JP3469015B2 - Silver halide color photographic materials - Google Patents

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a silver halide color photographic light-sensitive material containing a novel coupler.

[0002]

2. Description of the Related Art In silver halide color light-sensitive materials,
Using the exposed silver halide as an oxidizing agent, the oxidized aromatic primary amine-based color developing agent and the coupler react to react with indophenol, indoaniline, indamine,
It is well known that azomethine, phenoxazine, phenazine and dyes related thereto are formed and color images are formed. In such a photographic system, a subtractive color method is used, and a color image is formed by yellow, magenta and cyan dyes. Of these, phenol- or naphthol-based couplers have conventionally been generally used for forming a cyan dye image. However, since these couplers have unfavorable absorption in the green region, they have a serious problem of significantly reducing color reproducibility, and it is desired to solve these problems.

As means for solving this problem, the heterocyclic compounds described in US Pat. Nos. 4,728,598 and 4,873,183 and European Patent 0249453A2 have been proposed. However, these couplers have fatal problems such as low coupling activity. As couplers that overcome these problems, European Patent Publication Nos. 491197A1, 488248 and 545300.
Nos. 6,288,67A1, 4884909, U.S. Pat. No. 5,164,289, JP-A-6-347960 and the like have been proposed. These couplers are superior to conventional phenol- or naphthol-based couplers in terms of hue and coupling activity, and are also superior in that the dye has a large molecular absorption coefficient.
Further, couplers having a dissociative group introduced into the molecule are disclosed in JP-A-7-248594 and JP-A-8-146576 as couplers exhibiting sufficient color developability even in systems requiring higher activity couplers such as color reversal systems. No.

However, the dyes obtained from these pyrroloazole-based couplers tend to cause aggregation in the film, and there is a problem that the hue differs between the high-density portion and the low-density portion. This problem is particularly remarkable when the amount of the high-boiling organic solvent (oil) at the time of emulsification is small, and in terms of the coupler structure, the carboxyl group in the molecule as described in JP-A-8-146576 mentioned above. It was particularly remarkable in couplers having a dissociative group such as a group. further,
A problem with many pyrroloazole couplers is the presence of ferrous ions, which are formed in the bleaching bath or bleach / fix bath as a result of the reduction of ferric ion during the bleaching process. The point is that the dye is easily reduced to form a leuco dye.

[0005]

SUMMARY OF THE INVENTION Therefore, the object of the present invention is to provide a coupler which exhibits excellent color development even in a low oil amount, has a small concentration dependence of hue, and is excellent in stability against ferrous ion reduction. Another object of the present invention is to provide a silver halide color photographic light-sensitive material.

[0006]

Means for Solving the Problems The present inventors have made earnest studies on a pyrrolotriazole type coupler, and have found that the object of the present invention can be achieved by the following means.

(1) A silver halide color photographic light-sensitive material characterized in that at least one layer on a support contains a coupler represented by the following general formula (1).

[0008]

[Chemical 3]

In the general formula (1), R ₁ and R ₂ each represent an electron-withdrawing group having a Hammett's substituent constant σp value of 0.20 or more and 1.0 or less. R ₃ represents a substituent, and n represents an integer of 0 to 4. Q is -NHCO -, - NHSO ₂ -,
-CONH- or an -SO ₂ NH-. R ₄ represents a substituent substituted with an acidic dissociative group. R ₅ represents a substituent, and m represents an integer of 0 to 4. X represents a hydrogen atom or a group capable of splitting off upon coupling with an oxidized product of a color developing agent.

(2) In the above general formula (1), R ₁ is a cyano group, and R 2 is a group represented by the general formula (2). Silver color photographic light-sensitive material.

[0011]

[Chemical 4]

In the general formula (2), R ₁ 'and R ₂ ' each represent an aliphatic group, R ₃ ', R ₄ ' and R ₅ 'each represent a hydrogen atom or an aliphatic group, and Z represents 5 ~ Represents a group of non-metal atoms necessary to form an 8-membered ring.

(3) The silver halide color photographic light-sensitive material as described in (1) or (2) above, wherein the silver halide color light-sensitive material is a silver halide color reversal light-sensitive material.

[0014]

BEST MODE FOR CARRYING OUT THE INVENTION The compound of the present invention is described in detail below. In the coupler of the present invention, R ₁ and R ₂ are both electron-withdrawing groups having Hammett's substituent constant σp value of 0.20 or more and 1.0 or less, and the sum of R ₁ and R ₂ is 0.65 or more. preferable. The coupler of the present invention has excellent performance as a cyan coupler by introducing such a strong electron-withdrawing group. The sum of the σp values of R ₁ and R ₂ is preferably 0.7 or more, and the upper limit is about 1.8.

In the present invention, R ₁ and R ₂ have a Hammett substituent constant σp value (hereinafter, simply referred to as σp value) of 0.2.
The electron withdrawing group is 1.0 or more and 1.0 or less. Preferably, σp
An electron-withdrawing group having a value of 0.3 or more and 0.80 or less, more preferably 0.40 or more and 0.75 or less. Hammett's rule was published in 1935 in order to quantitatively discuss the effect of substituents on the reaction or equilibrium of benzene derivatives. P. The rule of thumb proposed by Hammett, which is widely accepted today. Substituent constants determined by the Hammett rule include σp value and σm value, and these values are described in many general textbooks. A. Dean edition “Lang
e's Handbook of Chemistry "12th Edition, 1979 (McGr
aw-Hill) and "Special Issue on Chemistry", No. 122, pp. 96-103,
1979 (Nankodo), Chemical Reviews, Volume 91, 165-19
Detailed on page 5, 1991. In the present invention, R ₁ and R ₂
Is defined by the σp value, but this does not mean that the values known from the literatures described in these publications are limited to certain substituents, and even if the values are unknown to the literatures, they were measured based on Hammett's rule. Of course, as long as it is included in the range, it is included.

Specific examples of R ₁ and R ₂ which are electron withdrawing groups having a σp value of 0.2 or more and 1.0 or less include an acyl group, an acyloxy group, a carbamoyl group, an aliphatic oxycarbonyl group, an aryloxycarbonyl group and a cyano group. , Nitro group, dialkylphosphono group, diarylphosphono group, diarylphosphinyl group, alkylsulfinyl group, arylsulfinyl group, alkylsulfonyl group, arylsulfonyl group, sulfonyloxy group, acylthio group,
Sulfamoyl group, thiocyanate group, thiocarbonyl group, alkyl group substituted with at least two or more halogen atoms, alkoxy group substituted with at least two or more halogen atoms, aryl substituted with at least two or more halogen atoms An oxy group, an alkylamino group substituted with at least two or more halogen atoms, an alkylthio group substituted with at least two or more halogen atoms, an aryl group substituted with another electron-withdrawing group having a σp value of 0.20 or more, Examples thereof include a heterocyclic group, a chlorine atom, a bromine atom, an azo group, and a selenocyanate group. The group which can be further substituted among these substituents may further have a ring-positioning group as described later for R ₃ .

The aliphatic oxycarbonyl group is an aliphatic moiety whose aliphatic moiety may be linear, branched or cyclic and which may contain a saturated or unsaturated bond.
The aliphatic oxycarbonyl group is alkoxycarbonyl,
It is substituted with cycloalkoxycarbonyl, alkenyloxycarbonyl, alkynyloxycarbonyl, cycloalkenyloxycarbonyl and the like. Hereinafter, the word “aliphatic” is used as a synonym.

Typical σp values of electron withdrawing groups having a σp value of 0.2 or more and 1.0 or less include bromine atom (0.23), chlorine atom (0.23), cyano group (0.66), nitro group (0.78),
Trifluoromethyl group (0.54), tribromomethyl group (0.29), trichloromethyl group (0.33) carboxyl group (0.45), acetyl group (0.50), benzoyl group (0.4
3), acetyloxy group (0.31), trifluoromethanesulfonyl group (0.92), methanesulfonyl group (0.72),
Benzenesulfonyl group (0.70), methanesulfinyl group (0.49), carbamoyl group (0.36), methoxycarbonyl group (0.45), ethoxycarbonyl group (0.45), phenoxycarbonyl group (0.44), pyrazolyl group (0.37), methanesulfonyloxy Group (0.36), dimethoxyphosphoryl group (0.60), sulfamoyl group (0.57) and the like.

Preferred examples of the substituent of R ₁ are cyano group, aliphatic oxycarbonyl group (linear or branched alkoxycarbonyl group having 2 to 36 carbon atoms, aralkyloxycarbonyl group, alkenyloxycarbonyl group, alkynyloxycarbonyl group). Group, cycloalkoxycarbonyl group, cycloalkenyloxycarbonyl group, for example, methoxycarbonyl, ethoxycarbonyl, isopropoxycarbonyl, dodecyloxycarbonyl, octadecyloxycarbonyl, 2-ethylhexyloxycarbonyl, sec-butyloxycarbonyl, oleyloxy. Carbonyl, benzyloxycarbonyl, propargyloxycarbonyl, cyclopentyloxycarbonyl, cyclohexyloxycarbonyl, 2,6-di-t-
Butyl-4-methylcyclohexyloxycarbonyl), a dialkylphosphono group (a dialkylphosphono group having 2 to 36 carbon atoms, such as dimethylphosphono, diethylphosphono, an alkyl or arylsulfonyl group (having 1 to 36 carbon atoms). An alkyl or aryl sulfonyl group, for example, a methane sulfonyl group, a butane sulfonyl group, a benzene sulfonyl group, a p-toluene sulfonyl group), a fluorinated alkyl group (a fluorinated alkyl group having 1 to 36 carbon atoms, such as trifluoromethyl A particularly preferred substituent for R ₁ is a cyano group, an aliphatic oxycarbonyl group, or a fluorinated alkyl group,
Most preferably, it is a cyano group.

As an example of the substituent of R ₂ , preferably R ₁
And the aliphatic oxycarbonyl group, carbamoyl group (C1-C36 carbamoyl group, for example, diethylcarbamoyl, dioctylcarbamoyl), sulfamoyl group (C1-C36 sulfamoyl group, for example, dimethylsulfyl group). Famoyl, dibutylsulfamoyl), a dialkylphosphono group as described in R ₁ and a diarylphosphono group (a diarylphosphono group having 12 to 48 carbon atoms, for example, diphenylphosphono, di (p-toluylphosphono)) , R ₁ represents a fluorinated alkyl group, and the substituent of R ₂ is particularly preferably an aliphatic oxycarbonyl group represented by the following general formula (2).

[0021]

[Chemical 5]

In the formula, R ₁ 'and R ₂ ' represent an aliphatic group having 36 or less carbon atoms, for example, a linear or branched alkyl group having 1 to 36 carbon atoms, aralkyl group, alkenyl group, alkynyl group, cyclo An alkyl group or a cycloalkenyl group, specifically, for example, methyl, ethyl, propyl, isopropyl,
t-butyl, t-amyl, t-octyl, tridecyl,
Represents cyclopentyl and cyclohexyl. R ₁ ',
R ₂ 'is preferably a branched or cyclic alkyl group having 3 to 30 carbon atoms, and more preferably 4 to 4 carbon atoms.
16 tertiary alkyl groups, particularly preferably tert-
A butyl group, a tert-amyl group, a tert-octyl group, a 1-methylcyclohexyl group, and a 1-methyl-1-cyclohexylethyl group. _{R 3 ', R 4',} R 5 ' represents a hydrogen atom or an aliphatic group. Examples of the aliphatic group include the groups mentioned above for R ₁ ′ and R ₂ ′. _{R 3 ', R 4',} R 5 ' is preferably a hydrogen atom.

Z represents a group of non-metal atoms necessary for forming a 5- to 8-membered ring, which may be substituted, saturated ring or unsaturated bond. good. The nonmetal atom is preferably a nitrogen atom, an oxygen atom, a sulfur atom or a carbon atom, and more preferably a carbon atom.

Examples of the ring formed by Z include a cyclopentane ring, a cyclohexane ring, a cycloheptane ring, a cyclooctane ring, a cyclohexene ring, a piperazine ring, an oxane ring and a thian ring, and these rings will be described later. It may be substituted with a substituent represented by R ₃ . The ring formed by Z is preferably a cyclohexane ring which may be substituted, and particularly preferably, the 4-position is an alkyl group having 1 to 24 carbon atoms (substituted by a substituent represented by R ₃ described later). Optionally substituted).

As a combination of R ₁ and R ₂ , one is a cyano group and the other is a fluorinated alkyl group or an aliphatic oxycarbonyl group. Particularly preferably, one is a cyano group and the other is an aliphatic oxycarbonyl group. At this time, the other is preferably an alkoxycarbonyl group having a branched chain or a cycloalkoxycarbonyl group having a cyclic alkoxy group, and particularly preferably a cycloalkoxycarbonyl group represented by the general formula (2). Most preferably, R ₁ is a cyano group and R ₂ is a cycloalkoxycarbonyl group represented by the general formula (2).

R ₃ represents a substituent, and n is 0 to
Represents an integer of 4. Examples of the substituent represented by R ₃ include a halogen atom, a cyano group, a hydroxyl group, a nitro group,
Carboxyl group, sulfo group, formyl group, aliphatic group, aryl group, heterocyclic group, aliphatic oxy group, aryloxy group, heterocyclic oxy group, acylamino group, sulfonylamino group, amino group, anilino group, heterocyclic amino group Group, ureido group, sulfamoylamino group, aliphatic thio group, arylthio group, heterocyclic thio group, aliphatic oxycarbonylamino group, aryloxycarbonylamino group, carbamoyl group, sulfamoyl group, acyl group, sulfonyl group, fat Group oxycarbonyl group, aryloxycarbonyl group, azo group, acyloxy group, carbamoyloxy group,
Sulfamoyloxy group, silyloxy group, imide group,
Examples thereof include a sulfinyl group, a phosphoryl group and a phosphonyl group. The substitutable group among the substituents listed here may be further substituted with the substituents listed herein.

More specifically, R ₃ is a halogen atom (eg, fluorine atom, chlorine atom, bromine atom), cyano group, hydroxyl group, nitro group, carboxyl group, sulfo group,
Formyl group, aliphatic group (preferably aliphatic group having 1 to 36 carbon atoms, for example, methyl, ethyl, propyl, isopropyl, t-butyl, t-amyl, t-octyl, tridecyl, cyclopentyl, cyclohexyl), aryl A group (preferably an aryl group having 6 to 36 carbon atoms, for example, phenyl, 1-naphthyl, 2-naphthyl), a heterocyclic group (preferably a heterocyclic group having 5 to 8 membered ring having 1 to 36 carbon atoms) , For example, 2-thienyl, 4-pyridyl, 2-furyl, 2
-Pyrimidinyl, 1-pyridyl, 2-benzothiazolyl, 1-
Imidazolyl, 1-pyrazolyl, benzotriazole-2
-Yl), an aliphatic oxy group (preferably having a carbon number of 1 to 36)
An aliphatic oxy group of, for example, methoxy, ethoxy, 1-
Butoxy, 2-butoxy, isopropoxy, t-butoxy, cyclopropyloxy, cyclopentyloxy, cyclohexyloxy), an aryloxy group (preferably an aryloxy group having 6 to 36 carbon atoms, for example, phenoxy, 2-naphthoxy), A heterocyclic oxy group (preferably a heterocyclic oxy group having 1 to 36 carbon atoms, for example, 1-phenyltetrazole-5-oxy, 2-tetrahydropyranyloxy, 2-furyloxy),

Acylamino group (preferably having 1 to 3 carbon atoms)
An acylamino group of 6, for example, acetamide, benzamide), a sulfonylamino group (preferably having a carbon number of 1 to 1).
36 sulfonylamino group, for example, methanesulfonylamino, benzenesulfonylamino), amino group (preferably an amino group having 1 to 36 carbon atoms, for example, amino, N-methylamino, N, N-diethylamino, N,
N-dioctadecylamino), anilino group (preferably an anilino group having 6 to 36 carbon atoms, for example, anilino, N
-Methylanilino), a heterocyclic amino group (preferably a heterocyclic amino group having 1 to 36 carbon atoms, for example, 4-pyridylamino group), a ureido group (preferably an ureido group having 1 to 36 carbon atoms, for example, N, N dimethylureido, N-phenylureido), sulfamoylamino group (preferably sulfamoylamino group having 1 to 36 carbon atoms, for example, N, N-dipropylsulfamoylamino, N-ethylsulfamoylamino) ), An aliphatic thio group (preferably an aliphatic thio group having 1 to 36 carbon atoms, for example, methylthio, ethylthio), an arylthio group (preferably an arylthio group having 1 to 36 carbon atoms, for example, phenylthio), a heterocycle Thio group (preferably a heterocyclic thio group having 1 to 36 carbon atoms, for example, 2-benzothiazolylthio, 2-pyridylthio, 1-phenylteto Zoriruchio), an aliphatic oxy carbonylamino group (preferably an aliphatic oxy carbonylamino group having 1 to 36 carbon atoms, e.g., methoxycarbonylamino, ethoxycarbonylamino, t-butoxycarbonylamino)

An aryloxycarbonylamino group (preferably an aryloxycarbonylamino group having 6 to 36 carbon atoms, for example, a phenoxycarbonylamino group), a carbamoyl group (a carbamoyl group having 1 to 36 carbon atoms, for example, carbamoyl, N, N-dimethylcarbamoyl, N
-Propylcarbamoyl), a sulfamoyl group (preferably a sulfamoyl group having 1 to 36 carbon atoms, for example, sulfamoyl, N, N-dimethylsulfamoyl, N-
Ethylsulfamoyl, N-phenylsulfamoyl), an acyl group (preferably an acyl group having 1 to 36 carbon atoms, for example, acetyl, pivaloyl, benzoyl), a sulfonyl group (preferably alkyl having 1 to 36 carbon atoms or An arylsulfonyl group such as methanesulfonyl,
Benzenesulfonyl), an aliphatic oxycarbonyl group (preferably an aliphatic oxycarbonyl group having 1 to 36 carbon atoms, for example, ethoxycarbonyl, t-butoxycarbonyl, cyclohexyloxycarbonyl), an aryloxycarbonyl group (preferably 6 carbon atoms). To 36 aryloxycarbonyl groups, for example, phenoxycarbonyl), azo groups (preferably C1 to C36 azo groups,
For example, phenylazo),

Acyloxy group (preferably having 1 to 3 carbon atoms)
6 acyloxy groups such as acetoxy, pivaloyloxy, benzoyloxy), carbamoyloxy groups (preferably C1-C36 carbamoyloxy groups such as N, N-dimethylcarbamoyloxy, N
-Butylcarbamoyloxy), a sulfamoyloxy group (preferably a sulfamoyloxy group having 1 to 36 carbon atoms, for example, N, N-diethylsulfamoyloxy, N-propylsulfamoyloxy), a silyloxy group (Preferably a silyloxy group having 1 to 36 carbon atoms,
For example, trimethylsilyloxy, t-butyldimethylsilyloxy, triphenylsilyloxy), an imide group (preferably an imide group having 4 to 36 carbon atoms, for example, N
-Succinimide group, N-phthalimide), sulfinyl group (preferably alkylsulfinyl group or arylsulfinyl group having 1 to 36 carbon atoms, for example, butanesulfinyl, benzenesulfinyl), phosphoryl group (preferably phosphoryl having 1 to 36 carbon atoms) The group represents, for example, diphenoxyphosphoryl, dioctyloxyphosphoryl, diphenylphosphoryl), a phosphonyl group (preferably a phosphonyl group having 1 to 36 carbon atoms, for example, phenylphosphonyl) and the like.

The substituent represented by R ₃ is preferably a halogen atom, hydroxyl group, carboxyl group, aliphatic group, aryl group, heterocyclic group, aliphatic oxy group, aryloxy group, heterocyclic oxy group, acylamino. Group, sulfonylamino group, amino group, anilino group, heterocyclic amino group, ureido group, sulfamoylamino group, aliphatic thio group, arylthio group, heterocyclic thio group, aliphatic oxycarbonylamino group, aryloxycarbonylamino Base,
Carbamoyl group, sulfamoyl group, acyl group, sulfonyl group, aliphatic oxycarbonyl group, aryloxycarbonyl group, acyloxy group, carbamoyloxy group,
Sulfamoyloxy group, sulfinyl group and the like, more preferably a halogen atom, an aliphatic group, an aryl group,
Heterocyclic group, aliphatic oxy group, aryloxy group, heterocyclic oxy group, acylamino group, sulfonylamino group, ureido group, sulfamoylamino group, aliphatic thio group, arylthio group, heterocyclic thio group, aliphatic oxy group Carbonylamino group, aryloxycarbonylamino group, carbamoyl group, sulfamoyl group, acyl group, acyloxy group, carbamoyloxy group, sulfamoyloxy group, particularly preferably halogen atom, aliphatic group, aryl group, heterocyclic group , An aliphatic oxy group, an aryloxy group,
It is a heterocyclic oxy group. Of the above-mentioned substituents, the substitutable group may be further substituted with the substituents described above for R ₃ .

When n is 2 or more, each R ₃ may be the same or different and may form a ring with each other. R ₃ may form a ring together with Q and R ₄ . n is preferably 0 or 1, and n is 1
In the case of, R ₃ is preferably substituted at the ortho position or para position of the pyrrolotriazole substituent, or at the ortho position or para position of the substitution position of Q. When n is 2 or more, R ₃ is preferably the same type of halogen atom.

Q is --NHCO--, --NHSO _2- , --C
ONH- or an -SO ₂ NH-. Q is preferably substituted at the meta or para position of the pyrrolotriazole substituent, and particularly preferably at the meta position. Q is -NHCO -, - NHSO ₂ - and more preferably, -NHSO ₂ - and more preferably a. R ₄ represents a substituent substituted with an acidic dissociative group.

R_FourExamples of the substituent represented by
Aliphatic group, aryl group, heterocyclic group, aliphatic oxy group, ant
Group, heterocyclic oxy group, amino group, anilino
Group, heterocyclic amino group, sulfamoylamino group, aliphatic
Thio group, arylthio group, heterocyclic thio group, acyl group,
Rufonyl group, aliphatic oxycarbonyl group, aryloxy
Cycarbonyl group, azo group, acyloxy group, carbamoy
Luoxy group, sulfamoyloxy group, silyloxy group
Group, imido group, sulfinyl group, phosphoryl group, phospho
Examples thereof include a nyl group. Among the substituents listed here,
The group substitutable in is R ₃Further substitution with substituents such as
It may be replaced. In addition, each unit listed here
For a detailed description of the substituents, see R₃These placements in
The same applies to the explanation of the substituent. Also, R_FourThe acid that we will explain later
It may be the sex-dissociating group itself.

When R ₄ is not the acidic dissociative group itself described below, examples of the substituent represented by R ₄ are preferably an aliphatic group, an aryl group, a heterocyclic group, an aliphatic oxy group, an aryloxy group, Heterocyclic oxy group, amino group, anilino group, heterocyclic amino group, sulfamoylamino group,
Aliphatic thio group, arylthio group, heterocyclic thio group, acyl group, sulfonyl group, aliphatic oxycarbonyl group, aryloxycarbonyl group, acyloxy group, carbamoyloxy group, sulfamoyloxy group, phosphoryl group, phosphonyl group. , And more preferably, aliphatic group, aryl group, heterocyclic group, aliphatic oxy group, aryloxy group, heterocyclic oxy group, sulfamoylamino group, aliphatic thio group, arylthio group, heterocyclic thio group, acyl A group, a sulfonyl group, an aliphatic oxycarbonyl group, an aryloxycarbonyl group, an acyloxy group, a carbamoyloxy group, a sulfamoyloxy group, and particularly preferably,
Aliphatic oxy group, aryloxy group, heterocyclic oxy group,
An acyloxy group, a carbamoyloxy group, and a sulfamoyloxy group.

The acidic dissociative group is a substituent capable of efficiently releasing hydrogen ions in the developing solution. That is, in an alkaline solution or in a base (eg ammonia, amines,
Among the substituents capable of releasing hydrogen ions in the presence of anilines, pyridine), those having a pka value of 10 or less are meant. The pka value is measured by "The Determination of Ioni
zation Constants "(Albart, A. and Serjeant, EP2nd E
dn, Chapman and Hall, London) It can be carried out according to the method described in Chapter 2 (pages 14 to 38) (however, using tetrahydrofuran-water 1: 1 solution as a solvent and 0.2N aqueous sodium hydroxide solution as a titrant). . Specific examples are -CO ₂ H, phenolic -OH, SOkH (k = 0-3), -SO ₂ N.
_{H 2, -SO 2 NHR ',} - SO 2 NHCOR', - SO 2 NHCO 2 R ', -SO 2 NHCON
R'R ", -CONHCOR ', -CONHCO ₂ R', -CONHSO ₂ R ', -CONHSO
₂ NR'R ", -SO ₂ NHOR", -SO ₂ N (R ') OH, -CON (R ") OH, -CON
HOR ', -CONH (OH) COR', -CON (NHCOR ') COR', -CON (NHSO ₂
R ') COR', -SO ₂ NHSO ₂ R ', -SO ₂ NHSO ₂ NR'R ", -SO ₂ NR" NHS
O ₂ R ', -SO ₂ NHNR "SO ₂ R'-SO ₂ N (OH) SO ₂ R'and the like, wherein R'represents an aliphatic group, an aryl group or a heterocyclic group, and R" Represents a hydrogen atom, an aliphatic group, an aryl group, or a heterocyclic group. The aliphatic group, aryl group and heterocyclic group represented by R ′ and R ″ have the same meanings as the aliphatic group, aryl group and heterocyclic group represented by R ₃ , respectively.

The acidic dissociative group substituted for R ₄ is preferably an acidic dissociative group having a pka of 8 or less, and more preferably
pka is an acidic dissociative group having a number of 3 or more and 8 or less, particularly preferably -CO ₂ H, phenolic -OH, -SO ₂ NHCOR ', -CONHCOR'.
, -CONHSO ₂ R '.

[0038] The substituting position of the on R ₄ of the acid dissociable group to be substituted with R ₄ is counted from atoms substituted phenyl group 1
It is preferably on the 6th atom. The substituting atom is not particularly limited, but a carbon atom is more preferable. When the acidic dissociative group substitutes on a carbon atom, that carbon atom is preferably a tertiary or quaternary carbon. Further, when the acidic dissociative group is a divalent or higher valent group, it does not matter at which position the R ₃ is substituted.

R ₅ represents a substituent, and m represents an integer of 0 to 4. R ₅ has the same meaning as R ₃ . When m is 2 or more, each R ₅ may be the same or different and may form a ring with each other. R ₅ may form a ring together with Q and R ₄ . m is preferably 0 or 1, and when m is 1, R ₅ is preferably substituted at the ortho or para position of R _{4 and} the ortho or para position of Q. When m is 2 or more, R ₃ is preferably the same type of halogen atom.

The most preferable combination of R ₄ , R ₅ and m is R ₄ is an aliphatic oxy group, m is 1, R ₅ is a quaternary alkyl group, and R ₄ is substituted at the para position. That is the case.

X represents a hydrogen atom or a group capable of splitting off upon coupling with an oxidized product of a color developing agent (hereinafter, simply referred to as splitting group). When X represents a leaving group, the leaving group may be a halogen atom (eg, fluorine atom, chlorine atom, bromine atom), an alkoxy group (eg, methoxy, ethoxy, methoxyethoxy), aryloxy (eg, phenoxy, 4-chloro). Phenoxy, 4-carboxyphenoxy, naphthyloxy), heterocyclic oxy group (for example, 5-
Phenyltetrazolyloxy, 2-benzothiazolyloxy), acyloxy group (eg, acetoxy, tetradecanoyloxy, benzoyloxy), alkyl, aryl, or heterocyclic sulfonyloxy group (eg,
Methanesulfonyloxy, benzenesulfonyloxy), a dialkyl or diarylphosphosphonooxy group (for example, dimethylphosphonooxy, diphenylphosphonooxy), a dialkyl or diarylphosphinooxy group (for example, dimethylphosphinooxy),

Alkyl, aryl, or heterocyclic sulfonyl groups (eg, methanesulfonyl, toluenesulfonyl, tetrazolylsulfonyl), alkyl, aryl, or heterocyclic sulfinyl groups (eg, phenyl, phenyl, ethylsulfinyl, tetrazolylsulfinyl). ), An acylamino group (for example, dichloroacetylamino, heptafluorobutylamino), an alkyl,
Aryl or heterocyclic sulfonamide (eg, methanesulfonamide, trifluoromethanesulfonamide, benzenesulfonamide), alkoxycarbonyloxy group (eg, methoxycarbonyloxy, ethoxycarbonyloxy), aryloxycarbonyloxy group (eg, phenoxycarbonyl) Oxy), carbamoyloxy group (diethylcarbamoyoxy, morpholinocarbonyloxy), alkyl, aryl, or heterocyclic thio group (eg, ethylthio, phenylthio, tetrazolylthio), carbamoylamino group (eg, N
-Methylcarbamoylamino, N-phenylcarbamoylamino), a 5- or 6-membered nitrogen-containing heterocyclic group (for example, imidazolyl, pyrazolyl, triazolyl, tetrazolyl) bonded to the coupling position at a nitrogen atom, an imide group (for example, succinimide) , Phthalimide), arylazo groups (eg, phenylazo), and the like.

[0043]

X is preferably a hydrogen atom, a chlorine atom, an alkoxy group, an aryloxy group, a heterocyclic oxy group, an acyloxy group, an alkoxycarbonyloxy group, an aryloxycarbonyloxy group or a carbamoyloxy group, more preferably a hydrogen atom. , An acyloxy group, an alkoxycarbonyloxy group or a carbamoyloxy group.

The coupler represented by the general formula (1) has R ₁
~ R ₅ or X group contains a residue of the coupler represented by the general formula (1) to form a dimer or higher multimer, or the group of R _{1 to} R ₅ or X is high. It may contain a molecular chain to form a homopolymer or a copolymer. The homopolymer or copolymer containing a polymer chain is a typical example is an addition polymer having a residue of a coupler represented by the general formula (1), a homopolymer or copolymer of an ethylenically unsaturated compound. is there. In this case, one or more kinds of cyan color-forming repeating units having a residue of the coupler represented by the general formula (1) may be contained in the polymer, and acrylic acid ester, methacrylic acid ester, maleic acid may be used as a copolymerization component. It may be a copolymer containing one or more non-color-forming, ethylene-type monomers that do not couple with the oxidation product of an aromatic primary amine developer such as acid ester. Specific examples of the coupler of the present invention are shown below, but the present invention is not limited thereto.

[0046]

[Chemical 6]

[0047]

[Chemical 7]

[0048]

[Chemical 8]

[0049]

[Chemical 9]

[0050]

[Chemical 10]

[0051]

[Chemical 11]

[0052]

[Chemical 12]

[0053]

[Chemical 13]

[0054]

[Chemical 14]

[0055]

[Chemical 15]

Next, a method for synthesizing the compound of the present invention will be described. The compound of the present invention is disclosed in, for example, JP-A-6-347960.
Nos. 7-48336 and 7-330771. Synthesis of Exemplified Compound 41 Compound Exemplified Compound 41 was synthesized according to the following scheme.

[0057]

[Chemical 16]

42.0 g of aniline (1) and 40.0 g of sulfonyl chloride (2) in 300 ml of acetonitrile at 50 ° C.
The mixture was stirred with and pyridine was added dropwise. After 6 hours, the reaction solution was poured into a dilute aqueous hydrochloric acid solution and extracted with ethyl acetate. The organic layer was washed with water and saturated aqueous sodium chloride solution, dried over anhydrous magnesium sulfate and concentrated to give a brown oil (101.6 g). This was purified by column chromatography and then recrystallized from acetonitrile to obtain 53.5 g of ethyl ester (3). 40.6 g of ethyl ester compound (3) was added to 400 ml of THF-MeOH.
It was dissolved in (5: 1) and stirred at room temperature. 40 ml here
What dissolved 8.2g of sodium hydroxide in the water of was slowly dripped. The reaction solution was poured into a dilute aqueous hydrochloric acid solution and extracted with ethyl acetate. The organic layer was washed with water and saturated aqueous sodium chloride solution, dried over anhydrous magnesium sulfate, and concentrated to give 43.4 g of an amorphous substance. This was recrystallized from acetonitrile to obtain 35.1 g of Compound Example 41. Other compounds can be synthesized by the same method.

The light-sensitive material of the present invention comprises the coupler of the present invention.
It is sufficient that at least one layer is contained on the support,
The layer containing the coupler of the present invention includes a parent on the support.
Any aqueous colloid layer may be used. Common photosensitive materials are
Blue-sensitive silver halide emulsion layer, green-sensitive halogenated on support
At least the silver emulsion layer and the red-sensitive silver halide emulsion layer
It can also be constructed by coating one by one in this order,
The order may be different from this. Also, red-sensitive halogen
The silver halide emulsion layer to at least one of the above-mentioned photosensitive emulsion layers.
It can be used instead. In these photosensitive emulsion layers
Is a silver halide emulsion having sensitivity in each wavelength range
And a color that forms a pigment that is complementary to the light that it sensitizes.
-By including a coupler, the color reproduction of the subtractive color method can be performed.
You can However, the photosensitive emulsion layer and the color coupler
Colored hue is a structure that does not have the above correspondence.
Good. Especially in the present invention, a red-sensitive silver halide emulsion is used.
It is preferably used as a cyan coupler in the layer. Book
The amount of the inventive coupler in the light-sensitive material is 1 m.²Around 0.
01g-10g, preferably 1m²0.1g to 2g per
And 1 × 10 per mol of silver halide in the same layer
^-3A proper amount is 1 to 1 mol, preferably 2 × 10.^-3Mo
Le ~ 3 x 10 ^-1It is a mole.

