JP2838143B2 - Silver halide color photographic materials - Google Patents

Description

Description: FIELD OF THE INVENTION The present invention relates to a silver halide color photographic light-sensitive material. More specifically, the present invention relates to a silver halide color photographic light-sensitive material containing at least two kinds of cyan couplers having a specific structure in the same layer, and making the light-sensitive material extremely light-sensitive. The present invention relates to a silver halide color photographic light-sensitive material which does not deteriorate in color developing performance even when stored at a low temperature.

(Prior Art) Using an exposed silver halide as silver oxide, an oxidized aromatic primary amine color developing agent reacts with a coupler to form indophenol, indoaniline, indamine,
It is well known that azomethine, phenoxazine, phenazine and similar dyes form and form color images.

Of these, phenolic couplers or naphthol couplers known as cyan image forming couplers have a low colorfastness to heat or light of a color image formed by color development, or a bleaching solution ( Bleach-fix solution) or tired bleach solution (bleach-fix solution)
It has been pointed out that a disadvantage arises in that the color density is lowered when a development process is carried out using the above. As a coupler which has improved such a defect, a 5-position-substituted haphtol cyan coupler has been proposed in European Patent Publication No. 161626A. Cyan dyes obtained from these cyan couplers were excellent in that they were excellent in light fastness and heat fastness and that the spectral absorption of the color image hardly depended on the color density.

These couplers have a problem that the sharpness is inferior when a high boiling point organic solvent is used in a large amount relative to the coupler, and a method in which only a small amount of the high boiling point organic solvent is used is disclosed in JP-A-62-2699.
No. 58 was proposed.

However, when a photographic material containing only a small amount of an organic solvent having a high boiling point for these couplers is stored at an extremely low temperature, the problem that the coloring property is remarkably reduced has become apparent.

On the other hand, JP-A-54-60924 discloses a photosensitive material containing two or more acylaminophenol-based cyan couplers, and JP-A-59-100440 and JP-A-60-242457 disclose acylaminophenol-based cyan couplers. Photosensitive materials using a cyan coupler and a diacylaminophenol-based cyan coupler in the same layer are known and have improved solubility, dispersion stability, spectral absorption characteristics, etc., but the naphthol-based cyan coupler of the present invention is The structure was completely different, and there was a problem in both the preservability of the cyan image and the color development.

A combination of the cyan coupler of the present invention with a phenolic cyan coupler having an arylureido group at the 2-position is disclosed in JP-A-62-75444, and a combination of a naphthol-based cyan coupler having an arylcarbamoyl group at the 2-position is disclosed in JP-A-62-75444. Although it is proposed in JP-A-62-91947, the composition and effect are different from those of the present invention. When the amount of the high-boiling organic solvent is reduced as in the present invention by the combination, the color image is reduced. The shelf life was not sufficient.

(Problems to be Solved by the Invention) The first object of the present invention is to provide a silver halide color photographic light-sensitive material exhibiting high color developability even when stored at an extremely low temperature (1 to 15 ° C. or lower). Secondly, to provide a photosensitive material having excellent cyan image preservability, and thirdly, to provide a photosensitive material which is stable in an emulsion of a coupler and a coating solution and has excellent production stability. A fourth object is to provide a photosensitive material having excellent film strength and excellent sharpness.
Another object of the present invention is to provide a light-sensitive material in which the cyan image density does not fluctuate even when it is processed with a bleaching solution and a bleach-fixing solution which has been fatigued.

(Means for Solving the Problems) An object of the present invention is to provide a silver halide color photographic material having at least one silver halide emulsion layer on a support, wherein at least one layer has the following general formula [A ]
Wherein at least one substituent of R ₁ , R ₂ and R ₃ is different, and the high-boiling organic solvent in the layer further comprises at least one of the following couplers: This was achieved by a silver halide color photographic material characterized in that the weight ratio was at most 0.3 with respect to the total amount of the cyan coupler.

General formula [A] In the general formula (A), R ₁ is a halogen atom, an aliphatic group, an aromatic group, a heterocyclic group, an amidino group, a guanidino group or COR ₄ , —SO ₂ R ₄ , —SOR ₄ , Represents a group represented by, R ₂ is a halogen atom, a hydroxyl group, a carboxyl group, a sulfo group, an amino group, a cyano group, a nitro group, an aliphatic group, an aromatic group, a carboxamide group, a sulfonamide group, a carbamoyl group, Sulfamoyl group, ureido group, acyl group, acyloxy group, aliphatic oxy group, aromatic oxy group, aliphatic sulfonyl group, aromatic sulfonyl group, aliphatic sulfinyl group, aromatic sulfinyl group, aliphatic oxycarbonyl group, aromatic Oxycarbonyl group, aliphatic oxycarbonylamino group, aromatic oxycarbonylamino group, sulfamoylamino group,
Represents a heterocyclic group or an imido group, l 'is 0 to an integer of 3, R ₃ represents a hydrogen atom or R ₆ U, T is cup hydrogen atom or an aromatic primary amine developing agent oxidized form Represents a group capable of leaving by a ring reaction. However, R ₄ and R ₅ each independently represent an aliphatic group, an aromatic group, a heterocyclic group, an amino group, an aliphatic oxy group, or an aromatic oxy group, and R ