%-!
×10 mol, preferably I×10−2 to J−X1
It is in the range of 0-1 mole.

The compound represented by the general formula (A) of the present invention is a compound represented by the general formula (A).
It is added in the same layer as the coupler represented by I). The amount added is 0.7 to 1 mole of the coupler of general formula (I).
3 moles, preferably in the range of 0.5 to 2 moles. Further, the compound represented by the general formula (A) can be added to a light-sensitive material in accordance with the method for adding a coupler to a light-sensitive material, which will be described later. Further, the compound represented by the general formula (A) and the compound represented by the general formula (I) may be added to the coating liquid at the same time, or may be added separately. Most preferably, the compound represented by the general formula (A) and the coupler represented by the general formula (I) are mixed and added to the coating liquid.

Couplers represented by general formula (I) and general formula (A)
Two or more kinds of compounds represented by may be used in the same layer, or the same compound may be used in different layers.

Useful color couplers that can be used in the present invention are cyan, magenta and yellow coloring couplers;
Typical examples of these are naphthol or phenolic compounds, pyrazolone compounds, and open-chain or heterocyclic ketomethylene compounds.・Disclosure (Resea)
rchDisclosure) / 76'I j
(/72/971) ■-D section and the same//7/7
It is described in the patent cited in (2019//2017).

The color coupler incorporated in the light-sensitive material must have a ballast group or be polymerized (preferably more diffusion resistant). A two-carrier color coupler that can reduce the amount of coated silver and achieve high sensitivity.A coupler in which the coloring dye has appropriate diffusivity, a colorless coupler, or a development inhibitor that is used in conjunction with the coupling reaction. DIR couplers that release or couplers that release a phenomenon enhancer 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. G0
7.270, same No. 2. ? 7, θ! No. 2 and No. 3
,2 Otsu! , and so-Otsu issue. The use of a two-wheel yellow coupler is preferred for the present invention, as described in U.S. Patent No. 3. G0♂, /9g issue, same number 3. Fugu 2,92♂,
Same No. 3,933. No. 07 and No. G, 02.2.

The oxygen atom dissociative yellow coupler described in Otsu No. 20, etc., or Tokuko Shoyo♂-7023 No., US Patent No. 4t, ¥θ/, 2! No. ko, No. 3, 3-! Otsu, No. 02, RD/lroyoj (/Monday 979), British Patent No. 1
, 1. No. t26.02θ, West German Application Publication No. 279
．． Wa/No. 2, Same No. 2, 2. ．． 2 Otsu/, 3 Otsu! No., No.
J, No. 29.677 and No. 2'733,! /2
A representative example of this is the nitrogen atom dissociative yellow coupler described in No. α-piparoylacetanilide couplers have excellent color fastness, particularly light fastness, while α-benzoylacetanilide couplers provide high color density.

Examples of magenta couplers that can be used in the present invention include oil-protected indacylon or cyanoacetyl couplers, preferably yoichi pyrazolone couplers. ! - Pyrazolone couplers are preferably those in which the 3-position is substituted with an arylamino group or an acylamino group from the viewpoint of the hue and color density of the coloring dye. No. 2, No. 2 and 3
Guj, No. 703, No. 2. ZaQo, 2! ♂ No. 2
, RiO♂, No. 123, No. j, No. 062.663, No. 3. /62,196 and 3,936.0//
It is written in the number etc. As a leaving group for a two-equivalent pyrazolone coupler, the nitrogen atom leaving group described in U.S. Pat.
Particularly preferred are the arylthio groups described in No. 36/, No. 97. Further, the pyrazolone coupler having a pallast group described in European Patent No. 73,63 can provide a high color density.

Cyan couplers that can be used in the present invention include oil-protected naphthol-based and phenol-based couplers. Gu2gu.

Naphthol couplers as described in US Pat. No. 293, preferably US Pat.

Typical examples include the oxygen atom-eliminating type two-equivalent naphthol couplers described in /G, <, No. 396, No. 22♂1233, and No. Q, No. 296.200. Further, specific examples of phenolic couplers include U.S. Pat. ♂9j, /IJ
It is written in the number etc.

Cyan couplers that are stable against humidity and temperature are preferably used in the present invention, and a typical example thereof includes an alkyl group higher than ethyl group at the meta position of the phenol nucleus described in U.S. Pat. No. 3,772.002. Phenolic cyan coupler having U.S. Pat. No. 2,772.162;
Same 3rd and 7th! ♂.

30♂ issue, same issue, /2t, 39g issue, same issue.

33g, 0// issue, same number da,! No. 27.173, West German Patent Publication No. 3, J19.7 Yuwa and Patent Application Shoj♂-'
727.7 / Issue, etc. -Diacylamino-substituted phenolic couplers and U.S. Patent Nos. 3 and 4
t4t≦, No. 322, No. 33J, No. 999, No. 9. Gu! /, f! No. Wa and No. %, '727.74
Examples include phenolic couplers having a phenylureido group at the 2-position and an acylamino group at the j-position, as described in No. 7.

In order to correct unnecessary absorption in the short wavelength range of dyes generated from magenta and cyan couplers, it is preferable to use colored couplers in combination with color sensitive materials for photographing. U.S. Patent No./4J, 470 and Japanese Patent Publication No. 7-
Yellow-colored magenta coupler described in 3 tag No. 73, etc. or U.S. Patent No.
3♂, 2j♂ and British Patent No. 1. Typical examples include the magenta-colored cyan coupler described in No. 3/Otsu and No. 3 Otsu♂.

Granularity can be improved by using a coupler in which the coloring dye has an appropriate diffusibility. Such blur couplers are described in U.S. Patent No. '1,31. T, 237 and British Patent No. 2. /26, J'70 contains a specific example of a magenta coupler, and European Patent No. 2 is also published.

! No. 20 and West German Application No. 3, 23'l, !
No. 33 describes specific examples of yellow, magenta or cyan couplers.

The dye-forming couplers and the special couplers described above may form dimers or more polymers. Typical examples of polymerized dye-forming couplers are described in U.S. Patent No. 3. Gu! /, /2
It is described in No. 0 and No. 6, θ10°2//. Specific examples of polymerized magenta couplers are described in British Patent No. 1, 102,123 and U.S. Patent No. 337.2.
It is described in No. 72.

In order to satisfy the characteristics required for the photosensitive material, two or more types of moderate couplers used in the present invention can be used together in the same photosensitive layer, or the same compound can be used in two different layers. It is also possible to introduce more than one.

The coupler used in the present invention can be introduced into the light-sensitive material by various known dispersion methods (for example, solid dispersion method, alkaline dispersion method, preferably latex dispersion method, more preferably oil-in-water dispersion method, etc.). For example, in the oil-in-water dispersion method, a high-boiling organic solvent with a boiling point of /; Dispersion is carried out in an aqueous medium such as water or an aqueous gelatin solution in the presence of an activator. Examples of high boiling organic solvents are described in US Pat. No. 2.3.2, 2.027, etc.

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 phthalate esters (dibutyl phthalate, dinochlorohexyl phthalate,
(Z-ethylhexyl phthalate, decyl phthalate, etc.), esters of phosphoric acid or phosphonic acid (triphenol phosphate, ) IJ Cresyl phosphate, 2-ethylhexyl diphenyl phosphate, tricyclohexyl phosphate, TolJ -, 2-ethylhexyl phosphate, tridodecyl phosphenite, tributoxyethyl phosphate, trichloropropyl phosphate, di-2-ethylhexyl phenyl phosphonate, etc.), benzoic acid esters (2-ethylhexyl benzoate, dodecyl benzoate, 2-ethyl hexyl-p-hydroxybenzoate, etc.), amides (diethyldodecanamide, N-tetradecylpyrrolidone, etc.), alcohols or phenols (stearyl alcohol, 21 goosey tert-amylphenol, etc.), aliphatic carboxylic acid esters (dioctyl azelate, glycerol tributyrate, isostearyl lactate, trioctyl citrate, etc.), aniline derivatives (N,N-dibutyl-2-ptoxy-5-te)
rt-octylaniline, etc.), hydrocarbons (paraffin, dodecylbenzene, diisopropylnaphthalene, etc.), and the like. Also, as an auxiliary solvent, the boiling point is preferably about 30°C or higher! Organic solvents having a temperature of 0°C or more and about 0°C or less can be used, and typical examples include ethyl acetate, butenopepropionate, methyl ethyl ketone, cyclohexanone, nee-ethoxyethyl acetate, dimethylformamide, and the like.

Examples of latex dispersion process steps, effects, and latex for impregnation are provided in U.S. Pat. No. K,/99.

3g3, West German Patent Application (OLS) No. 2. ! evening/.

No. 22y and No. 2. ! 230, etc.

The silver halide emulsion used in the present invention usually contains a solution of a water-soluble silver salt (for example, silver nitrate) and a solution of a water-soluble... It is produced by mixing in the presence of a water-soluble polymer solution such as gelatin. Typical silver halides produced in this manner include silver chloride, silver bromide, and mixed silver halides such as silver chlorobromide, silver chloroiobromide, and silver iodobromide. The silver halide preferably used in the present invention is silver chloroiodobromide, silver iodochloride, or silver iodobromide, which does not contain silver iodide or contains less than 3% by mole of silver iodide. The silver halide grains may have different phases inside and on the surface, may have a multiphase structure such as a bonded structure, or may consist of a uniform phase throughout the grain. Moreover, they may be mixed. For example, silver chlorobromide grains having different phases may have a core or single or multiple layers within the grain that are richer in silver bromide than the average halogen composition. Alternatively, the grains may have a core rich in silver chloride than the average chloride composition or a single or multiple layers within the grains.

Therefore, the grain surface layer may be covered with a layer richer in silver bromide than the average logen composition, or vice versa. The average grain size of silver halide grains (in the case of spherical or nearly spherical grains, the grain diameter is taken as the grain size, and in the case of cubic grains, the ridge-long grain size is taken as the average grain size, and the projected area is also calculated as the average) is λμ or less is preferably 0.7 μ or more, and particularly preferably 0.7 μ or less! μ or more. The particle size distribution may be narrow or wide. Measurement of average particle size by number of particles or weight 0
More than 70 particles of all particles within 1, especially ri! A so-called monodisperse silver halide emulsion having a narrow grain size distribution containing more than 10% of grain size can be used in the present invention. In addition, in order to satisfy the target gradation of a light-sensitive material, one or more monodispersed silver halide emulsions with different grain sizes are mixed in the same layer or in separate layers in emulsion layers having substantially the same color sensitivity. Can be applied in multiple layers. Furthermore, two or more types of polydisperse silver halide emulsions or a combination of a monodisperse emulsion and a polydisperse emulsion may be mixed or layered for use.

The shape of the silver halide grains used in the present invention is regular (cubic, octahedral, dodecahedral, dodecahedral, etc.).
), may have an irregular crystal shape such as a spherical shape, or may have a composite shape of these crystal shapes. Further, tabular grains may be used, and in particular, an emulsion in which tabular grains having a length/thickness ratio of 5 or more, particularly ♂ or more, account for 60% or more of the total projected area of the grains may be used. An emulsion consisting of a mixture of these various crystal forms may also be used. These various emulsions may be either a surface latent image type in which a latent image is mainly formed on the surface or an internal latent image type in which a latent image is formed inside the grains.

The photographic emulsion used in the present invention contains P, graphide (p,
Qlafkides), Chimie etphys Photographic (Chimie etphys)
ique photography), (
Ball-Mo7te/I/ (Paul Montel), 1979), G, F, Duffin (G, F, 1)
) uffin), ``7.t Spiky Emulsion Chemistry (photographic E
Mulsion Chemistry) ;'(Focal Solé, z, (1;'ocal press, /
(1963), V.L., Zerichman (V.L.).

Making and Coating Photographic Emulsions (Maki
ng and coating photography
icEmulsion)” I (Focal Press (F
ocal press), /9! ; 9). That is, any of the acid method, neutral method, ammonia method, etc. may be used.
Further, as a method for reacting the soluble silver salt and the soluble halogen salt, any one of a one-sided mixing method, a simultaneous mixing method, a combination thereof, etc. 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 halogenide 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 with a regular crystal shape and a nearly uniform grain size can be obtained.

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.

After grain formation, silver halide emulsions are usually subjected to physical ripening, desalting and chemical ripening before being used for coating.

When physical ripening is performed in the presence of a known silver halide solvent,
A monodisperse emulsion with a regular crystalline shape and a near-uniform grain size distribution is obtained.

The silver halide emulsion used in the present invention can be chemically sensitized by sulfur or selenium sensitization, reduction sensitization, noble metal sensitization, etc. alone or in combination. Namely, the sulfur sensitization method uses a sulfur-containing compound that can react with activated gelatin or silver, the reduction sensitization method uses a reducing substance, the noble metal sensitization method uses a metal compound, etc. Can be used together.

The photographic emulsion used in the present invention is spectrally sensitized with a photographic sensitizing dye. The dyes used include cyanine dyes, merocyanine dyes, complex cyanine dyes, complex merocyanine dyes, holopolar-cyanine dyes, hemicyanine dyes, styryl dyes and hemioquinol dyes. Particularly useful dyes are those belonging to the cyanine dyes, merocyanine dyes and complex merocyanine 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,
Aminostilbene compounds substituted with nitrogen-containing heterocyclic groups (
For example, US Pat. No. 2,933,390, US Pat. No. 3,1.
3! , Nos. 7 and 7), aromatic organic acid formaldehyde condensates (such as those described in U.S. Pat. Nos. 3,2, 3,6),
70), cadmium salts, azaindene compounds, etc. U.S. Patent No. 3. ≦/j,,6
No. 73, 3. Otsu/! , 6g/issue, 316/2. Ko9
Particularly useful are the combinations described in Yu issue and ibid., issue 636.72/.

The photographic emulsion used in the present invention can contain various compounds for the purpose of preventing capri during the manufacturing process, storage, or photographic processing of the light-sensitive material, or for stabilizing photographic performance. Namely, azoles such as benzothiazolium salts, benzimidazolium salts, imidazole necks, benzimidazoles (preferably!-nitro(nizimidazoles), nitroindazoles, benzotriazoles (preferably termethylbenzotriazoles) ), triazoles, etc.; mercapto compounds, such as mercaptothiazoles, mercaptobenzothiazoles, mercaptobenzimidazoles, mercaptobenzoxazoles, mercaptooxadiazoles, mercaptothiadiazoles, mercaptotriazoles, mercaptotetrazoles (especially ( (2/-phenyl!-mercaptotetrazole, etc.), mercaptopyrimidines, mercaptotriazines, etc.; thiocarbonyl compounds such as oxazolinthion; azaindenes, such as triazaindenes, tetraazaindenes (especially g-hydroxy- Methyl(/
+ 3+ 33+ 2) Tetraazaindene), hantaazaindenes, etc.; benzenethiosulfo7HUA,
Benzene sulfinic acid can be added with a number of compounds known as anti-capri agents or stabilizers, such as benzene sulfonic acid amides: purines such as adenine, and the like.

For more specific examples of anti-capri agents or stabilizers and their use, see, for example, US Pat. No. 3,9! the law of nature,
Ri 2gu No. 3, 972, Ri 4! No. 7, Tokuko Sho! 2
−, 2♂6≦0, Research Disclosure (R
esearch 1) isclosure)/2 Otogu 3
(72/7922) VIA-VIM and E. J. Birr, ``Stabilization of Photographic''/Luz: - Halide Emulsions (3 tabilization of photo)
graphicSilver Halide Emul
sion)”, (7 Ocal Press (lli'oca)
It is described in publications such as ``I Press'' and ``/97''.

The light-sensitive materials produced using the present invention may contain hydroquinone derivatives, amine phenol derivatives, amines, gallic acid derivatives, catechol derivatives, ascorbic acid derivatives, colorless couplers, sulfonamide phenols as color antifogging agents or color mixing inhibitors. It may also contain derivatives and the like.

Various anti-fading agents can be used in the light-sensitive material of the present invention. Organic anti-fading agents include hydroquinones,
Hindered phenols focused on 6-hydroxychroman a, j-hydroxycoumarans, spirochroman m, p-alkoxyphenols, and bisphenols,
Typical examples include gallic acid derivatives, methylene dioxy (methylene dioxy), amine phenol, hindered amine, and phenolic hydroxyl/lylated and alkylated ether or ester derivatives of these compounds. Metal complexes such as nickel complexes (oximado) and nickel (bis-N,N-dialkyl ditheocarbamado) complexes can also be used.

Specific examples of organic antifading agents are described in the following patent specifications:

Hydroquinones are covered by U.S. Patent Nos. 2 and 3 Otsu 0. -22θ No. 2. G/♂, No. 673, No. 2,700.253
No. 2, 70/, 797, No. 2, 2? ,6
No. 52, No. 2,732, jθ0, No. U, 73!
, 74! No. 3, 9♂2.9 tag issue, No. G, G, F10. No. 2, British IMI patent number 1,! 1. !
, No. 92/, U.S. Pat. No. 3.3.2.300, No. J', !73
．． No. 060, No. 3, No. 52, No. 622, No. 3 + Go 9
♂, No. 209, No. 3, 2≦&, No. 337, JP-A-Shoj
Spiroindanes are disclosed in U.S. Pat. , 74! No. 2.061.97! No., Tokukai Akira! 9-10! No. 39, Special Publication Show J7-/97gq, etc., the hindered phenol is described in U.S. Patent No. 3゜7θO2! ! No., Tokukai Showa 2
-7222! No., U.S. Patent No. 22J', 236, Special Publication! ! -6623, etc., gallic acid derivatives, methylenedioxybenzenes, and amine phenols are disclosed in U.S. Pat. ♂ No. 6, Tokko Akira! ;6-2//Kuku etc., hindered amines are disclosed in U.S. Patent No. 3,336゜13
No. 6, Da, Koroto, No. 523, British Patent No. 1.3, No. 6,122, No. 1, 3! Google, 3/3, 1st and 4th
110. Rgu Otsu No., Tokuko Sho J/-/ri 2Q No., Toku Kai Sho!
♂-//gu No. 036, same! ? -33 (r4tza issue, same!
Ether and ester derivatives of phenolic hydroxyl groups are disclosed in US Patent No. 9-2♂3, /! ;J, 766
No. q, /7 g, 2JO No. 11tI approved! Gu,
No. 276, No. 26, No. 2, No. 30, No. 30 of the same! ! -Otsu 32/issue, same jt-10! ;
/4t No.7, same! Tar 10! No. 39, Tokko Akira! 2-37
No. 56, US Patent No. 279.990, Special Publication!
3-j,! ≦No. 3, etc., metal complexes are disclosed in U.S. Patent No.
jO, No. 93♂, No. gu, Cog/.

/! ! No., British Patent No. 2, O'27, 7J'/
(A), etc., respectively. These compounds are usually for their corresponding color couplers! The purpose can be achieved by co-emulsifying with a coupler and adding it to the photosensitive layer in an amount of 1 to 100% by weight. To prevent thermal and especially light-induced deterioration of cyan dye images,
It is effective to introduce an ultraviolet absorber into the layers (1) on both sides adjacent to the cyan coloring layer.

In the photosensitive material of the present invention, an ultraviolet absorber can be added to the hydrophilic colloid layer. For example, U.S. Patent No. 3
, ! ! 3, 7 tag No. 3, No. 23, O73, Special Publication Shoj/-Otsuj No. 0, and European Patent No. J'7. /
6θ No. t (A benzotriazole substituted with an aryl group described in U.S. Patent No. 60, !,?
No. 9 and the same No. 9, /ri! , U.S. Pat. No. 706.706 and U.S. Pat. No. 3,707.32! Nisder cinnamic acid crystals described in U.S. Patent No. 3,2/6,63θ and British Patent No. 1
゜! 2/, ode to benzophenone described in No. 366,
U.S. Pat. No. 3,7t/, 272 and U.S. Pat.

A polymer compound having an ultraviolet absorbing residue can be used as described in Japanese Patent No. 3/726.

U.S. Patent No. 3,4t Ota No. 262 and U.S. Patent No. 3゜70
Ultraviolet absorbing fluorescent brighteners described in No. 0 and Zjj may also be used. A typical example of a UV absorber is research
Disclosure (Research page)
L o s u r e ) A 2g, 232 (1
927 (month)).

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 or irradiation. As such dyes, oxonol dyes, hemioquinol dyes, steryl dyes, merocyanine dyes, anthraquinone dyes, and ano dyes are preferably used; in addition, /anine dyes, azomethine dyes, triarylmethane dyes, and phthalocyanine dyes are also useful. It is.

An oil-soluble dye can also be emulsified by an oil-in-water dispersion method and added to the hydrophilic colloid layer.

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.

Gelatin includes general-purpose lime-processed gelatin, as well as acid-processed gelatin and Bulletin of the Society of Scientific Photography.
Japan (13ul let 1nof the
5ociety of Scientific Ph.
otography of Japan),
Enzyme-treated gelatin as described in A, /B, page 30 (/9B, B) may be used, and gelatin hydrolysates and enzymatic decomposition products may also be used.

In the photographic material of the present invention, an inorganic or organic hardening agent may be contained in any hydrophilic colloid layer constituting the photographic light-sensitive layer or the back layer.

The photosensitive material of the present invention contains one or more surfactants for various purposes such as a coating aid, antistatic properties, improved slipperiness, emulsification and dispersion, prevention of adhesion, and improvement of photographic properties (for example, development acceleration, high contrast, and sensitization). But that's fine.

The photosensitive material of the present invention (2) contains additives other than the above-mentioned additives (2) various stabilizers, anti-staining agents, developing agents or their precursors, development accelerators or their precursors, lubricants, mordants,
Matting agents, antistatic agents, plasticizers, and other various additives useful for photographic materials may be added. Representative examples of these additives are listed in Research Disclosure (R
e5earchDisclosure), /76
'l 3 (/72/971) and the same/za 2/
It is described in Otsu (/979/July).

The invention is also applicable to multilayer, multicolor photographic materials having at least two different spectral sensitivities on the support.

Multilayer natural color photographic materials usually have a red-sensitive emulsion layer on a support,
It has at least one green-sensitive emulsion layer and at least one blue-sensitive emulsion layer. The order of these layers can be arbitrarily selected depending on the necessity (==.The preferred order of layer arrangement is from the support side to red sensitivity, green sensitivity, blue sensitivity, or from the support side to blue sensitivity, red sensitivity,
I have a green sensibility. Further, each of the above-mentioned emulsion layers may be composed of two or more emulsion layers having different sensitivities, or a non-photosensitive layer may be present between two or more emulsion layers having the same sensitivity. 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 (-yellow-forming coupler), but different combinations may be used depending on the case. .

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

The color developing solution used in the development of the light-sensitive material of the present invention is preferably an alkaline aqueous solution containing an aromatic primary amine color developing agent as a main component. Although amine phenol compounds are also useful as color developing agents, p-phenylenediamine compounds are preferably used, representative examples of which include 3-methyl-Z-amino-N, N-diethylaniline, 3-methyl -guamino-N-ethyl-N-
β-hydroxylethylaniline, 3-methyl-Q-7
Mi/-N-ethyl-N-β-methanesulfonamidoethylaniline, 3-methyl-guamino-N-ethyl-N
- β-methoxy7ethylaniline and their sulfates,
Examples include hydrochloride and p-toluenesulfonate. These diamines are generally more stable in their salt form than in their free state, and are therefore preferably used.

The color developer contains pH buffering agents such as alkali metal carbonates, borates or phosphates, development inhibitors or anti-capri agents such as bromides, iodides, benzimidazoles, benzothiazoles or mercapto compounds. Generally, it includes such things as Also, if necessary, preservatives such as hydroxylamine or sulfites, organic solvents such as triethanolamine, diethylene glycol,
Penzil arcono? Development accelerators such as lyethylene glycol, dye-forming couplers, competitive couplers, nucleating agents such as sodium boron hydride, auxiliary developers such as /-phenyl-3-pyrazolidone, tackifiers, aminopolycarboxylic acids. , various chelating agents such as aminopolyphosphonic acid, alkylphosphonic acid, and phosphonocarboxylic acid, West German patent application (published) No.
Wow! An antioxidant described in No. θ may be added to the color developing solution.

In the development process for reversal color photosensitive materials, black and white development is usually performed followed by color development. This black and white developer (= is dihydroxybenzenes such as hydroquinone, 3-pyrazolidones such as phenyl-3-pyrazolidone, or N
Known black and white developers such as amine phenols such as -methyl-p-amine phenol can be used alone or in combination.

After color development, the photographic emulsion layer 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 (III)
), cobalt ([1), chromium (■), copper (■) and other polyvalent metal compounds, peracids, quinones, nitrone compounds, etc. are used. Typical bleaching agents include ferricyanide; dichromate; iron (III) or cobalt (I[
l), such as ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, nitrilotriacetic acid, /, 3-
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. Among these, ethylenediaminetetraacetic acid iron (1) salt and persulfate are preferred from the viewpoint of rapid processing and environmental pollution. Furthermore, the ethylenediaminetetraacetic acid iron ([) complex salt is particularly useful in both stand-alone bleach solutions and -bath bleach-fix solutions.

If necessary, various accelerators may be used in combination with the bleaching solution and bleach-fixing solution. For example, in addition to bromide ion and iodide ion, U.S. Patent No. 3,701. , J-67, Tokuko Sho ¥! −♂! 0
No. 3, No. 9-26SZt, JP-A-63-32733
Same issue! 3-3 Thiourea compounds as shown in Otsu No. 233 and No. 63-3701t; JP-A-63-72
<1 Gukoku No. 63-6737, No. 63-67F3
7th issue, same, f3-3273 Otsu issue, same j3-Otsu! No. 232, same! Goo! No. 2!3 and U.S. Patent No. 3. ♂wa 3,
♂! ! Thiol-based compounds as shown in No. 4: '4
Kaisho getter! ? Otsugugu issue, same ro-/ri 0729 issue, same j3-27gu 2 otsu issue, same! 3-/41/l, No. 23, No. 63-70, No. 232 and J! -3! Heterocyclic compounds described in No. 727, etc.; JP-A-Sho! Knee 20♂32,
same! ! -2606 issue and the same! ! -2≦Thioether compounds described in rot, etc.: Tertiary amines described in JP-A No. 4tJ'-♂Gugugu O; JP-A No. 4T-9239
Compounds such as thiocarbamoyl m described in No. 9 may be used alone or in combination of two or more. Bromine ions, iodide ions, thiol-based or disulfide-based compounds are preferred bleach accelerators. These bleaching accelerators are particularly effective when color photosensitizing (a-white fixing of three materials) for photography.

Examples of the fixing agent include thiosulfate, thiocyanate, the thioether compound thiourea, and a large amount of iodide, but thiosulfuric acid sulfate is commonly used. As the preservative for the bleach-fix solution and the fix solution, sulfites, bisulfites, or carbonyl bisulfite adducts are preferred.

After bleach-fixing or fixing, washing with water is usually performed. Various known compounds may be added to the water washing process for the purpose of preventing precipitation and saving water. For example, to prevent precipitation, use water softeners such as inorganic phosphoric acid, aminopolycarboxylic acid, and organic phosphoric acid, hardening agents such as magnesium salts and aluminum salts, or to prevent drying load and unevenness. A surfactant and the like can be added as necessary. Orori, E. West (L.

E. West), °゛Water Qualit y Cr i
ter i;+)”.

°' Photographic Science and Engineering = 7 Rings
A compound described in "ceand I:nginserir+g)", Vol.

In the washing process, it is common to use countercurrent washing in tanks larger than one to conserve water. Furthermore, instead of the washing process, we use Tokukaisho! 2
−♂! A multistage countercurrent stabilization treatment step as described in No. 3 may also be carried out. In the case of this step, a countercurrent column with 2 to 9 tanks is required. Various compounds are added to this stabilizing bath for the purpose of stabilizing images. For example, various buffering agents (e.g., borates, metaborates, borax, phosphates, carbonates, potassium hydroxide, sodium hydroxide, aqueous ammonia) to adjust membrane pH (e.g., pH 3 to ♂) (using a combination of monocarboxylic acid, dicarboxylic acid, polycarboxylic acid, etc.) and formalin are representative examples. In addition, water softeners (inorganic phosphoric acid, aminopolyphosphonic acid, organic phosphoric acid, aminopolyphosphonic acid, phosphonocarboxylic acid, etc.), surfactants, fluorescent whitening agents, hardening agents, etc. may be added as necessary. Various additives may be used, and two or more of the same or different desired compounds may be used in combination.

In addition, ammonium chloride,
It is preferable to add various ammonium salts such as ammonium nitrate, ammonium sulfate, ammonium phosphate, ammonium sulfite, and ammonium thiosulfate.

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

For example, the indoaniline compounds described in U.S. Pat. ．． 3y! λ, No. 599,
Research Disclosure
sclosure) /￥♂j0 and same/j/6
Schiff base-type compounds described in No. Wa, aldol compounds described in No. 392, metal salt complexes described in U.S. Pat. Including the urethane compounds of
623 evening issue, same j Otsu-/6/33 issue, same evening issue 132
Same issue! g-32? Gu No. 2, same j6-♂323 Gu No., same! Otsu-13736, same! g-♂3733, same! 23rd evening issue, 61-J'7737, 66-! '
No. 74130, No. 3 to No. 106.297, No. j4-1
No. 0723≦, same j7-97. f37 issue and the same! 2-
♂3taotsu! Examples include various salt-type precursors described in No. 1, etc.

The silver halide color light-sensitive material of the present invention may contain various /-phenyl-3-pyrazolidones, if necessary, for the purpose of promoting color development. A typical compound is Tokkai Sho! otsu-6gu No. 339, same j2-/gugu! Group 2
No., same J7-2///G2, same Ta ♂-60! ;No.32, Douza-50! No.36, Douj♂-yo0 No.33, Dou!
♂－! 0yo 3rd issue, same! ♂－! ;0!3J- issue and the same! It is described in ♂-//, f'131 rc, etc.

The various processing solutions used in the present invention are at 10°C-! Used at 0°C. The typical temperature is 33°C to 3z0C, but higher temperatures can be used to accelerate processing and shorten processing time, or lower temperatures can be used to improve image quality and stability of the processing solution. I can do it. Furthermore, in order to save silver on photosensitive materials, treatment using cobalt intensification or hydrogen peroxide intensification as described in West German Patent No. 770 or U.S. Pat. No. 3.62G, 999 may be performed. good.

(Examples) The present invention will be explained in more detail below using Examples, but the present invention is not limited thereto.

Example 1 Exemplary coupler (7)/! To r2, add 2 ml of tri(2-ethylhexyl)phos 7-ether, 2 rnl of ethyl acetate.
Add and heat to dissolve. On the other hand, gelatin IO? Aqueous solution 1 containing sodium dodecylbenzenesulfonate/, Of
Add the above coupler solution to 100ml and prepare a fine emulsified dispersion of the coupler solution by high speed mechanical stirring.