The coupler of the present invention can be introduced into a light-sensitive material by various known dispersion methods, is dissolved in an organic solvent having a high boiling point (a low boiling point solvent is optionally used in combination), and is emulsified and dispersed in an aqueous gelatin solution to form a silver halide. The oil-in-water dispersion method of adding to the emulsion is preferred. Examples of the high boiling point solvent used in the oil-in-water dispersion method are described in US Pat. No. 2,322,027. In addition, the steps of latex dispersion method as one of the polymer dispersion methods, effects, and specific examples of latex for impregnation are as follows.
US Patent No. 4,199,363, West German Patent Application No. (O
LS) No. 2,541,274, No. 2,541,230
No. 3, Japanese Patent Publication No. 53-41091 and European Patent Publication No. 02.
9104 and the like, and regarding the dispersion by an organic solvent-soluble polymer, PCT International Publication No. WO8
8/00723.

As the high boiling point solvent which can be used in the above oil-in-water dispersion method, phthalic acid esters (eg, dibutyl phthalate, dioctyl phthalate, dicyclohexyl phthalate, di-2-ethylhexyl phthalate, decyl phthalate, bis (2 , 4-di-tert-
Amylphenyl) isophthalate, bis (1,1-diethylpropyl) phthalate), esters of phosphoric acid or phosphonic acid (eg diphenylphosphate, triphenylphosphate, tricresylphosphate, 2
-Ethylhexyl diphenyl phosphate, dioctyl butyl phosphate, tricyclohexyl phosphate, tri-2-ethylhexyl phosphate, tridodecyl phosphate, di-2-ethylhexyl phenyl phosphate), benzoic acid esters (for example, 2-ethylhexyl benzoate, 2,4-dichloro) Benzoate, dodecylbenzoate, 2-ethylhexyl-p-
Hydroxybenzoate), amides (eg, N, N
-Diethyldodecane amide, N, N-diethyllaurylamide), alcohols or phenols (eg,
Isostearyl alcohol, 2,4-di-tert-amylphenol, aliphatic esters (for example, dibutoxyethyl succinate, di-2-ethylhexyl succinate, 2-hexyldecyl tetradecanoate, tributyl citrate, diethyl azetate) Rate, isostearyl lactate, trioctyl silate), aniline derivative (for example, N, N-dibutyl-2-butoxy-5-tert-octylaniline), chlorinated paraffins (chlorine content 10)
% To 80% paraffins), trimesic acid esters (eg tributyl trimesate), dodecylbenzene, diisopropylnaphthalene, phenols (eg 2,4-di-tert-amylphenol, 4-dodecyloxyphenol, 4 -Dodecyloxycarbonylphenol, 4- (4-dodecyloxyphenylsulfonyl) phenol, carboxylic acids (for example, 2- (2,2
4-di-tert-amylphenoxybutyric acid, 2-ethoxyoctanedecanoic acid), alkylphosphoric acids (for example, di-
(2-ethylhexyl) phosphoric acid, diphenylphosphoric acid) and the like. In addition to the above high boiling point solvents, it is also preferable to use, for example, the compounds described in JP-A-6-258803 as high boiling point solvents. As the auxiliary solvent, an organic solvent having a boiling point of 30 ° C. or higher and about 160 ° C. or lower (eg, ethyl acetate, butyl acetate, ethyl propionate, methyl ethyl ketone, cyclohexanone, 2-ethoxyethyl acetate, dimethylformamide) may be used in combination.

Each color-sensitive emulsion layer of the light-sensitive material of the present invention is composed of at least one light-sensitive emulsion layer, and each color-sensitive layer is composed of two or more light-sensitive emulsion layers having different sensitivities. Is also preferable, and each unit preferably has three photosensitive emulsion layers having different sensitivities. When the photosensitive layer has a unit structure composed of a plurality of photosensitive emulsion layers having different sensitivities, it is preferable that the low-sensitivity emulsion layer and the high-sensitivity emulsion layer are coated in this order from the side closer to the support.

The content of the coupler of the present invention in the light-sensitive material is 0.01 to 10.0 g, and preferably 0.1 to 3.0 g per m ² of the light-sensitive material. When it is contained in the light-sensitive emulsion layer, 1 × is used for 1 mol of silver halide in the same layer.
10 ⁻³ mol to 1 mol is suitable, and preferably 2 × 10 3.
^{-3 to} 5 x 10 ^-1 mol. In the light-sensitive material of the present invention, it is also preferable to use a competitive compound (a compound that competes with an image-forming coupler and reacts with an oxidized product of a color developing agent and does not form a dye image), if necessary. Competitive compounds include hydroquinones, catechols, hydrazines,
Reducing compounds such as sulfonamide phenols, or compounds that couple with oxidized color developing agent but do not substantially form a color image (eg German Patent 1,1
55,675, British Patent 861,138, U.S. Pat. Nos. 3,876,428 and 3,912,513, or a non-color coupler, or JP-A-6-83.
Outflow couplers such as those disclosed in No. 002).

The competing compound is preferably added to a light-sensitive emulsion layer containing the cyan coupler of the present invention or a layer immediately adjacent thereto, particularly preferably to the same light-sensitive emulsion layer as the cyan coupler of the present invention. The amount of the competing compound added is 0.01 g to 10 g, preferably 0.10 g to 1.0 g, per 1 m ² of the light-sensitive material, and 1 to 500 mol%, preferably 50 mol% based on the cyan coupler of the present invention.
Used at ~ 300 mol%. When the competing compound is added to the same light-sensitive emulsion layer as the cyan coupler, the competing compound is preferably a compound which couples with an oxidized product of a color developing agent but does not substantially form a color image,
Outflow couplers are particularly preferred.

Further, in the light-sensitive material of the present invention, it is also preferable to coat a non-color-forming intermediate layer in a photosensitive unit having the same color-sensing property, and a compound which can be selected as the above-mentioned competing compound is further added to the intermediate layer. It is also preferable to contain it.

Research Disclosure No. 308119 (19) generally describes various techniques and inorganic / organic materials which can be used for the silver halide photographic emulsion of the present invention and the silver halide photographic light-sensitive material using the same.
1989) and those described in the same 37038 (1995) can be used. In addition to this, more specifically, for example, as to the technique and inorganic / organic material which can be used for a color photographic light-sensitive material to which the silver halide photographic emulsion of the present invention can be applied, see EP 436,938A2. It is described below and in the patents cited below.

[0067]       Item This location 1) Layer structure, page 146, line 34 to page 147, line 25 2) Can be used together Page 147, line 26 to Page 148, line 12     Silver halide emulsion 3) Combined use, page 137, line 35 to page 146, line 33, line 14     Yellow Coupler Page 9, lines 21-23 4) Concomitant use, page 149, lines 24 to 28; European Patent No. 42     Magenta Coupler No. 1,453A1, page 3, line 5 to page 25, line 55                           Eye 5) Combined use, page 149, lines 29-33; European Patent 432     Cyan coupler 804A2, page 3, line 28 to page 40, line 2 6) Polymer coupler, page 149, lines 34-38; European Patent 435                           , 334A2, page 113, line 39 to page 123                           37th line 7) Colored coupler, page 53, line 42 to page 137, line 34, line 149                           Page 39th line to 45th line 8) Page 7, line 1 to page 53, line 41, page 149, 46, which can be used in combination     Functional Coupler Line-Page 150 Line 3; EP 435,33                           4A2, page 3, line 1 to page 29, line 50 9) Antiseptic and antifungal agents, page 150, lines 25-28 10) Formalin Page 149, lines 15-17     Scavenger 11) Combined use, page 153, lines 38-47; EP 421     Other additives, 453A1, page 75, line 21 to page 84, 56                           Line, page 27, line 40 to page 37, line 40 12) Dispersion method Page 150, lines 4-24 13) Support, page 150, lines 32 to 34 14) Film thickness and film properties Page 150, lines 35-49 15) Color development step, page 150, line 50 to page 151, line 47 16) Desilvering process, page 151, line 48 to page 152, line 53 17) Automatic processor, page 152, line 54 to page 153, line 2 18) Washing / stabilization process Page 153, lines 3 to 37

[0068]

【Example】

(Example-1) The present invention will be specifically described below with reference to examples, but the invention is not limited thereto. Preparation of Sample 101 A multilayer color light-sensitive material composed of each layer having the following composition was prepared on an undercoated cellulose triacetate film support having a thickness of 127 μm to prepare Sample 101. The numbers represent the amount added per m ² . The effect of the added compound is not limited to the described use.

