JP2607905B2 - Silver halide color photographic materials - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION (Industrial Application Field) The present invention is excellent in sharpness and color reproducibility,
The present invention relates to a silver halide photographic light-sensitive material which stably provides a high cyan image density even when subjected to a bleaching process with a fatigued bleaching solution.

(Prior Art) A color developing agent such as oxidized aromatic primary amines reacts with a dye-forming coupler by exposing a silver halide photographic material to light and then developing the color to form a color image. . In general, in this method, a color reproduction method based on a subtractive color method is used, and in order to reproduce blue, green, and red, respective color images of yellow, magenta, and cyan, which have complementary colors, are formed. In this case, phenols or naphthols are often used as cyan dye-forming couplers.

Many studies have been made on color photographic light-sensitive materials for the purpose of improving color reproducibility, sharpness and sensitivity. One technique for improving color reproducibility and sharpness is a coupler (DI
R couplers) are known. For example, U.S. Pat.No. 4,248,9
No. 62, No. 4,409,323, No. 4,421,845, No. 4,438,193
And the compounds described in JP-A-4,546,073 and the like. However, it is still insufficient, and further improvement has been desired.

On the other hand, one drawback of the conventional cyan coupler is that a sufficiently high density cyan image cannot be obtained in the processing through the bleaching step having a weak oxidizing power. For example, in a process that passes through a contaminated Fe (III) -EDTA bleaching process or a persulfate bleaching process, the cyan image does not have a sufficient density. This problem has always been an unavoidable problem in the study of photosensitive materials for the purpose of increasing the sensitivity, and improvement has been desired more than before.

Regarding the improvement, for example, JP-A-60-237448, 6
1-153640, 61-145557, 63-141055, 62-151
Nos. 847 and 62-87960.

Although the above two problems have been individually improved to some extent, there is no known means for solving them simultaneously when they are assembled as a photosensitive material. In other words, a high-sensitivity photosensitive material is inferior in color reproducibility and sharpness, and a photosensitive material excellent in color reproducibility and sharpness is inevitably low in sensitivity.

(Object of the Invention) An object of the present invention is to provide a halogen which gives a sufficiently high density cyan image even when treated with a bleaching solution or a bleaching solution which is excellent in color reproducibility and sharpness and has low oxidizing power. An object of the present invention is to provide a silver halide color photosensitive material.

(Constitution of the Invention) The object described above is to provide at least one coupler having l + m + p + n of 3 and at least one coupler having l + m + p + n of 0, 1, or 2 among the couplers represented by the following general formula (I). A silver halide color photographic light-sensitive material characterized by being contained in the same light-sensitive layer and containing at least one cyan coupler represented by the following general formula (II) or (III): .

General formula (I) In the formula, A represents a group which reacts with an oxidized form of an aromatic primary amine developing agent to cleave {(L ₁ ) l- (B) m} p- (L ₂ ) n-DI; ₁ represents the general formula right side of the join after binding of the left L ₁ is cleaved represented by (I) ((B) binding to m) is a group that is cleaved, B reacts with oxidized developer,
Formula right binding of B represented by formula (I) represents a group which cleaves, L ₂ is Formula right side of the join after binding of the left L ₂ is cleaved represented by the formula (I) (binding with DI) Represents a group that can be cleaved, DI represents a development inhibitor, l, m and n each represent 0 or 1, and p represents an integer of 0 to 3.
Here, when there are a plurality of p, p (L ₁ ) l- (B) m represent the same or different ones.

Provided that l and m are both 1 and p is 0
, L and m are both 0, and p is not a positive number.

General formula (II) General formula (III) In the formula, R ₁ represents an aromatic group or a heterocyclic group, R ₂ represents a group that can be substituted on a benzene ring, R ₃ represents an aliphatic group, a represents an integer of 0 to 3, and b represents And Z ₁ represents a hydrogen atom or a coupling-off group, and Z ₁ in the general formulas (II) and (III) represents an integer of 0 to 3.
₁ may be different from each other. Z ₂ is -O-, -S-,
Or Represents Provided that R ₄ represents a hydrogen atom or an organic substituent, and when a and b are plural, R ₂ in the general formulas (II) and (III) may be the same or different; They may combine to form a ring. In the general formula (III), R ₂ and Z ₂ , or Z ₂ and Z ₁ may be bonded to each other to form a ring. Also, R ₁ ,
R ₂ , R ₃ , R ₄ , Z ₂ or Z ₁ may form a dimer or higher multimer.

First, the compound represented by formula (I) will be described. The compound represented by the general formula (I) can exhibit various performances by selecting l, m, n and p in the process of releasing DI. That is, the present application includes a group of compounds that can be molecularly designed according to various purposes.

In a preferred embodiment of the present invention, l + m + n + p
Particularly preferred is a compound of ≧ 3, wherein l + m + n + p = 3. At this time, the compound represented by the general formula (I) had a strong overlay effect and an edge effect, and was excellent in color reproducibility and sharpness. In a further preferred embodiment, l +
This is when a compound in which m + n + p is 0 to 2 is used in combination. That is, it is preferable to use such two kinds of compounds in combination in order to adjust the gradation and obtain a uniform layering effect.

The reaction process in which the compound represented by the general formula (I) releases DI at the time of development is represented by, for example, the following reaction formula.
An example when p = 1 is shown.

Where A, L₁, B, L_Two, DI, l, m and n are of the general formula
Represents the same meaning as described in (I), Is
It means an oxidized developing agent.

Next, the compound represented by formula (I) will be described in detail below.

In the general formula (I), A specifically represents a coupler residue or a redox group.

Examples of the coupler residue represented by A include yellow coupler residues (for example, open-chain ketomethylene-type coupler residues such as acylacetanilide and malondianilide),
Magenta coupler residues (for example, coupler residues such as 5-pyrazolone type, pyrazolotriazole type or pyrazoloimidazole type), cyan coupler residues (for example, phenol type, naphthol type or European patent publication No. 249,
No. 453) and non-colored coupler residues (for example, coupler residues such as indanone type and acetophenone type). Also, U.S. Pat.Nos. 4,315,070, 4,183,752, 4,174,
It may be a heterocyclic coupler residue described in 969, 3,961,959 or 4,171,223.

When A represents a redox group, the redox group is a group that can be cross-oxidized by an oxidized developing agent, and examples thereof include hydroquinones, catechols, pyrogallols,
Examples thereof include 4-naphthohydroquinones, 1,2-naphthohydroquinones, sulfonamidophenols, hydrazides and sulfonamidonaphthols. These groups are specifically described, for example, in JP-A-61-230135 and JP-A-62-251746.
Nos. 61-278,852; U.S. Pat.Nos. 3,364,022; 3,37
9,529, 3,639,417, 4,684,604 or J.Org.C
hem., 29 , 588 (1964).

Linking group represented by L ₁ and L ₂ in the general formula (I), for example, U.S. Patent No. 4,146,396, Use group cleavage reactions hemiacetal with a described in the 4,652,516 Patent, or Nos 4,698,297, U.S. Patent 4,248,962 The timing group which causes a cleavage reaction using an intramolecular nucleophilic reaction described in No. 4, a timing group which causes a cleavage reaction using an electron transfer reaction described in U.S. Pat.No. 4,409,323 or 4,421,845, U.S. Pat.No. 4,546,073 describes a group that initiates a cleavage reaction by utilizing an imino ketal hydrolysis reaction or a group that initiates a cleavage reaction by utilizing an ester hydrolysis described in German Patent Publication No. 2,626,317. Is mentioned. L ₁ and L ₂ are each a hetero atom, preferably an oxygen atom, a sulfur atom or a nitrogen atom, represented by A or A- (L ₁ ) 1- (B) m
Combine with etc.

The group represented by B in the general formula (I) is A- (L ₁ )
a group that becomes an oxidation-reduction group or a group that becomes a coupler after being cleaved from 1 and has the same meaning as described above for A. The group represented by B has a group capable of reacting with an oxidized developing agent and leaving (that is, a group bonded to the right side of B in the general formula (I)). Examples of the group represented by B include a group represented by B in JP-A-63-6550, a group represented by COUP (B) in U.S. Pat. No. 4,438,193, and a group represented by RED in U.S. Pat. No. 4,618,571. . B represents A at a hetero atom, preferably an oxygen atom, a sulfur atom or a nitrogen atom contained therein.
Preferably, it binds to-(L ₁ ) l.

The group represented by DI in the general formula (I) is, for example, a tetrazolylthio group, a thiadiazolylthio group, an oxadiazolylthio group, a triazolylthio group, a benzimidazolylthio group, a benzthiazolylthio group, a tetrazolylseleno group, A benzoxazolylthio group, a benzotriazolyl group, a triazolyl group or a benzoindazolyl group. These groups are, for example, U.S. Pat.No. 3,227,554,
3,384,657, 3,615,506, 3,617,291, 3,7
33,201, 3,933,500, 3,958,993, 3,961,95
9, 4,149,886, 4,259,437, 4,095,984,
No. 4,477,563 or British Patent No. 1,450,479.

Next, preferred ranges of the compound represented by the formula (I) will be described.

 In the formula, p is preferably 0 to 2.

In the formula, the linking groups represented by L ₁ and L ₂ include a methyleneoxy group, a 4-methylene-3-pyrazolyloxy group,
Preferred examples are a 2 (or 4) -methylene phenoxy group or a 2-carbonylaminomethyl phenoxy group.
In these oxygen atoms, L ₁ or L ₂ of the general formula (I)
To the left hand. Further, these divalent groups may have a substituent at a substitutable position (for example, in a methylene group or a benzene ring), and a typical substituent is an alkyl group (for example, methyl, ethyl, isopropyl, Dodecyl), acyl groups (eg, benzoyl, acetyl), alkoxy groups (eg, methoxy, ethoxy),
Alkoxycarbonyl group (for example, methoxycarbonyl,
Butoxycarbonyl), a carebamoyl group (eg, ethylcarbamoyl), a nitro group, a carboxyl group, a sulfonyl group (eg, methanesulfonyl), an aryl group (eg, 4-nitrophenyl, 4-carboxyphenyl), a halogen atom (eg, a chlorine atom, a fluorine atom) Or a sulfamoyl group (eg, octadecylsulfamoyl).

Compound represented by the general formula (I) preferably represents a nondiffusible type, particularly preferably nondiffusible group is when included A, to L ₁ or L _2.

A particularly preferred compound in formula (I) is when A represents a coupler residue.

Particularly preferred compounds in the general formula (I) are l = 1, m
= 0, p = 1 and n = 1, l = 1, m = 1, p = 1 and n
= 0, m = 1, p = 1 and n = 1, or l = 0, m = 1, p = 2 and n = 0. These compounds are particularly excellent in color reproducibility due to the layering effect and sharpness due to the edge effect.

For examples of the compound represented by the general formula (I) and the synthesis method, a known patent or literature cited for the description of the general formula (I) for A, L ₁ , B, L ₂ and DI; -37346 and 61-156127.

(Compound example) Next, the compounds represented by formulas (II) and (III) will be described in detail below.

Examples of the aromatic group represented by R ₁ include a substituted or unsubstituted aromatic group having 6 to 30 carbon atoms in an aromatic residue.

Examples of the aliphatic group represented by R ₃ include a substituted or unsubstituted aliphatic group having 1 to 30 carbon atoms in an aliphatic residue.

Examples of the heterocyclic group represented by R ₁ include a substituted or unsubstituted heterocyclic group having 2 to 30 carbon atoms in the heterocyclic residue.

R ₂ represents a group (including an atom, the same applies hereinafter) which can be substituted on a naphthol ring or a phenol ring, and representative examples include a halogen atom, an alkoxyacylamino group, a carboxyl group,
Sulfonic acid group, cyano group, aromatic group, heterocyclic group, carbonamide group, sulfonamide group, carbamoyl group, sulfamoyl group, ureido group, acyl group, acyloxy group, aliphatic oxy group, aromatic oxy group, aliphatic Thio group,
Aromatic thio group include an aliphatic sulfonyl group, an aromatic sulfonyl group, and a sulfamoylamino group, or an imido group, number of carbon atoms contained in the R ₂ is 0-30. When there are _two R ₂ , examples of the cyclic R ₂ include a dioxymethyl group.

Z ₂ represents O, S or R ₄ N, and R ₄ represents hydrogen or a monovalent group. The monovalent group is preferably of the following general formula (V
R ₁₀ (Z ₃ ) (VI) represented by I) wherein Z ₃ represents CO or SO ₂ , d represents zero or 1, R ₁₀ is a hydrogen atom, an aliphatic having 1 to 30 carbon atoms. group, an aromatic group having 6 to 30 carbon atoms, a heterocyclic group having 2 to 30 carbon _{atoms, -OH, -OR 11, -COR 11} , -SO 2 R 11, Are shown, wherein R ₁₁ and R ₁₂ represents an aliphatic group, an aromatic group, a heterocyclic group or a hydrogen atom, NR ₁₁ in R ₁₂ R ₁₁
And R ₁₂ may be the same or different.

In R _10, attached R ₁₁ and R ₁₂ of -NR ₁₁ R ₁₂ with each other, a nitrogen-containing heterocyclic (morpholine ring, piperidine ring, pyrrolidine ring, etc.) may be formed.

Z ₁ represents a hydrogen atom or a coupling leaving group (including a leaving atom; the same applies hereinafter). Representative examples of the coupling-off group include a halogen atom, -OR ₁₃ , Heterocyclic groups having 1 to 30 carbon atoms and linked to the coupling active position of the coupler by a nitrogen atom (succinimide group, phthalimide group, hydantoinyl group, pyrazolyl group, 2-benzotriazolyl group, etc.) may be mentioned. it can. Here, R ₁₃ represents an aliphatic group having 1 to 30 carbon atoms, an aromatic group having 6 to 30 carbon atoms, or a heterocyclic group having 2 to 30 carbon atoms.

In the present invention, the aliphatic group is saturated / unsaturated,
It may be unsubstituted, linear, branched, or cyclic, and typical examples include a methyl group, an ethyl group, a hydroxyethyl group, a butyl group, a cyclohexyl group, an allyl group,
Propargyl group, methoxyethyl group, n-decyl group, n
-Dodecyl group, n-hexadecyl group, trifluoromethyl group, heptafluoropropyl group, dodecyloxypropyl group, 2,4-di-tert-amylphenoxypropyl group, 2,4-di-tert-amylphenoxy group And a sibutyl group.

The aromatic group may be substituted or unsubstituted. Typical examples include phenyl, naphthyl, tolyl, 2-tetradecyloxyphenyl, pentafluorophenyl, 4-tert. -Octylphenyl group, 2-
Chloro-5-dodecyloxycarbonylphenyl group, 4
-Chlorophenyl group, 4-methoxyphenyl group, 4-hydroxyphenyl group and the like.

The heterocyclic group may be substituted or unsubstituted. Typical examples include a 2-pyridyl group, a 4-pyridyl group, a 2-furyl group, a 4-thienyl group, a quinolinyl group,
A pyrazolyl group, and the like.

 Preferred examples of the substituent will be described below.

R ₁ is preferably an aromatic group, particularly preferably a phenyl group and a naphthyl group. Preferred substituents on the aromatic group include an alkoxy group (eg, a tetradecyloxy group, a methoxy group), an alkoxycarbonyl group (eg, a dodecyloxycarbonyl group, a methoxycarbonyl group), and an acylamino group (eg, 4- (2,4-di- tert-amylphenoxy) butanamide group, tetradecaneamide group), sulfonamide group (eg, hexadecylsulfonamide group), sulfamoyl group (eg, 3- (2,4-di-tert)
-Amylphenoxypropylsulfamoyl group, N, N-
Diethylsulfamoyl group, hexadecylsulfamoyl group), carbamoyl group (for example, dodecylcarbamoyl group, 4- (2,4-di-tert-amylphenoxy) butylcarbamoyl group), imide group (for example, dodecylsuccinimide group, octade Senylsuccinimide group), sulfonyl group (eg, dodecylsulfonyl group, propanesulfonyl group, methanesulfonyl group), aliphatic thio group (eg, dodecylthio group, ethylthio group), halogen atom, cyano group, aliphatic group (eg, methyl group, t-butyl group).

In the general formula (II), preferably, a = 2, particularly preferably a = 1, and R ₂ is an acylamino group (for example, an acetamido group, a 2- (2,4-di-t-amylphenoxy) butanamide group) 2- (2,4-di-t-amylphenoxy) hexanamide group, 2- (2,4-di-
t-amylphenoxy) isobutanamide group), alkoxyacylamino group (for example, butoxyacylamino group), halogen atom (for example, chloro atom, fluorine atom)
And the like are particularly preferred examples.

In the general formula (III), it is particularly preferable that b = 0.

Examples of the aliphatic group represented by R ₃ include a methyl group, a propyl group, a butyl group, a tert-butyl group, a pentyl group, a tridecyl group, and a case where these groups have a substituent. As a preferable substituent on the aliphatic group, an aromatic oxy group (e.g., 2,4-di-tert-amylphenoxy group, 2,4-di-tert-hexylphenoxy group, 2,4-di-tert-octyl group) Enoxy group, 2-chlorophenoxy group, 4- (4
-Hydroxyphenylsulfonyl) phenoxy group), aliphatic oxy group (eg, methoxy group, ethoxy group, dodecyloxy group, hexadecyloxy group), sulfonamide group (eg, methanesulfonamide group, 4-methylbenzenesulfonamide group) And the like.

Preferred Z ₂ is R ₄ N, wherein R ₄ is -COR
₁₀ (formyl, acetyl, trifluoroacetyl, chloroacetyl, benzoyl, pentafluorobenzoyl, p-chlorobenzoyl, etc.), -COOR
₁₁ (a methoxycarbonyl group, an ethoxycarbonyl group, butoxycarbonyl group, decyloxycarbonyl group, methoxyethoxy group, etc. phenoxyethanol carbonyl group), - SO ₂ R ₁₀ (methanesulfonyl group, ethanesulfonyl group, butanesulfonyl group, Hexadecanesulfonyl group, benzenesulfonyl group, trienesulfonyl group, p
-Chlorobenzenesulfonyl group), -CONR ₁₁ R
₁₂ (N, N-dimethylcarbamoyl group, N, N-diethylcarbamoyl group, N, N-dibutylcarbamoyl group, morpholinocarbonyl group, piperidinocarbonyl group, 4-cyanophenylcarbonyl group, 3,4-dichlorophenyl carbamoylmethyl group, such as 4-methanesulfonyl-phenylene carbamoyl _{group), - SO 2 NR 11 R} 12 (N, N- dimethyl sulfamoylamino group, N, N-diethyl-sulfamoylamino group, N, N-Jipuropirusuru Famoyl group). Especially preferred
Z ₂ is —COR ₁₀ , —COOR ₁₁ and —SO ₂ R ₁₀ . Where R
₁₁ and R ₁₂ have the same meaning as before.

Preferred Z ₁ is a hydrogen atom, a halogen atom, an aliphatic oxy group, or an aromatic oxy group.

Specific examples of the coupler represented by formula (II) and the synthesis method thereof are described in, for example, JP-A Nos. 61-72245 and 61-65241.
No. 61-42658, No. 60-50533, or U.S. Patent No. 45
No. 79813.

Specific examples of the coupler represented by the general formula (III) and a synthesis method thereof are described in, for example, JP-A Nos. 60-237448 and 61-237448.
No. 153640 or 61-145557.

Examples of compounds represented by general formulas (II) and (III) As the magenta coupler used in the present invention, any may be used, but preferably at least one of the magenta couplers represented by the general formula (IV) or (V) is used.

In the formula, R represents a hydrogen atom or a substituent, and Za and Zb
Represents a methine group or a nitrogen atom, X represents a hydrogen atom or a coupling-off group, R ₂₀ represents an aromatic amino group, an aromatic acylamino group or an aliphatic acylamino group, and Ar represents an aromatic group. Where the general formula (I
In V), a multimer of dimer or more may be formed in R, X, Za or Zb. In the general formula (V), R ₂₀ ,
In X or Y, a dimer or more multimer may be formed.

For the magenta coupler represented by the general formula (IV),
This is described in detail below. Among the magenta couplers represented by the general formula (IV), preferred are those represented by the following general formula (M-
1), (M-2), (M-3), (M-4) or (M-
5).

In the general formulas (M-1) to (M-5), R and X
Has the same meaning as defined in formula (IV),
₂₁ and R ₂₂ each represent a hydrogen atom or a substituent,
q represents an integer of 0 to 4.

The pyrazoloazole magenta couplers represented by formulas (M-1) to (M-5) will be described in detail.

R ₁ , R ₂₁ and R _{22 each} represent a hydrogen atom, a halogen atom (such as a fluorine atom or a chlorine atom), an alkyl group (such as methyl, ethyl, isopropyl, 1-butyl, t-butyl, 1-octyl), or an aryl group ( Phenyl, p-tolyl, 4-nitrophenyl, 4-ethoxyphenyl, 2- (2-octyloxy-5-t-octylbenzenesulfonamido) phenyl, 3-dodecanesulfonamidophenyl, 1-naphthyl, etc., hetero Ring group (4-pyridyl, 2-furyl etc.), hydroxyl group, alkoxy group (methoxy, ethoxy, 1-butoxy, 2-phenoxyethoxy, 2-
(2,4-di-t-amylphenoxy) ethoxy and the like), an aryloxy group (phenoxy, 2-methoxyphenoxy, 4-methoxyphenoxy, 4-nitrophenoxy,
3-butanesulfonamidophenoxy, 2,5-di-t-
Amylphenoxy, 2-naphthoxy, etc.), heterocyclic oxy group (2-furyloxy, etc.), acyloxy group (acetoxy, pivaloyloxy, benzoyloxy, dodecanoyloxy, etc.), alkoxycarbonyloxy group (ethoxycarbonyloxy, t-butoxycarbonyloxy) , 2-ethyl-1-hexyloxycarbonyloxy, etc.), an aryloxycarbonyloxy group (such as phenoxycarbonyloxy), a carbamoyloxy group (N, N-
Dimethylcarbamoyloxy, N-butylcarbamoyloxy, etc.), sulfamoyloxy group (N, N-diethylsulfamoyloxy, N-propylsulfamoyloxy, etc.), sulfonyloxy group (methanesulfonyloxy, benzenesulfonyloxy, etc.) ), Carboxyl group,
Acyl groups (acetyl, pivaloyl, benzoyl, etc.), alkoxycarbonyl groups (ethoxycarbonyl, etc.), aryloxycarbonyl groups (phenoxycarbonyl, etc.),
Carbamoyl group (N, N-dibutylcarbamoyl, N-ethyl-N-octylcarbamoyl, N-propylcarbamoyl, etc.), amino group (amino, N-methylamino, N,
N-dioctylamino, etc.), anilino group (N-methylanilino, etc.), heterocyclic amino group (4-pyridylamino, etc.), amide group (acetamide, benzamide, etc.), urethane group (N-hexylurethane, N, N-dibutylurethane) Ureido group (N, N-dimethylureido, N-
Phenylureido, etc.), sulfonamide group (butanesulfonamide, p-toluenesulfonamide, etc.), alkylthio group (ethylthio, octylthio, etc.), arylthio group (phenylthio, 4-dodecylphenylthio, etc.),
A heterocyclic thio group (eg, 2-benzothiazolylthio, 5-tetrazolylthio), a sulfinyl group (eg, benzenesulfinyl), a sulfonyl group) methanesulfonyl, octanesulfonyl, p-toluenesulfonyl, etc.), a sulfo group,
Examples include a cyano group and a nitro group.

X represents a hydrogen atom, a halogen atom (a fluorine atom, a chlorine atom, a bromine atom, etc.), a carboxyl group, or a group linked by an oxygen atom (acetoxy, benzoyloxy, phenoxy,
-Cyanophenoxy, tolyloxy, 4-methanesulfonylphenoxy, 4-ethoxycarbonylphenoxy,
2-naphthoxy, ethoxy, 2-cyanoethoxy, 2-
Benzothiazolyloxy, etc.), groups linked by nitrogen atoms (benzenesulfonamide, heptafluorobutanamide, pentafluorobenzamide, octanesulfonamide, p-cyanophenylureido, 1-piperidinyl, 5,5-dimethyl-2) , 4-Dioxo-3-oxazolidinyl, 1-benzyl-5-ethoxy-3-hydantoinyl group, 1-imitazolyl, 1-pyrazolyl, 3-chloro-1-pyrazolyl, 3,5-dimethyl-1,2,4- Triazol-1-yl, 5- or 6-bromobenzotriazol-1-yl, etc.) or a group linked by a sulfur atom (phenylthio, 2-butoxy-5-t-octylphenylthio, 4-methanesulfonylphenylthio) , 4-dodecyloxyphenylthio, 2-cyanoethylthio, 1-ethoxycarbonyltridecyl It represents O, benzothiazolylthio, 1-phenyl-1,2,3,4-tetrazol-5-thio, etc.). X is preferably a group linked by a halogen atom or a sulfur atom.

Among the pyrazoloazole magenta couplers represented by formulas (M-1) to (M-5), preferred are those represented by formulas (M-2) and (M-3).

The compound examples of the pyrazoloazole magenta couplers represented by formulas (M-1) to (M-5) are shown below. These compounds are described, for example, in U.S. Pat.
No. 0,654, 4,548,899, JP-A-60-172982, 61-65
No. 246, No. 61-65245, No. 61-72238, or No. 61-6524
The compound can be synthesized by the method described in No. 7 or a similar method.

Next, the compound represented by formula (V)-will be described in detail below.

When R ₂₀ is a group containing an aromatic group, and for Ar, the definition of the aromatic group is as described above (for example, the general formula (I
Is the same as the) meaning described R ₁ in I).

When R ₂₀ is a group containing a moiety of an aliphatic group, the definition of the aliphatic group is the same as that described above (for example, R _{3 in the} general formula (III)).

When X represents a coupling-off group, the detailed definition of X has the same meaning as described above (for X in formula (IV)).

The preferred range of the compound represented by formula (V) will be described below.

R ₂₀ is preferably an anilino group (eg, 2-chloro-5
A tetradecanamidoanilino group, a 2-chloro-5-octadesensuccinimidoanilino group, 2-chloro-5
-{2- (3-t-butyl-4-hydroxyphenoxy) dodecaneamide} anilino group, 2-chloro-5-tetradecyloxycarbonylanilino group or 2,4-dichloroanilino group), benzamide group (For example, 5- ｛2
-(2,4-di-t-amylphenoxy) butanamide}
A benzamide group, a 5- (2,4-di-t-amylphenoxyacetamide) benzamide group, a 4-dodecanesulfonamidobenzamide group or a 5-tetradecanamidobenzamide group) or an alkaneamide group (for example, 2,2
A dimethylpropanamide group, a butanamide group or 4
-(2,4-di-t-amylphenoxy) butanamide group).

In the general formula (V), X is preferably a nitrogen-containing unsaturated 5-membered ring (for example, 1-pyrazolyl group, 4-chloro-1-pyrazolyl group, 4-methyl-1-pyrazolyl group, 4- {3
-(2-decyl-4-methyl) phenoxyacetoxy}
Propylpyrazol-1-yl group, 5-chloro-1,2,4
-Triazol-1-yl group or 5-phenoxycarbonylbenzotriazol-1-yl group), arylthio group (for example, 2-butoxy-5-t-octylphenylthio group, 4-nonylphenylthio group or 4 -Carboxyphenylthio group) or an aliphatic thio group (for example, 2-dodecyloxycarbonylmethylthio group, 2-hydroxyethylthio group, 2-carboxyethylthio group, 1-carboxyethylthio group, or 2,3-dihydroxypropylthio Group).

In the general formula (V), Ar is preferably a phenyl group (for example, 2,4,6-trichlorophenyl group, 2,5-dichlorophenyl group, 2,3-dichlorophenyl group, 2,6-dichloro group) -4-methoxyphenyl group or 4- {2- (2,4
-Di-t-amylphenoxy) butanamide {phenyl group).

Hereinafter, examples of the compound represented by Formula (V) are shown. However, it is not limited to these. These compounds can be synthesized, for example, by the method described in JP-A-60-185951, JP-A-60-2953, U.S. Patent Nos. 4,264,723, 4,351,897, 4,522,915, or 4,310,619 or a similar method. .

The yellow coupler used in the present invention is preferably represented by the following general formula (VII).

General formula (VII) (In the general formula (VII), R ₁ represents a tertiary alkyl group or an aryl group, R ₂ represents a hydrogen atom, a halogen atom, an alkoxy group or an aryloxy group, and R ₃ represents a halogen atom, an alkyl group, an aryl group, or an alkoxy group. An alkoxycarbonyl group, an aryloxycarbonyl group, a carbonamide group, a sulfonamide group, a carbamoyl group, a sulfamoyl group, an alkylsulfonyl group, an arylsulfonyl group,
A ureido group or an alkoxycarbonylamino group is represented by X
Represents a heterocyclic group or an aryloxy group bonded to the coupling active position of the yellow dye-forming coupler represented by formula (VII) with a nitrogen atom, and l represents an integer of 0 to 4, respectively. However, when 1 is plural, R ₃ may be the same or different. The yellow dye-forming coupler represented by formula (VII) is described in detail below.

In the general formula (VII), R ₁ preferably represents an optionally substituted tertiary alkyl group having 4 to 30 carbon atoms or an optionally substituted aryl group having 6 to 30 carbon atoms. When R ₁ represents a tertiary alkyl group, the substituent is a halogen atom (for example, fluorine, chlorine,
Bromine, iodine), alkoxy groups (eg, methoxy, ethoxy, methoxyethoxy, dodecyloxy), aryloxy groups (eg, phenoxy, p-methoxyphenoxy)
And the like. When R ₁ represents an aryl group, the substituent is a halogen atom (for example, fluorine,
Chlorine, bromine, iodine), an alkyl group (eg, methyl, ethyl, i-propyl, sec-butyl, t-butyl, cyclohexyl, allyl, t-octyl, n-dodecyl, trifluoromethyl), an alkoxy group (eg, methoxy, Ethoxy, methoxyethoxy, n-tetradecyloxy), carbonamide group (for example, acetoa In the general formula (VII), R ₂ is a hydrogen atom, a halogen atom (for example, fluorine, chlorine, bromine, iodine), preferably 1 carbon atom) Represents an optionally substituted alkoxy group or an aryloxy group having 6 to 30 carbon atoms when R ₂ represents an alkoxy group, and the substituent is a halogen atom (for example, fluorine, chlorine, bromine, Iodine), alkoxy groups (eg, methoxy, ethoxy, methoxyethoxy,
n-butoxy, n-hexyloxy, n-octyloxy, 2-ethylhexyloxy, n-dodecyloxy,
n-tetradecyloxy, n-hexadecyloxy) and the like. When R ₂ represents an aryloxy group, the substituent may be a halogen atom (eg, fluorine, chlorine, bromine,
Iodine), an alkyl group (eg, methyl, ethyl, isopropyl, t-butyl), an alkoxy group (eg, methoxy,
Ethoxy). Other hydrogen atoms and halogen atoms examples of R _2, a methoxy group, an ethoxy group, n- butoxy group, methoxyethoxy group, a benzyloxy group, n- tetradecyloxy group, a phenoxy group.

In the general formula (VII), R ₃ is preferably a halogen atom (for example, fluorine, chlorine, bromine, iodine), having 1 to 1 carbon atoms.
30 alkyl groups, 6 to 30 carbon atom aryl groups, 1 to 30 carbon atom alkoxy groups, 2 to 30 carbon atom alkoxycarbonyl groups, 7 to 30 carbon atom aryloxycarbonyl groups, carbon atoms A carbonamide group having 1 to 30 carbon atoms, a sulfonamide group having 1 to 30 carbon atoms, a carbamoyl group having 1 to 30 carbon atoms, a sulfamoyl group having 0 to 30 carbon atoms, and an alkylsulfonyl group having 1 to 30 carbon atoms ,
Represents an arylsulfonyl group having 6 to 30 carbon atoms, a ureido group having 1 to 30 carbon atoms or an alkoxycarbonylamino group having 2 to 30 carbon atoms, and when the above substituent contains an alkyl group, Is a halogen atom (eg, fluorine, chlorine, bromine, iodine), a cyano group, a nitro group, an aryl group (eg, phenyl, p-tolyl, 2-
Methoxyphenyl), an alkoxy group [for example, methoxy,
Ethoxy, butoxy, benzyloxy, n-hexyloxy, 2-ethylhexyloxy, n-octyloxy, n-decyloxy, n-dodecyloxy, n-dodecyloxyethoxy, 2- (2,4-di-t-pentylph) Enoxy) ethoxy], an alkoxycarbonyl group (eg, methoxycarbonyl, ethoxycarbonyl, n-butoxycarbonyl, n-dodecyloxycarbonyl), a carbamoyl group (eg, N, N-dimethylcarbamoyl, N
-Methyl-N-octadecylcarbamoyl, N-dodecyl-N-phenylcarbamoyl), aryloxy groups (e.g. phenoxy, p-dodecyloxyphenoxy,
2,4-di-t-pentylphenoxy, pt-octylphenoxy) and the alkylthio, arylthio, sulfonyl, sulfinyl, sulfimyl and imides mentioned above when R ₁ is a tertiary alkyl group. When the above substituent contains an aryl group, the substituent may be a halogen atom (for example, fluorine, chlorine, bromine, iodine) or an alkyl group (for example, methyl, ethyl, i- Propyl, allyl, benzyl, t-butyl, sec-butyl, cyclopentyl, cyclohexyl, t-octyl, n-decyl, n
-Dodecyl), aryl groups (eg phenyl, p-tolyl), alkoxy groups (eg methoxy, ethoxy, n-
Dodecyloxy) and alkoxycarbonyl groups (eg, methoxycarbonyl, ethoxycarbonyl, dodecyloxycarbonyl).

In the general formula (VII), X represents a heterocyclic group which is bonded to a coupling active position by a nitrogen atom. More specifically, these heterocyclic rings are a monocyclic or condensed 5- to 7-membered heterocyclic ring which may be substituted. And examples thereof are succinimide,
Maleimide, phthalimide, diglycolimide,
Pyrrole, pyrazole, imidazole, 1,2,4-triazole, tetrazole, indole, benzopyrazole, benzimidazole, benzotriazole, imidazolidin-2,4-dione, oxazolidin-2,4-dione, thiazolidine-2,4- Dione, imidazoline-2-
On, oxazolin-2-one, thiazolin-2-one, benzimidazolin-2-one, benzoxazolin-2-one, benzothiazolin-2-one, 2-pyrrolin-5-one, 2-imidazolin-5-one Indoline-2,3-dione, 2,6-dioxypurine, parabanic acid, 1,2,4-triazolidine-3,5-dione, 2-pyridone, 4-pyridone, 2-pyrimidone, 6-pyridazone,
2-pyrazone, 2-amino-1,3,4-thiazolidine, 2
-Imino-1,3,4-thiazolidine-4-one and the like,
These heterocycles may be substituted. Examples of the substituent include a halogen atom (for example, fluorine, chlorine, bromine, and iodine), a hydroxy group, a nitro group, a cyano group, a carboxy group, a sulfo group, a carboxylate group, a sulfonate group,
Sulfinate group, alkyl group (eg, methyl, ethyl, n-decyl, t-butyl, trifluoromethyl, carboxymethyl), alkoxy group (eg, methoxy, ethoxy, methoxyethoxy), acyl group (eg, acetyl, benzoyl), alkoxy Carbonyl groups (eg, methoxycarbonyl, ethoxycarbonyl, i-propoxycarbonyl, n-dodecyloxycarbonyl), carbamoyl groups (eg, N, N-dimethylcarbamoyl, N-
Methoxyethylcarbamoyl, N-tetradecylcarbamoyl), sulfonyl group (for example, methanesulfonyl group,
Benzenesulfonyl group, 4-hydroxybenzenesulfonyl group), sulfamoyl group (for example, N-methylsulfamoyl, N-phenylsulfamoyl, N-dodecylsulfamoyl), carbonamide group (for example, acetamido, benzamido, trifluoro) Acetamide, pentafluorobenzamide), sulfonamide group (eg, methanesulfonamide, p-toluenesulfonamide), amide group (eg, amino, N, N-dimethylamino, N, N-diethylamino, pyrrolidino, piperidino)
Etc.

Next, for each of the substituents R ₁ , R ₂ , R ₃ and X described above, the substituents preferably used in the present invention will be described.

R ₁ is preferably a tert-butyl group, a phenyl group or a phenyl group substituted by a chlorine atom, a methyl group or a methoxy group, and more preferably a t-butyl group, a phenyl group or a 4-methoxyphenyl group.

R ₂ is preferably a chlorine atom or an alkoxy group having 1 to 8 carbon atoms, more preferably a chlorine atom or a methoxy group, and most preferably a chlorine atom.

R ₃ is preferably a halogen atom (eg, fluorine, chlorine,
Bromine, iodine), an alkoxy group (eg, methoxy, ethoxy, butoxy, methoxyethoxybenzyloxy, dodecyloxy, tetradecyloxy), an alkoxycarbonyl group [eg, ethoxycarbonyl, dodecyloxycarbonyl, (1-dodecyloxycarbonyl) ethoxycarbonyl, (1-dodecyloxycarbonyl) pentyloxycarbonyl], an aryloxycarbonyl group (for example, phenoxycarbonyl, 2,5-di-t-pentyl, phenoxycarbonyl), a carbonamide group (for example, acetamido, tetradecaneamido, -Hexyldecaneamide, 2- (2,4-di-t-pentylphenoxy) butanamide, 4- (2,4-di-t-pentylphenoxy) butanamide, 3-dodecanesulfonyl-2-
Methylpropanamide, benzamide, 4-dodecyloxybenzamide] sulfonamide group (for example, methanesulfonamide, dodecanesulfonamide, hexadecanesulfonamide, N-methylhexadecanesulfonamide, benzenesulfonamide, toluenesulfonamide, 4-dodecylbenzenesulfonamide , 4-tetradecyloxybenzenesulfonamide), carbamoyl groups [for example, N-methylcarbamoyl, N, N-dihexylcarbamoyl, pyrrolidinocarbonyl, N-tetradecylcarbamoyl, N-phenylcarbamoyl, N- (4
-Tetradecyloxyphenyl) carbamoyl] or a sulfamoyl group (for example, N-methylsulfamoyl,
N-butylsulfamoyl, N-hexadecylsulfamoyl, piperidinosulfonyl, N, N-dioctylsulfamoyl, N-phenylsulfamoyl), more preferably an alkoxycarbonyl group, a carbonamide group Or a sulfonamide group.

l is preferably an integer of 0 to 2, and more preferably 1.

X is preferably a group represented by the following general formula (VIII).

In the general formula (VIII), Z is Represents Here, R ₄ , R ₅ , R ₈ and R ₉ represent a hydrogen atom, an alkyl group, an aryl group, an alkoxy group, an aryloxy group, a naralkylthio group, an arylthio group, an alkylsulfonyl group, an arylsulfonyl group or an amino group, R ₆ and R ₇ represent a hydrogen atom, an alkyl group, an aryl group, an aryl group, an alkylsulfonyl group, an arylsulfonyl group or an alkoxycarbonyl group, and R ₁₀ and R ₁₁
Represents a hydrogen atom, an alkyl group or an aryl group. R
₁₀ and R ₁₁ may form a benzene ring bonded to each other. R ₄ and R ₅ , R ₅ and R ₆ , R ₆ and R ₇ or R ₄ and R ₈ are bonded to each other to form a ring (eg, cyclobutane, cyclohexane, cycloheptane, cyclohexene, pyrrolidine, piperidine)
May be formed.

In the general formula (VIII-b), R ₁₂ represents an arylsulfonyl group, an alkylsulfonyl group, an arylsulfonamide group, an alkylsulfonamide group, an alkoxycarbonyl group, a carbamoyl group, or a sulfamoyl group, and m is an integer of 1 to 4. And R ₁₃ represents an organic substituent other than the substituents listed for R ₁₂ , and n represents 0 to 1. Examples of R ₁₃ include an alkyl group, an aryl group, a cyano group, and a halogen atom. However, m + n is 5 or less.

In the general formula (VII), X is preferably a general formula (VII)
It is a heterocyclic group represented by I).

Particularly preferred among the heterocyclic groups represented by the general formula (VIII) are those wherein Z in the general formula (VIII) Is a heterocyclic group.

The total number of carbon atoms of the heterocyclic group represented by the general formula (VIII) is 2 to 30, preferably 4 to 20.

Examples of the heterocyclic group represented by the general formula (VIII) include a succinimide group, a maleimide group, a phthalimide group,
-Methyl imidazolidine-2,4-dione-3-yl group,
1-benzylimidazolidin-2,4-dione-3-yl group, 5,5-dimethyloxazolidine-2,4-dione-3-
Yl group, 5-methyl-5-propyloxazolidine-2,
4-dione-3-yl group, 5,5-dimethylthiazolidine-
2,4-dione-3-yl group, 5,5-dimethylimidazolidine-2,4-dione-3-yl group, 3-methylimidazolidintrion-1-yl group, 1,2,4-triazolidine-
3,5-dione-4-yl group, 1-methyl-2-phenyl-1,2,4-triazolidine-3,5-dione-4-yl group,
1-benzyl-2-phenyl-1,2,4-triazolidine-3,5-dione-4-yl group, 5-hexyloxy-1
-Methyl imidazolidine-2,4-dione-3-yl group,
There are a 1-benzyl-5-ethoxyimidazolidin-2,4-dione-3-yl group, a 1-benzyl-5-dodecyloxyimidazolidin-2,4-dione-3-yl group and the like.

The coupler represented by the general formula [I] has a substituent R ₁ , X or May form a dimer or a multimer which bonds to each other via a divalent or divalent or higher valent group.
In this case, the number of carbon atoms may not be within the range specified for each substituent.

Specific examples of the yellow dye-forming coupler represented by formula (VII) are shown below, but the present invention is not limited thereto.

Other examples of compounds and / or synthetic methods of these couplers represented by the general formula [XI] are described, for example, in US Pat.
No. 3409439, No. 3730722, No. 3770445, No. 384
No. 2576, No. 3941601, No. 3973968, No. 3990896
No. 3998641 No. 4008086 No. 4012259 No.
No. 40222620, No. 4032347, No. 4046755, No. 4
No. 049458, No. 4075432, No. 4115121, No. 413395
No. 8, No. 4138263, No. 4138557, No. 4201584,
No. 4203768, No. 4206278, No. 4229577, No. 4
No.266019, No.4269936, No.4286053, No.428984
No. 7, No. 4288591, No. 4238564, No. 4248961,
No. 4289847, No. 4304845, No. 4314023, No. 4
326024, 4327175, 4336327, 435625
No. 8, No. 4404274, No. 4443536, No. 4617256,
UK Patent No. 1580999, 2011398, West German Patent No. 3107
No. 173, European Patent Application (EP) No. 30747, JP-A-48-66835
No. 48-99432, No. 50-108925, No. 50-132926, No.
50-158329, 51-3631, 51-145319, 52-5892
No. 2, No. 52-115219, No. 54-121126, No. 55-538, No. 5
5-598, 55-93153, 55-163538, 56-30126
Nos. 56-30127, 56-74250, 56-92539, 56
-153343, 56-161543, 56-164343, 57-2223
No. 8, No. 57-155538, No. 58-21738, No. 58-42046, No.
59-159163, 59-222837, 60-35730, 60-144
No. 740, No. 60-166948 and Research Disclosure Magazine (R
D) No. 18053 (1979).

The addition amount of the yellow coupler of the present invention is preferably 0.01 to 20 mmol, more preferably 0.1 to 5 per 1 m ^{2 of the} color photographic light-sensitive material.
It is on the order of millimoles.

General formulas (I) to
The couplers represented by (V) and (VII) may form a multimer through a divalent or higher valent group in the substituent.

When the coupler represented by the above general formula forms a multimer, a homopolymer or a copolymer of an addition-polymerizable ethylenically unsaturated compound (color-forming monomer) having a dye-forming coupler residue is a typical example. In this case, the multimer has the general formula (IX)
The repeating unit represented by the general formula (IX) may contain one or more kinds of repeating units, and one or two kinds of non-color-forming ethylene-like monomers may be used as a co-polymerization. A copolymer containing the above may be used.

In the formula, R ₂₃ represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms or a chlorine atom, E represents —CONH—, —COO—, or a substituted or unsubstituted phenylene group, and G represents a substituted or unsubstituted group. Represents an alkylene group, a phenylene group or an aralkylene group, and T represents -CONH-, -NHCONH-, NHCOO-,
-NHCO-, -OCONH-, -NH-, -COO-, -OCO-, -C
_{O, -O -, - SO 2} -, - NHSO 2 - or represents a -SO ₂ NH-. f, g, and t represent 0 or 1. QQ is the general formula (IV)
Or a coupler residue from which a hydrogen atom has been released from the compound represented by (V).

As the multimer, a copolymer of a color-forming monomer giving the coupler unit of the general formula (IX) and the following non-color-forming ethylene-like monomer is preferable.

Non-color-forming ethylene-like monomers that do not couple with the oxidation products of aromatic primary amine developing agents include acrylic acid, α-chloroacrylic acid, α-alkacrylic acid (eg, methacrylic acid) derived from these acrylic acids. Ester or amide (eg, acrylamide, methacrylamide, n-butylacrylamide, t
-Butyl acrylamide, diacetone acrylamide,
Methylenebisacrylamide, methyl acrylate, ethyl acrylate, n-propyl acrylate, n-butyl acrylate, t-butyl acrylate, iso-butyl acrylate, 2-ethylhexyl acrylate,
n-octyl acrylate, lauryl acrylate, methyl methacrylate, ethyl methacrylate, n-butyl methacrylate and β-hydroxy methacrylate), vinyl esters (eg, vinyl acetate, vinyl propionate and vinyl laurate), acrylonitrile, methacrylonitrile, aromatic Vinyl compounds (eg, styrene and its derivatives such as vinyl toluene, divinylbenzene, vinyl acetophenone and sulfostyrene), itaconic acid, citraconic acid, crotonic acid, vinylidene chloride, vinyl alkyl ethers (eg, vinyl ethyl ether), maleic acid esters , N-vinyl-2-pyrrolidone, N-vinylpyridine and 2- and -4-butenylpyridine.

In particular, acrylates, methacrylates, and maleates are preferred. Two or more non-color-forming ethylene-like monomers used herein can be used together. For example, methyl acrylate and butyl acrylate, butyl acrylate and styrene, butyl methacrylate and methacrylic acid, and methyl acrylate and diacetone acrylamide can be used.

As is well known in the field of polymer couplers, the general formula (IX)
When a repeating unit represented by is contained, the non-color-forming ethylene-like monomer which is copolymerized with the ethylene-like monomer having a dye-forming residue of the present invention is formed by forming a physical unit of the copolymer to be formed. The properties and / or chemical properties, such as solubility, compatibility of the photographic colloid composition with binders such as gelatin, its flexibility, thermal stability, etc., can be selected to be favorably affected.

A polymer coupler used in the present invention (a lipophilic polymer coupler obtained by polymerization of a vinyl monomer to give a coupler unit represented by the above general formula (IX)) dissolved in an organic solvent is mixed with an aqueous gelatin solution. And may be prepared by emulsifying and dispersing in the form of, or directly by an emulsion polymerization method.