The total amount of this emulsified dispersion is Br! In addition to the silver chlorobromide emulsion containing 0 mol/00f (Age, jtfj (including)), 10ml of flathead dichloro-4-hydroxy-s-triazine sodium salt of 2 μm was added as a hardening agent.
A sample was prepared by coating it on a paper support laminated with polyethylene on both sides so that the amount of silver coated was -ZOOm97 m'', and then coating a gelatin layer on top of this coated layer.This will be referred to as sample A. Next, an emulsified dispersion was prepared in the same manner as described above, except that addition compounds (1), (4), αB, and (c) in equimolar amounts as the coupler were added together with the exemplary coupler (i2.ry). Ag was coated on the same support using the same emulsion in the same amount.
Samples were prepared by applying the same amount. These samples are designated as B, C, D and E, respectively.

These samples A to E were subjected to wedge exposure of 1000C, M, and S, and were treated with the following processing solution.

Developer benzyl alcohol /jml diethylenetriamine! Acetic acid jlKBr
O, HirotNa2SOa
6? Na2COa
30 f hydroxyamine sulfate
2 2μm Amino-3-methyl-N-β- (methanesulfonamido)ethylaniline・3/λH2SO4・H2O 11,1? Adjust to 1000 with water to pH 10, / Bleach-fix ammonium thiosulfate (70wt%) lyo□m1 Na2SO3! ? Na(Fe(EDTA)) ao f
EDTA Hiroshi
? pHA adjusted to 1000- with water, r Processing process temperature Time Developing solution 33°C 3 minutes 30 seconds Bleach-fixing solution 33°C 7 minutes 30 seconds Washing with water, 2r~3! The magenta color image of each sample obtained in this manner for 0C3 minutes was a color image with good hue and high saturation.

When the photographic characteristics of these color images were measured, the following results were obtained.

Table 1 Photographic properties Relative value of exposure site giving density of *Cub+)+0.1 Sample A was used as the standard (100).

From these results, it was found that the addition of the additive of the present invention resulted in excellent photographic properties in terms of sensitivity, gradation, and maximum density.

Example λ The first layer (lowest layer) to the seventh layer (uppermost NI) as shown in Table 3 were coated on a paper support laminated with polyethylene on both sides to form color photographic materials F, G, H. ,I
, J. created KSL.

At this time, the composition of the coating solution containing the emulsified dispersion and emulsion of the magenta coupler used in the third layer was a solution prepared according to Example.

These samples F to L were attached with a B-G-R three-color separation filter, exposed to light in exactly the same manner as in Example 1, and then processed.

The photographic properties obtained are shown in Table ■.

Table ■ Photographic properties * Relative value of exposure amount giving density of +0.1 Sample F was used as reference (100).

These results show that even in multilayer samples, the additive of the present invention contributes to improving the coloring ability and provides excellent photographic quality. It can be seen that the sample L uses the additive of the present invention as a solvent and gives similarly excellent photographic properties.

Claims (1)

[Scope of Claims] A silver halide color characterized by containing a pyrazoloazole coupler represented by the following general formula [I] and a compound represented by the general formula (A) in the same photographic layer. Photographic material. General formula (I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ In the above formula, R^1 represents a hydrogen atom or a substituent, and X represents a hydrogen atom or a coupling reaction with an oxidized aromatic primary amine developer. Represents a group that can be separated by Za, Zb
and Zc is methine, substituted methine, =N- or -NH
- represents a Za-Zb bond and a Zb-Zc bond, one of which 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. General formula (A) Y-O-(R'-O)-n_R In the above formula, Y is a substituted or unsubstituted aryl group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted heterocyclic group, ▲Math. , there are chemical formulas, tables, etc. ▼ groups, or ▲ there are mathematical formulas, chemical formulas, tables, etc. ▼ represents groups. R' represents a substituted or unsubstituted alkylene group, a substituted or unsubstituted arylene group, or a substituted or unsubstituted aralkylene group, and R represents a substituted or unsubstituted alkyl group, or a substituted or unsubstituted aryl group. . However, Y and R are never an alkyl group at the same time. R_4 and R_5 are substituted or unsubstituted alkyl groups,
It represents a substituted or unsubstituted aryl group, a substituted or unsubstituted amino group, a substituted or unsubstituted alkoxy group, or a substituted or unsubstituted aryloxy group. n represents an integer from 1 to 5.