First layer: antihalation layer Black colloidal silver 0.10 g Gelatin 2.00g UV absorber U-1 0.10g UV absorber U-3 0.040g UV absorber U-4 0.10g High boiling organic solvent Oil-1 0.10 g 0.10 g of microcrystalline solid dispersion of Dye E-1

Second layer: intermediate layer Gelatin 0.40g Compound Cpd-A 5.0 mg High boiling organic solvent Oil-3 0.05g Dye D-4 0.80 mg

Third layer: Fine grained silver iodobromide emulsion with the surface and inside of the intermediate layer fogged (average grain size 0.06 μm, coefficient of variation 18%, AgI content 1 mol%) silver amount 0.050 g yellow colloidal silver silver amount 0.030g Gelatin 0.40g High boiling organic solvent 0il-3 0.05g

Fourth layer: low-sensitivity red-sensitive emulsion layer Emulsion A Silver amount 0.35g Emulsion B Silver amount 0.40g Gelatin 0.80g Coupler C-1 0.13g Coupler C-7 0.02g Compound Cpd-C 5.0 mg High boiling organic solvent Oil-2 0.08g Additive P-1 0.10g

Fifth layer: Medium sensitivity red-sensitive emulsion layer Emulsion B Silver amount 0.30g Emulsion C Silver amount 0.25g Gelatin 0.80g Coupler C-1 0.20g High boiling organic solvent Oil-2 0.10 g Additive P-1 0.10g

Sixth layer: High-sensitivity red-sensitive emulsion layer Emulsion D Silver amount 0.40g 1.50 g gelatin Coupler C-1 0.90g High boiling organic solvent Oil-2 0.45g Additive P-1 0.10g

Seventh layer: intermediate layer Gelatin 0.70 g Additive M-1 0.30g Compound Cpd-I 2.6 mg Dye D-5 0.020 g Dye D-6 0.010g High boiling organic solvent Oil-3 0.10 g

Eighth layer: Fine grained silver iodobromide emulsion with fogged surface and inner surface (average grain size 0.06 μm, coefficient of variation 18%, AgI content 1 mol%) silver amount 0.010 g yellow colloidal silver silver amount 0.020g Gelatin 1.00g Additive P-1 0.05g Cpd-J 0.10g Color mixing inhibitor Cpd-C 0.15g High boiling organic solvent Oil-3 0.20g

Ninth layer: low-sensitivity green-sensitive emulsion layer Emulsion E Silver amount 0.30g Emulsion F Silver amount 0.20g Emulsion G Silver amount 0.25g Gelatin 0.65g Coupler C-2 0.10g Coupler C-5 0.10g Coupler C-6 0.05g Compound Cpd-B 0.030 g Compound Cpd-D 0.020 g Compound Cpd-E 0.020 g Compound Cpd-F 0.040 g Compound Cpd-K 0.02 g High boiling organic solvent Oil-1 0.02g High boiling organic solvent Oil-2 0.20g

Tenth layer: Medium sensitivity green-sensitive emulsion layer Emulsion G Silver amount 0.20g Emulsion H Silver amount 0.18g Gelatin 0.60 g Coupler C-2 0.05g Coupler C-5 0.10g Coupler C-6 0.05g Compound Cpd-B 0.030 g Compound Cpd-D 0.020 g Compound Cpd-E 0.020 g Compound Cpd-F 0.050 g High boiling organic solvent Oil-2 0.010 g

Eleventh layer: High-sensitivity green-sensitive emulsion layer Emulsion I Silver amount 0.35g Gelatin 1.00g Coupler C-2 0.35g Coupler C-5 0.05g Coupler C-6 0.050g Compound Cpd-B 0.080 g Compound Cpd-E 0.020 g Compound Cpd-F 0.040 g High boiling organic solvent Oil-1 0.020 g High boiling organic solvent Oil-2 0.020g

Twelfth layer: intermediate layer Gelatin 0.60 g Compound Cpd-K 0.05 g High boiling point organic solvent Oil-1 0.05 g

Thirteenth layer: Yellow filter layer Yellow colloidal silver Silver amount 0.010g Gelatin 1.10g Color mixing inhibitor Cpd-A 0.10g High boiling organic solvent Oil-3 0.05g Microcrystalline solid dispersion of Dye E-2 0.030 g Microcrystalline solid dispersion of Dye E-3 0.020 g

14th layer: intermediate layer Gelatin 0.60 g Fifteenth layer: low-sensitivity blue-sensitive emulsion layer Emulsion J Silver amount 0.30g Emulsion K Silver amount 0.20g Gelatin 0.80g Coupler C-3 0.20g Coupler C-4 0.05g Coupler C-8 0.40g Compound Cpd-I 0.02 g

Sixteenth layer: Medium sensitivity blue-sensitive emulsion layer Emulsion L Silver amount 0.25g Emulsion M Silver amount 0.25g Gelatin 0.90g Coupler C-3 0.15g Coupler C-4 0.05g Coupler C-8 0.50g

Seventeenth layer: High-sensitivity blue-sensitive emulsion layer Emulsion N Silver amount 0.20g Emulsion O Silver amount 0.20g 1.20 g of gelatin Coupler C-3 0.10g Coupler C-4 0.15g Coupler C-8 0.60g High boiling organic solvent Oil-2 0.10 g

Eighteenth layer: First protective layer Gelatin 0.70 g UV absorber U-1 0.20g UV absorber U-2 0.050g UV absorber U-5 0.30g Color mixing inhibitor Cpd-A 0.10g Formalin scavenger Cpd-H 0.40g Dye D-1 0.15g Dye D-2 0.050g Dye D-3 0.10g High boiling organic solvent Oil-3 0.10 g

Layer 19: Second protective layer Yellow colloidal silver Silver amount 0.12 mg Fine grain silver iodobromide emulsion (average grain size 0.06 μm, AgI content 1
Mol%) Silver amount 0.10 g Gelatin 0.35 g

20th layer: Third protective layer Gelatin 0.45 g Polymethylmethacrylate (average particle size 1.5 μ) 0.10 g Copolymer of methylmethacrylate and methacrylic acid 6: 4 (average particle size 1.5 μ) 0.10 g Silicone oil SO-1 0.030g Surfactant W-1 3.0mg Surfactant W-2 0.030g

In addition to the above composition, additives F-1 to F-6 were added to all emulsion layers. In addition to the above composition, gelatin hardener H-1 and coating and emulsifying surfactants W-3, W-4, W-5 and W-6 were added to each layer. Further, phenol, 1,2-benzisothiazolin-3-one, 2-phenoxyethanol, phenethyl alcohol and butyl benzoate were added as antiseptic and antifungal agents.

[0089]

[Table 1]

[0090]

[Table 2]

[0091]

[Table 3]

[0092]

[Chemical 17]

[0093]

[Chemical 18]

[0094]

[Chemical 19]

[0095]

[Chemical 20]

[0096]

[Chemical 21]

[0097]

[Chemical formula 22]

[0098]

[Chemical formula 23]

[0099]

[Chemical formula 24]

[0100]

[Chemical 25]

[0101]

[Chemical formula 26]

[0102]

[Chemical 27]

[0103]

[Chemical 28]

[0104]

[Chemical 29]

[0105]

[Chemical 30]

Preparation of Dispersion of Organic Solid Disperse Dye Dye E-1 was dispersed by the following method. That is, 200 g of Pluronic F88 (ethylene oxide-propylene oxide block copolymer) manufactured by BASF was added to 1430 g of a wet cake of a dye containing 30% of methanol and stirred to obtain a slurry having a dye concentration of 6%. Next, 1700 ml of zirconia beads having an average particle diameter of 0.5 mm was filled in Ultra Visco Mill (UVM-2) manufactured by IMEX Co., Ltd.,
Peripheral speed of about 10 m / sec through the slurry, discharge rate 0.51
The powder was crushed for 8 hours at a speed of min / min. The beads are filtered off, water is added to dilute to a dye concentration of 3%, and then 90% for stabilization.
Heated at ° C for 10 hours. The dye particles thus obtained had an average particle size of 0.60 μm and a broad particle size distribution (particle size standard deviation × 100 / average particle size) of 18%.

Similarly, solid dispersions of Dyes E-2 and E-3 were obtained. Average particle size is 0.54μm and 0.56μ
It was m.

The evaluation was carried out by five people who are involved in image evaluation at Fuji Photo Film Co., Ltd. Ashigara Research Laboratories, and "no discomfort at all compared to the print from Gray Patch A" was given.
A total score of 5 people was evaluated with a score of 5 points, “Gray is acceptable but gray is acceptable if alone” and “Gray is not acceptable” as 0 points. The treatment of "Fujichrome paper type 35" was performed by the standard treatment of RP-303 recommended by Fuji Photo Film Co., Ltd. The above results are also shown in Table 4.

[0109]

[Table 4]

[0110]

[Chemical 31]

As shown in Table 4, first, samples 102 to
Comparison couplers A, B, C, D as shown in 113
Compared to, the coupler of the present invention has improved color developability,
In particular, the difference in color development due to the amount of the high boiling point organic solvent is small, which is preferable. Further, Samples 102 to 109 or 114 and 115 using the conventional pyrroloazole coupler have a problem that the cyan concentration is largely decreased due to the compositional change of the bleaching solution (addition of ferrous ion). This problem is ameliorated in couplers 110 to 116 and 119. This indicates that the dye produced from the coupler of the present invention is stable to ferrous ion reduction.
Although the comparative couplers C and D have improved color forming properties as compared with the comparative couplers A and B, the stability of the comparative couplers C and D against reduction of ferrous ion is deteriorated. It is surprising that the stability against iron ion reduction could be improved at the same time. In addition, in samples 102 to 109, 117 and 118 using conventional couplers,
In particular, in the case of a sample with a small amount of high-boiling organic solvent, there was a concentration dependency of gray reproduction when printed, and there was a problem that gray patches A and B could not be reproduced under the same filter conditions. Samples 110 of the present invention
116 and 119 were improved to the same level as Sample 101. Further, the samples 101 to 119 were cut into 135 sizes,
It was processed into a Patrone form, loaded into a camera, and a Macbeth Color Checker Chart was photographed. When shooting, adjust the filters so that the gray balance is the same in Neutral 6.5 of the color checker chart,
The development processing was the following development processing-A. A sensory evaluation of the respective photographed results revealed that the coupler of the present invention was superior in color reproducibility of cyan, green and yellow green as compared with C-1 and comparative couplers A to D.

(Development Processing-A) Sample 2 was used for the processing.
50% of 01 was completely exposed to white light and passed through until the replenishment amount was 3 times the tank volume before use. Treatment process time Temperature Tank capacity Replenishment amount 6 minutes 38 ° C 12 liters 2200 ml / m ² Second washing 2 minutes 38 ° C 4 liters 7500 ml / m ² Inversion 2 minutes 38 ° C 4 liters 1100 ml / m ² Color development Development 6 minutes 38 ° C 12 liters 2200 ml / m ² pre-bleaching 2 minutes 38 ° C 4 liters 1100 ml / m ² Bleaching 6 minutes 38 ° C 12 liters 220 ml / m ² Settling 4 minutes 38 ° C 8 liters 1100 ml / m ² Second washing 4 minutes 38 ℃ 8 liters 7500ml / m ² Final rinse 1 minute 25 ℃ 2 liters 1100ml / m ²

The composition of each treatment liquid was as follows. [First developer] [Tank liquid] [Replenisher]   Nitrilo-N, N, N-trimethylenephosphonic acid     ・ 5 sodium salt 1.5 g 1.5 g   Diethylenetriamine pentaacetic acid / 5 sodium salt 2.0 g 2.0 g   Sodium sulfite 30 g 30 g   Hydroquinone / potassium monosulfonate 20 g 20 g   Potassium carbonate 15 g 20 g   Potassium bicarbonate 12 g 15 g   1-phenyl-4-methyl-4-hydroxymethyl     -3-Pyrazolidone 1.5 g 2.0 g   Potassium bromide 2.5 g 1.4 g   Potassium thiocyanate 1.2 g 1.2 g   Potassium iodide 2.0 mg −   Diethylene glycol 13 g 15 g   Add water 1000 ml 1000 ml     pH 9.60 9.60 The pH was adjusted with sulfuric acid or potassium hydroxide.

[0114] [Reversal liquid] [Tank liquid] [Replenisher]   Nitrilo-N, N, N-trimethylenephosphonic acid tank liquid     ・ Same as 3.0 g of 5 sodium salt   Stannous chloride / dihydrate 1.0 g   p-aminophenol 0.1 g   Sodium hydroxide 8 g   Glacial acetic acid 15 ml   1000 ml with water     pH 6.00 The pH was adjusted with acetic acid or sodium hydroxide.

[0115] [Color developer] [Tank solution] [Replenisher]   Nitrilo-N, N, N-trimethylenephosphonic acid     ・ 5 sodium salt 2.0 g 2.0 g   Sodium sulfite 7.0 g 7.0 g   Trisodium phosphate dodecahydrate 36 g 36 g   Potassium bromide 1.0 g −   Potassium iodide 90 mg −   Sodium hydroxide 3.0 g 3.0 g   Citrazine acid 1.5 g 1.5 g   N-ethyl-N- (β-methanesulfonamidoethyl)     -3-Methyl-4-aminoaniline ・ 3/2 sulfuric acid ・     1 water salt 11 g 11 g   3,6-dithiaoctane-1,8-diol 1.0 g 1.0 g   Add water 1000 ml 1000 ml     pH 11.80 12.00 The pH was adjusted with sulfuric acid or potassium hydroxide.

[0116] [Pre-bleaching] [Tank solution] [Replenisher]   Ethylenediaminetetraacetic acid ・ disodium salt ・ dihydrate 8.0 g 8.0 g   Sodium sulfite 6.0 g 8.0 g   1-thioglycerol 0.4 g 0.4 g   Formaldehyde sodium bisulfite adduct 30 g 35 g   Add water 1000 ml 1000 ml     pH 6.30 6.10 The pH was adjusted with acetic acid or sodium hydroxide.

[0117] [Bleaching solution] [Tank solution] [Replenisher]   Ethylenediaminetetraacetic acid ・ disodium salt ・ dihydrate 2.0 g 4.0 g   Ethylenediaminetetraacetic acid-Fe (III) -Ammonium     ・ Dihydrate 120 g 240 g   Potassium bromide 100 g 200 g   Ammonium nitrate 10 g 20 g   Add water 1000 ml 1000 ml     pH 5.70 5.50 The pH was adjusted with nitric acid or sodium hydroxide.

[0118] [Fixer] [Tank] [Replenisher]   Ammonium thiosulfate 80 g Same as tank liquid   Sodium sulfite 5.0 g 〃   Sodium bisulfite 5.0 g 〃   Add water to 1000 ml 〃     pH 6.60 The pH was adjusted with acetic acid or aqueous ammonia.

[0119] [Stabilizer] [Tank liquid] [Replenisher]   1,2-benzisothiazolin-3-one 0.02g 0.03g   Polyoxyethylene-p-monononylphenyl ether     (Average degree of polymerization 10) 0.3 g 0.3 g   Polymaleic acid (average molecular weight 2,000) 0.1 g 0.15 g   Add water 1000 ml 1000 ml     pH 7.0 7.0

Example-2 1) Support The support used in this example was prepared by the following method. 100 parts by weight of a commercially available polyethylene-2,6-naphthalate polymer and 2 parts by weight of Tinuvin P.326 (manufactured by Ciba-Geigy Co., Ltd.) as an ultraviolet absorber were dried by a conventional method and then melted at 300 ° C. After that, it is extruded from the T-die and longitudinally stretched 3.0 times at 140 ° C, and then 130 ° C.
Was transversely stretched by 3.0 times and further heat set at 250 ° C. for 6 seconds to obtain a PEN film having a thickness of 90 μm. Further, a part thereof was wound around a stainless steel core having a diameter of 20 cm and subjected to a heat history of 110 ° C. for 48 hours. 2) Application of undercoat layer The above-mentioned support is subjected to corona discharge treatment, UV discharge treatment, glow discharge treatment, and flame treatment on both sides thereof,
An undercoat liquid having the following composition was applied to each surface, and an undercoat layer was provided on the high temperature surface side during stretching. Pillar Pill for corona discharge treatment
A 30 cm wide support is treated at 20 m / min using a ar solid state corona processor 6KVA model. At this time,
From the current and voltage readings, the object to be processed is 0.375 KV
・ A · min / m ² was processed. The discharge frequency during the treatment was 9.6 KHz, and the gap clearance between the electrode and the dielectric roll was 1.6 mm. UV discharge treatment is 75
Discharge treatment was performed while heating at ℃. Further, the glow discharge treatment was performed by irradiating with a cylindrical electrode at 3000 W for 30 seconds. Gelatin 3 g Distilled water 25 ml Sodium α-sulfo-di-2-ethylhexyl succinate 0.05 g Formaldehyde 0.02 g Salicylic acid 0.1 g Diacetyl cellulose 0.5 g p-Chlorophenol 0.5 g Resorcin 0.5 g Cresol 0 0.5 g (CH ₂ = CHSO ₂ CH ₂ CH ₂ NHCO) ₂ CH ₂ 0.2 g Aziridine 3-fold molar adduct of trimethylolpropane 0.2 g Trimethylolpropane-toluene diisocyanate 3-fold molar adduct 0.2 g methanol 15 ml acetone 85 ml formaldehyde 0.01 g acetic acid 0.01 g concentrated hydrochloric acid 0.01 g