A method for emulsifying and dispersing a lipophilic polymer coupler in the form of a latex in an aqueous gelatin solution is disclosed in U.S. Pat.
No. 1,820, US Patent No. 4,080,211 for emulsion polymerization
No. 3,370,952.

In the general formula (IX), the coupler residue represented by QQ is preferably a magenta coupler residue represented by the general formula (IV) or (V). Particularly, at this time, the merits when polymerizing are large. That is, in the case of a magenta coupler, when a polymer is used, the color density is high, that is, the color density per unit weight is high. As a result, the weight of the coupler added to the emulsion layer can be reduced, and the layer can be made thinner. At this time, light scattering of incident light at the time of exposure can be reduced, and the effect of improving sharpness is remarkable. This effect is even more remarkable when used together with the compound represented by the general formula (I).

The compounds of the general formulas (I) to (V) and (VII) or (IX) of the present invention can be used in a multilayer multicolor photographic material having at least three different spectral sensitivities on a support, mainly for improving sharpness and sensitivity. It can be applied for the purpose of improving color reproducibility. Multilayer natural color photographic materials usually have at least one red-sensitive emulsion layer, one green-sensitive emulsion layer, and one blue-sensitive emulsion layer on a support. The order of these layers can be arbitrarily selected as needed. The compound of the present invention is used in an emulsion layer or an adjacent layer. Further, the compound of the present invention can be used in any layer such as a high-sensitivity layer, a low-sensitivity layer or a medium-sensitivity layer.

The amount of the compound of the formula (I) varies depending on the structure of the compound, but is preferably 1 × 10 ⁻⁶ to 0.5 mol, particularly preferably 1 × 10 ⁻⁶ to 1 mol of silver present in the same layer or an adjacent layer.
It is from × 10 ^-5 to 1 × 10 ^-1 mol.

The amount of the compound represented by the general formulas (II) to (V), (XII) or (IX) varies depending on the structure of the compound, but is preferably 1 × 10 ⁻⁵ per mol of silver in the same layer or an adjacent layer.
To 1 mol, particularly preferably 1 × 10 ⁻⁴ to 0.5 mol.

Compounds of general formula (I) and general formulas (II) to (V), (VI
The molar ratio of (I) or (IX) (image forming coupler) used is (I) / (image forming coupler) = (0.001 / 99.999) to
(50/50) preferably (I) / (image forming coupler) =
(1/99) to (30/70).

In the photographic emulsion layer of the photographic light-sensitive material used in the present invention,
Any of silver bromide, silver iodobromide, silver iodochlorobromide, silver chlorobromide and silver chloride may be used. Preferred silver halides are silver iodobromide or silver iodochlorobromide containing up to about 30 mol% silver iodide. Particularly preferred is about 2 mol%
To about 25 mol% of silver iodide.

Silver halide grains in photographic emulsions are cubic, octahedral,
So-called regular particles having regular crystals such as tetradecahedron may be used, or those having irregular crystal forms such as spheres, those having crystal defects such as twin planes, or their complex forms May be.

The grain size of the silver halide may be fine grains of about 0.1 μm or less, or large grains having a projected area diameter of about 10 μm, and may be a monodisperse emulsion having a narrow distribution or a polydisperse emulsion having a wide distribution. Good.

The silver halide photographic emulsion that can be used in the present invention can be produced by a known method. For example, Research Disclosure (RD), No. 17643 (December, 1978), pp. 22-23, "I. Emulsion Production ( Emulsion preparation and types) ”and No. 18716 (November 1979), p.648.

The photographic emulsion used in the present invention is described in "Physics and Chemistry of Photography" by Grafkid, published by Paul Montell (P. Glafkides, Ch.
imie et Physique Photographique Paul Montel, 196
7), Duffin “Photographic Emulsion Chemistry”, published by Focal Press (GFDuffin, Photographic Emulsion Chemistry)
(Focal Press, 1966), "Manufacture and coating of photographic emulsions" by Zerikuman et al., Published by Focal Press (VLZelikman et.
al, Making and Coating Photographic Emulsion, Focal
Press, 1964) and the like. That is, any of an acidic method, a neutral method, an ammonia method, and the like may be used, and a method of reacting a soluble silver salt and a soluble halide may be any one of a one-sided mixed solution, a simultaneous mixing method, and a combination thereof. Good. A method of forming grains in the presence of excess silver ions (a so-called reverse mixing method) can also be used. As one type of the double jet method, a method in which pAg in a liquid phase in which silver halide is formed is kept constant, that is, a so-called controlled double jet method can be used. According to this method, a silver halide emulsion having a regular crystal form and a nearly uniform grain size can be obtained.

Two or more types of silver halide emulsions formed separately may be used as a mixture.

The silver halide emulsion consisting of the above-mentioned regular grains,
It is obtained by controlling pAg and pH during particle formation.
For details, see, for example, Photographic Science and Eng.
ineering, Vol. 6, pp. 159-165 (1962);
Journal of Pho
tographic Science), 12, 242-251 (1964), U.S. Pat. No. 3,655,394 and British Patent 1,413,748.

Monodisperse emulsions are silver halide grains having an average grain diameter of greater than about 0.1 micron, at least about
Emulsions where 95% by weight are within ± 40% of the average grain diameter are typical. Average particle diameter of about 0.25 to 2 microns, at least about 95% by weight or at least about 95% by volume
The emulsion in which the silver halide grains of the formula (1) are within the range of an average grain diameter of ± 20% can be used in the present invention. Methods for preparing such emulsions are described in U.S. Pat. Nos. 3,574,628 and 3,655,394 and British Patent 1,413,748. JP-A-48-8600, JP-A-51-39027, JP-A-51-83097, JP-A-53-13
7133, 54-48521, 54-99419, 58-37635,
Monodisperse emulsions such as those described in JP-A-58-49938 can be preferably used in the present invention.

Tabular grains having an aspect ratio of about 5 or more can also be used in the present invention. Tabular grains are described by Gatoff, Gutoff, Photographic Science and Engineerin.
g), 14, 248-257 (1970); U.S. Pat.
No. 226, 4,414,310, 4,433,048, 4,439,520 and British Patent No. 2,112,157, and can be easily prepared. When tabular grains are used, there are advantages such as improvement in color sensitization efficiency by a sensitizing dye, improvement in graininess and increase in sharpness, which are described in detail in U.S. Patent No. 4,434,226 cited above. ing.

The crystal structure may be uniform, the inside and the outside may be composed of different halogen compositions, or may have a layered structure. These emulsion grains are described in GB 1,027,146.
And U.S. Pat. Nos. 3,505,068 and 4,444,877 and Japanese Patent Application No. 58-248469. Further, silver halides having different compositions may be joined by an epitaxial junction, or may be joined to a compound other than silver halide, such as, for example, rhodan silver or lead oxide. These emulsion grains are described in U.S. Pat.Nos. 4,094,648 and 4,142,900.
No. 4,459,353, UK Patent No. 2,038,792, U.S. Pat.Nos. 4,349,622, 4,395,478, 4,433,501, 4,4
No.63,087, No.3,656,962, No.3,852,067, JP-A-59-1
No. 62540 and the like.

 Also, a mixture of particles of various crystal forms may be used.

The emulsion of the present invention is usually subjected to physical ripening, chemical ripening and spectral sensitization. The additive used in such a process is Research Disclosure No. 17643
And No. 18716, and the relevant locations are summarized in the table below.

Known photographic additives that can be used in the present invention are also described in the above two Research Disclosures, and their locations are shown in the table below.

Various color couplers can be used in the present invention, and specific examples are described in the patents described in the above-mentioned Research Disclosure (RD) No. 17643, VII-C-G. As the dye-forming coupler, a coupler that provides the three primary colors of the subtractive color method (that is, yellow, aagenta and cyan) by color development is important, and specific examples of the diffusion-resistant 4-equivalent or 2-equivalent coupler are described in RD17643, VII- C
In addition to the couplers described in the patents described above and around D, the following can be preferably used in the present invention.

Representative examples of the yellow coupler that can be used in the present invention include a hydrophobic acylacetamide-based coupler having a ballast group. An example is U.S. Pat.
Nos. 407,210, 2,875,057 and 3,265,506. In the present invention, the use of a two-equivalent yellow coupler is preferred, and U.S. Pat.
No. 3,447,928, Nos. 3,933,501 and 4,022,620, etc., and an oxygen atom desorbable yellow coupler or JP-B-58-10739, U.S. Pat. Nos. 4,401,752, 4,326,024, RD18053 (April 1979) , UK Patent No. 1,
No. 425,020, West German Application Publication No. 2,219,917, No. 2,261,36
No. 1, No. 2,329,587, and No. 2,433,812 are examples of the nitrogen atom-elimination type yellow couplers. α-pivaloylacetanilide-based couplers are excellent in the fastness of color-forming dyes, especially in light fastness, while α-benzoylacetoanilide-based couplers can provide high color density.

Magenta couplers that can be used in the present invention include hydrophobic, indazolone-based or cyanoacetyl-based, preferably 5-pyrazolone- and pyrazoloazole-based couplers having a ballast group. 5-pyrazolone-based couplers are preferably couplers 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. Representative examples thereof are described in U.S. Pat.
No. 311,082, No. 2,343,703, No. 2,600,788, No.
Nos. 2,908,573, 3,062,653, 3,152,896, and 3,936,015. Two equivalents of 5
-As a leaving group of a pyrazolone-based coupler, U.S. Pat.
Particularly preferred are nitrogen atom leaving groups described in 310,619 or arylthio groups described in US Pat. No. 4,351,897. Further, a 5-pyrazolone-based coupler having a ballast group described in European Patent No. 73,636 can obtain a high color density. U.S. Patent No.
Pyrazolobenzimidazoles described in U.S. Pat. No. 3,369,879, preferably pyrazolo [5,1-c] [1,2,4] triazoles described in U.S. Pat. No. 3,725,067, Research Disclosure 24220 (June 1984) ) And JP-A-60-33
Pyrazolotetrazole described in JP-A-552 and Research Disclosure 24230 (June 1984) and pyrazolopyrazoles described in JP-A-60-43659. The imidazo (1,2-) described in U.S. Pat.No.4,500,630 in terms of low yellow side absorption and light fastness of the coloring dye.
b] pyrazoles are preferred, and pyrazolo [1,5-b] [1,2,4] triazole described in U.S. Pat. No. 4,540,654 is particularly preferred.

Cyan couplers that can be used in the present invention include hydrophobic and diffusion-resistant naphthol-based and phenol-based couplers, and naphthol-based couplers described in U.S. Pat.No. 2,474,293, preferably U.S. Pat.
Representative examples thereof include oxygen atom-eliminating double-equivalent naphthol couplers described in 4,146,396, 4,228,233 and 4,296,200. Specific examples of phenolic couplers are described in U.S. Patent Nos. 2,369,929 and 2,801,1.
No. 71, 2,772,162 and 2,895,826. Humidity and temperature-resistant cyan couplers are preferably used in the present invention. Typical examples thereof include phenolic compounds having an alkyl group or more at the meta position of the phenolic nucleus described in U.S. Pat.No. 3,772,002. Cyan coupler, U.S. Pat. No. 2,772,162,
2,758,308, 4,126,396, 4,334,011, 4,327,173, West German Patent Publication 3,329,729 and European Patent 121,365, etc. issue,
No. 4,333,999, No. 4,451,559 and No. 4,427,76
Phenol couplers having a phenylureido group at the 2-position and having an acylamino group at the 5-position, and 5-aminonaphthol-based couplers described in European Patent No. 161,626A described in, for example, No. 7.

In order to correct unnecessary absorption of various coloring elements, it is preferable to perform masking by using a colored coupler in combination with a color photographic material for photography. U.S. Pat.No. 4,163,670 and Japanese Patent Publication No. 5
Typical examples include a yellow-colored magenta coupler described in JP-A-7-39413 or a magenta-colored cyan coupler described in U.S. Pat. Nos. 4,004,929, 4,138,258 and British Patent 1,146,368. Other colored couplers are described in RD17643, VII-G.

Granularity can be improved by using a coupler in which the coloring dye has an appropriate diffusibility. Such couplers are disclosed in U.S. Pat.No. 4,366,237 and British Patent 2,125,570.
No. 1 contains specific examples of magenta couplers, and EP 96,5
No. 70 and West German Application Publication No. 3,234,533 have yellow,
Specific examples of magenta or cyan couplers are described.

Dye-forming couplers and the above-mentioned special couplers may form polymers of dimers or more. Typical examples of polymerized dye-forming couplers are described in U.S. Patent Nos. 3,451,820 and 4,080,211. Specific examples of polymerized magenta couplers are described in British Patent No. 2,102,173 and US Patent No. 4,367,282.

Couplers that release a photographically useful residue upon coupling can also be preferably used in the present invention. As the DIR coupler releasing the development inhibitor, the couplers of the patents described in the aforementioned RD17643, VII-F are useful.

Preferred in combination with the present invention is described in JP-A-57-1
Developer inactivated type represented by 51944; U.S. Pat. No. 4,248,9
No. 62 and Japanese Patent Application Laid-Open No. 57-154234; and a reaction type represented by Japanese Patent Application No. 59-39653. Particularly preferred are those disclosed in Japanese Patent Application Laid-Open Nos. 57-151944 and 58-217932. issue,
JP-A-59-75474, JP-A-59-82214, JP-A-59-82214 and JP-A-59-90438 describe a developer-inactivating type DIR coupler and JP-A-59-39653. It is a reactive DIR coupler.

In the light-sensitive material of the present invention, a coupler which releases a nucleating agent or a development accelerator or a precursor thereof in an image-like manner during development can be used. Specific examples of such compounds are described in British Patent Nos. 2,097,140 and 2,131,188. Couplers which release a nucleating agent having an adsorbing action on silver halide are particularly preferred, and specific examples thereof are described in JP-A-59-157638 and JP-A-59-170840.

Suitable supports that can be used in the present invention include, for example, those described above.
From page 28 of RD.No.17643 and from page 647 of No.18716, right column
It is described in the left column on page 648.

The color photographic light-sensitive material according to the present invention includes the RD, N
Developing can be carried out by a conventional method described in o. 17643, pp. 28-29, and No. 18716, p. 651, left column to right column.

The color photographic light-sensitive material of the present invention is usually subjected to a washing treatment or a stabilization treatment after the development, bleach-fixing or fixing treatment.

In the water washing step, two or more tanks are generally countercurrently washed to save water. As a stabilizing treatment, a multi-stage countercurrent stabilizing treatment as described in JP-A-57-8543 may be mentioned as a representative example instead of the washing step. In the case of this step, 2 to 9 countercurrent baths are required. Various compounds are added to the stabilizing bath for the purpose of stabilizing an image. For example, various buffers (for example, borate, metaborate, borax, phosphate, carbonate, potassium hydroxide, sodium hydroxide, aqueous ammonia) for adjusting the membrane pH (for example, pH 3 to 8) Carboxylic acid, dicarboxylic acid, polycarboxylic acid, etc.) and formalin. In addition, if necessary, water softeners (inorganic phosphoric acid, aminopolycarboxylic acid, organic phosphoric acid, aminopolyphosphonic acid, phosphonocarboxylic acid, etc.), bactericides (benzoisothiazolinone, irithiazolone, 4-thiazoline benzimidazole) , Halogenated phenols, etc.), surfactants, optical brighteners, hardeners and the like, or two or more of the same or different desired compounds may be used in combination.

Also, ammonium chloride as a membrane pH adjuster after treatment,
It is preferable to add various ammonium salts such as ammonium nitrate, ammonium sulfate, ammonium phosphate, ammonium sulfite, and ammonium thiosulfate.

The present invention can be applied to various color light-sensitive materials. Typical examples include color negative films for general use or movies, color reversal films for slides or televisions, color papers, color positive films, and color reversal papers. The present invention also relates to Research Disclosure 17123 (July 1978).
The present invention can also be applied to black-and-white light-sensitive materials utilizing a mixture of three-color couplers described in the above.

Example 1. On a subbed cellulose triacetate film support, a sample 101, which is a multilayer color photosensitive material composed of each layer having the following composition, was prepared.

The amount coated amount (Composition of photosensitive layer) is represented in units of g / m ² of silver for silver halide and colloidal silver, also couplers, the amount for the additives and gelatin, expressed in units of g / m ^2, The sensitizing dyes are shown in terms of moles per mole of silver halide in the same layer.

First layer (anti-halation layer) Black colloidal silver 0.2 Gelatin 1.3 ExM-9 0.06 UV-1 0.03 UV-2 0.06 UV-3 0.06 So1v-1 1.15 Solv-2 0.05 Solv-3 0.05 Second layer (Intermediate layer) Gelatin 1.0 UV-1 0.03 ExC-4 0.02 ExF-1 0.004 Solv-1 0.1 Solv-2 0.1 Third layer (low-sensitivity red-sensitive emulsion layer) Silver iodobromide emulsion Silver coating amount 1.2 (4 mol% AgI, uniform AgI type, Equivalent sphere diameter 0.5 μm, Coefficient of variation of equivalent sphere diameter 20%, tabular grain, diameter / thickness 3.0) Silver iodobromide emulsion Silver coating 0.6 (AgI 3 mol%, uniform AgI type, equivalent sphere diameter 0.3 μm, equivalent sphere) Coefficient of variation of diameter 15%, spherical particles, diameter / thickness 1.0) Gelatin 1.0 ExS-1 4 × 10 ^-4 ExS-2 5 × 10 ^-5 ExC-1 0.05 ExC-2 0.50 ExC-3 0.01 ExC-4 0.12 ExC -5 0.04 4th layer (high-sensitivity red-sensitive emulsion layer) Silver iodobromide emulsion Silver coating amount 0.7 (AgI 6 mol%, internal shell high AgI type with core shell ratio 1: 1, equivalent sphere diameter 0.7 μm, variation in equivalent sphere diameter) Coefficient 1 5%, plate-like particles, diameter / thickness ratio 5.0) Gelatin 1.0 ExS-1 3 × 10 ^-4 ExS-2 2.3 × 10 ^-5 ExC-6 0.11 ExC-7 0.05 ExC-4 0.05 Solv-1 0.05 Solv-3 0.05 5th layer (intermediate) Gelatin 0.5 Cpd-1 0.1 Solv-1 0.05 6th layer (low-sensitivity edge-sensitive emulsion layer) Silver iodobromide emulsion Silver coating 0.35 (AgI4 mol%, core height 1: 1 surface height) AgI type, equivalent sphere diameter 0.5 μm, coefficient of variation of equivalent sphere diameter 15%, plate-like grains, diameter / thickness ratio 4.0) Silver iodobromide emulsion Coating amount 0.20 (AgI 3 mol%, uniform AgI type, equivalent sphere diameter 0.3) μm, coefficient of variation of equivalent sphere diameter 25%, spherical particle, diameter / thickness ratio 1.0) Gelatin 1.0 ExS-3 5 × 10 ^-4 ExS-4 3 × 10 ^-4 ExS-5 1 × 10 ^-4 ExM-8 0.32 ExM-9 0.02 ExM-10 0.01 ExY-13 0.03 Solv-1 0.3 Solv-4 0.05 7th layer (high-sensitivity green-sensitive emulsion layer) Silver iodobromide emulsion Silver coating amount 0.8 (AgI4 mol%, core shell ratio 1: 3) High internal AgI type, equivalent ball diameter 0.7 μm, equivalent ball diameter Variation coefficient 20%, tabular grain, diameter / thickness ratio 5.0) Gelatin ^{0.5 ExS-3 5 × 10 -4} ExS-4 3 × 10 -4 ExS-5 1 × 10 -4 ExM-8 0.13 ExM-9 0.02 ExY -11 0.03 ExC-2 0.03 ExM-14 0.01 Solv-1 0.2 Solv-4 0.01 Eighth layer (intermediate layer) Gelatin 0.5 Cpd-1 0.05 Solv-1 0.02 Ninth layer (donor layer of multilayer effect on red sensitive layer) Silver iodobromide emulsion coated silver amount 0.35 (2 mol% AgI, internal high AgI type with a core shell ratio of 2: 1, equivalent sphere diameter 1.0 μm, coefficient of variation of equivalent sphere diameter 15%, plate-like grains, diameter / thickness ratio 6.0) Silver iodobromide emulsion Silver coating 0.20 (2 mol% AgI, internal high AgI type with a core shell ratio of 1: 1, equivalent sphere diameter 0.4 μm, coefficient of variation of equivalent sphere diameter 20%, plate-like grains, diameter / thickness ratio 6.0) Gelatin 0.5 ExS-3 8 × 10 ^-4 ExY-13 0.11 ExM-12 0.03 ExM-14 0.10 Solv-1 0.20 Layer 10 (yellow filter layer) Yellow colloidal silver 0.05 Gelatin 0.5 Cpd-2 0.13 Solv-1 0.13 Cpd- 1 0 .10 Eleventh layer (low-sensitivity blue-sensitive emulsion layer) Silver iodobromide emulsion Silver coating 0.3 (AgI 4.5 mol%, uniform AgI type, equivalent spherical diameter 0.7 μm, coefficient of variation of equivalent spherical diameter 15%, plate shape Grain, diameter / thickness ratio 7.0) Silver iodobromide emulsion Silver coating 0.15 (AgI 3 mol%, uniform AgI type, equivalent sphere diameter 0.3 μm, coefficient of variation of equivalent sphere diameter 25%, plate-like particle, diameter / thickness ratio 7.0 ) Gelatin 1.6 ExS-6 2 × 10 ^-4 ExC-16 0.05 ExC-2 0.10 ExC-3 0.02 ExY-13 0.07 ExY-15 1.0 Solv-1 0.20 12th layer (high-sensitivity blue-sensitive emulsion layer) Silver iodobromide Emulsion Coating silver amount 0.5 (AgI 10 mol%, internal high AgI type, equivalent spherical diameter 1.0 μm, coefficient of variation of equivalent spherical diameter 25%, multiple twin grains, diameter / thickness ratio 2.
0) Gelatin 0.5 ExS-6 1 × 10 ^-4 ExY-15 0.20 ExY-13 0.01 Solv-1 0.10 Layer 13 (first protective layer) Gelatin 0.8 UV-4 0.1 UV-5 0.15 Solv-1 0.01 Solv-2 0.01 14th layer (2nd protective layer) Fine grain silver bromide emulsion 0.5 (2 mol% AgI, uniform AgI type, equivalent sphere diameter 0.07 μm) Gelatin 0.45 Polymethyl methacrylate particles 0.2 (1.5 μm diameter) H-1 0.4 Cpd-5 0.5 Cpd-6 0.5 In addition to the above components, each layer contains an emulsion stabilizer Cpd-3.
(0.04 g / mp ² ) Surfactant Cpd-4 (0.02 g / m ² ) was added as a coating aid.

 The sample manufactured as described above was used as Sample 101.

Samples 102 to 110 were prepared by using cyan couplers ExC-2 and ExC-6 and DIR coupler E in the red-sensitive emulsion layer of Sample 101.
It was produced in the same manner as in Sample 101 except that xC-5 was changed as shown in Table 1.

Samples 101 to 110 were subjected to red exposure using a continuous wedge, and further to uniform green exposure. The processing described below was performed, and the density of the developed film was measured through red and green filters. The cyan color image showed almost the same sensitivity and gradation.

ΔD as defined below for red exposure
(G) was determined. The results are summarized in Table 1.

ΔD (G) = D (G) −Dmin (G) Here, D (G) represents an optical density through a green filter at a certain exposure amount. Dmin (G) represents the magenta density at the exposure amount that gives the minimum cyan density.

Next, the chemical structural formulas or chemical names of the compounds used in the examples are described.

H-1 (hardener) The following processing was performed on the sample by an automatic developing machine. The processing steps shown in Table 1 are referred to as development processing A.

In the above process, stable,
The countercurrent method was adopted. The amount of fixer brought into the stability tank was 2 ml per meter.

Further, development processing B is performed in the same manner as in the previous processing method A.
And the cyan density were compared. In the developing process B, the bleaching solution of the developing process A was changed to the following persulfuric acid bleaching solution. Except for the bleaching solution, the substantially same method as in the development processing A was used. Persulfuric acid bleaching bath for processing B Prescription value Water at 24 to 38 ° C 800ml Gelatin 0.5g Sodium persulfate 33g Sodium chloride 15.0g Sodium monobasic phosphate (anhydrous) 9.0g Phosphoric acid (58%) 2.5ml Add water 1.0l pH (27 ° C) 2.3 ± 0.2 The results obtained are shown in Table 1.

As is clear from Table 1, in the present invention, a substantially uniform magenta color density is obtained, and it is clear that the combination of the coupler of the present invention is excellent. In order to obtain a uniform magenta density with the combination of the couplers of the comparative examples,
Further, it is necessary to increase the amount of the DIR coupler, and at this time, there is a problem that the sensitivity of cyan color cannot be reduced.

Further, in the case of the combination of the couplers of the comparative examples, a sufficient cyan density was not obtained in the developing treatment B, which indicates that the cyan coupler was not suitable in the persulfuric acid bleaching step.

Example 2 In the sample 101 manufactured in Example 1, the sixth layer and the ninth layer
Samples 202 to 207 were produced in the same manner as in Sample 101 except that the couplers shown in Table 2 were used instead of the ExY-13 layers, the eleventh layer, and the twelfth layer.

After the sample 101 and the prepared samples 202 to 207 were cut into strips, they were exposed through a chart for MTF evaluation for sharpness evaluation. These were processed through the development processing (A) used in Example 1.

Table 2 shows the results.

The results in Table 2 show that all the samples have high sensitivity and excellent sharpness. In particular, among the couplers represented by the general formula (I), samples using couplers (n (2), (4), (5), (17), and (31)) with n + m + 1 + p = 3 are sharp. The degree was high. Further, in Samples 205 and 207 produced by using the coupler represented by the general formula (I) in an appropriate combination, the linearity of the gradation portion was good when exposed using a continuous wedge, and the uniformity was obtained over a wide exposure range. It is clear that they exhibit a development suppressing effect and are preferable in color reproduction.

Continuation of the front page (56) References JP-A-62-166334 (JP, A) JP-A-63-17448 (JP, A) JP-A-62-272246 (JP, A) JP-A-61-267046 (JP) , A) JP-A-64-4743 (JP, A)

Claims (1)

(57) [Claims] (1) Among the couplers represented by the following general formula (I), at least one coupler having l + m + p + n of 3 and at least one coupler having l + m + p + n of 0, 1, or 2 are formed in the same photosensitive layer. A silver halide color photographic light-sensitive material, characterized by containing at least one cyan coupler represented by the following general formula (II) or (III). Formula (I) A-{(L ₁ ) 1- (B) m} p- (L ₂ ) n-DI In the formula, A reacts with an oxidized aromatic primary amine developer to form A L ₁ represents a group that can be cleaved from a bond other than a residue, and L ₁ cleaves a bond on the right side (bond with (B) m) when a bond on the left side of L ₁ represented by the general formula (I) is cleaved. B represents a group that reacts with an oxidized developing agent to cleave the bond on the right side of B represented by the general formula (I), and L ₂ represents a group on the left side of L ₂ represented by the general formula (I) Represents a group in which the bond on the right is cleaved when the bond is cleaved, DI represents a development inhibitor, l, m and n each represent 0 or 1, and p represents 0 or 1.
Represents an integer of 1 to 3. Here, when there are a plurality of p, p (L ₁ ) l- (B) m represent the same or different ones. However, both l and m are 1 and p is not 0, and both l and m are 0 and p is not a positive number. In the formula, R ₁ represents an aromatic group or a heterocyclic group, R ₂ represents a group that can be substituted on a benzene ring, R ₃ represents an aliphatic group, a represents an integer of 0 to 3, and b represents And Z ₁ represents a hydrogen atom or a coupling-off group, and Z ₁ in the general formulas (II) and (III) represents an integer of 0 to 3.
₁ may be different from each other. Z ₂ is -O-, -S-,
Or Represents Provided that R ₄ represents a hydrogen atom or an organic substituent, and when a and b are plural, R ₂ in the general formulas (II) and (III) may be the same or different, and To form a ring. In the general formula (III), R ₂ and Z ₂ or Z ₂ and Z ₁ may be bonded to each other to form a ring. Also, R ₁ ,
R ₂ , R ₃ , R ₄ , Z ₂ or Z ₁ may form a dimer or higher multimer.