3) Coating of Back Layer An antistatic layer, a magnetic recording layer, and a sliding layer having the following compositions were coated as back layers on one surface of the above-mentioned support after undercoating. 3-1) Coating of antistatic layer 3-1-1) Preparation of conductive fine particle dispersion (tin oxide-antimony oxide composite dispersion) 230 parts by weight of stannic chloride hydrate and antimony trichloride 2
3 parts by weight was dissolved in 3000 parts by weight of ethanol to obtain a uniform solution. A 1N aqueous sodium hydroxide solution was added dropwise to this solution until the pH of the solution reached 3, to obtain a coprecipitate of colloidal stannic oxide and antimony oxide. The obtained coprecipitate was left at 50 ° C. for 24 hours to obtain a reddish brown colloidal precipitate.

The reddish brown colloidal precipitate was separated by centrifugation. To remove excess ions, water was added to the precipitate and washed by centrifugation. This operation was repeated 3 times to remove excess ions. 200 parts by weight of the colloidal precipitate from which excess ions have been removed is redispersed in 1500 parts by weight of water, and 650
The powder was sprayed in a firing furnace heated to ℃ to obtain fine powder of tin oxide-antimony oxide composite having a bluish average particle size of 0.005 μm. The specific resistance of this fine particle powder was 5 Ω · cm. A mixed solution of 40 parts by weight of the above fine particle powder and 60 parts by weight of water was adjusted to pH 7.0, and roughly dispersed by a stirrer, and then a horizontal sand mill (trade name: Dynomill; WILLYA.BA).
CHOFENAG) and dispersed until the residence time reached 30 minutes. At this time, the average particle size of the secondary aggregate was about 0.04 μm.

3-1-2) Coating of Conductive Layer A conductive layer having the following formulation was coated so that the dry film thickness would be 0.2 μm, and dried at 115 ° C. for 60 seconds. Conductive fine particle dispersion prepared in 3-1-1) 20 parts by weight Gelatin 2 parts by weight Water 27 parts by weight Methanol 60 parts by weight p-Chlorophenol 0.5 parts by weight Resorcinol 2 parts by weight Polyoxyethylene nonylphenyl ether 0. 01 parts by weight The resistance of the obtained conductive film was 10 ^8.0 (100 V), and it had excellent antistatic performance. 3-2) Coating of magnetic recording layer Co-coated γ-Fe ₂ O ₃ (long axis 0.14 μm, single axis 0.
Needle-shaped 03μm, specific surface area 41m ² / g, saturation magnetization 89em
u / g, the surface is treated with 2% by weight of Fe ₂ O ₃ with aluminum oxide and silicon oxide respectively, coercive force 930 Oe, Fe ⁺²
/ Fe ⁺³ ratio was 6/94) 1100 g, water 220 g and poly (polymerization degree 16) oxyethylenepropyltrimethoxysilane silane coupling agent 150 g were added, and well kneaded in an open kneader for 3 hours. The roughly dispersed viscous liquid was dried at 70 ° C. for one day to remove water,
Surface-treated magnetic particles were prepared by heating at 110 ° C. for 1 hour. Further, the following formulation was used, and the mixture was kneaded again in an open kneader.

[0124]   1000 g of the above surface-treated magnetic particles   Diacetyl cellulose 17g   Methyl ethyl ketone 100g   Cyclohexanone 100g   Furthermore, with the following formulation, finely disperse at 200 rpm for 4 hours with a sand mill (1 / 4G). did.   100g of the above kneaded product   Diacetyl cellulose 60g   Methyl ethyl ketone 300g   Cyclohexanone 300g In addition, diacetyl cellulose and trimethyl
Roll propane-toluene diisocyanate 3 times mole
20 wt% of the adduct was added to the binder. Obtained
Liquid so that the viscosity of the liquid is about 80 CP.
Diluted with luketone and cyclohexanone. Also, the application is
1.2μm thickness on the above conductive layer with a bar coater
I went to The amount of magnetic material is 62 mg / m²Will be
It was applied on the seaweed. In addition, silica particles (0.3
μm) and abrasive aluminum oxide (0.5 μm)
10 mg / m²Was added. Drying at 115 ℃, 6
Minutes (all the rollers and conveyors in the drying zone
115 ° C). With status M of X-light
D of the magnetic recording layer when using a blue filter ^BThe color of
The increase in concentration was about 0.1. In addition, the magnetic recording layer
Saturation magnetization moment is 4.2emu / m², Coercive force 923 Oe,
The squareness ratio was 65%.

3-3) Preparation of Sliding Layer The following formulation liquid was applied so that the solid coating amount of the compound was as follows, and dried at 110 ° C. for 5 minutes to obtain a sliding layer. Diacetyl cellulose 25 mg / m ² C ₆ H ₁₃ CH (OH) C ₁₀ H ₂₀ COOC ₄₀ H ₈₁ (compound a) 6 mg / m ² C ₅₀ H ₁₀₁ O (CH ₂ CH ₂ O) ₁₆ H (compound b) 9 mg / m ² Compound a / Compound b (6: 9) was xylene and propylene glycol monomethyl ether (volume ratio 1:
1) Heat and dissolve in a solvent at 105 ° C.
C.) to give a fine dispersion. After further diluting in 5 times the amount of acetone, it was redispersed with a high-pressure homogenizer (200 atm) to form a dispersion (average particle diameter 0.01 μm), which was then added and used. The performance of the obtained sliding layer is such that the dynamic friction coefficient is 0.06 (5 mmφ stainless hard ball, load 100).
g, speed 6 cm / minute), static friction coefficient 0.07 (clip method), and excellent properties. The sliding property with respect to the emulsion surface, which will be described later, also had a dynamic friction coefficient of 0.12.

4) Coating of light-sensitive material layer Next, on the side opposite to the back layer obtained above, Example-1
The same layers as those of Samples 101 to 116 were applied in multilayers to form Samples 201 to 216, respectively.

When samples 201 to 216 were exposed and developed in the same manner as in Example-1, good results were obtained in the present invention as in Example-1.

─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Naoto Matsuda 210 Nakanuma, Minamiashigara City, Kanagawa Prefecture Fuji Shashin Film Co., Ltd. (56) Reference JP-A-8-146576 (JP, A) JP-A-8-201999 (JP, A) (58) Fields investigated (Int.Cl. ⁷ , DB name) G03C 7/38

Claims (3)

(57) [Claims] 1. A silver halide color photographic light-sensitive material characterized in that at least one layer on a support contains a coupler represented by the following general formula (1). General formula (1) In the general formula (1), R ₁ and R ₂ each represent an electron-withdrawing group having a Hammett's substituent constant σp value of 0.20 or more and 1.0 or less. R ₃ represents a substituent, and n represents an integer of 0 to 4. Q is _{-NHCO -, - NHSO 2 -,} - CONH-
Or an -SO ₂ NH-. R ₄ represents a substituent substituted with an acidic dissociative group. R ₅ represents a substituent, and m represents an integer of 0 to 4. X represents a hydrogen atom or a group capable of splitting off upon coupling with an oxidized product of a color developing agent. 2. The silver halide according to claim 1, wherein R ₁ in the general formula (1) is a cyano group and R ₂ is a group represented by the general formula (2). Color photographic light-sensitive material. [Chemical 2] In the general formula (2), R ₁ ′ and R ₂ ′ each represent an aliphatic group, R ₃ ′, R ₄ ′ and R ₅ ′ each represent a hydrogen atom or an aliphatic group, and Z represents 5 to 8 members. Represents a group of non-metal atoms necessary for forming a ring. 3. A silver halide color light-sensitive material is a silver halide color reversal light-sensitive material.
Or the silver halide color photographic light-sensitive material described in 2.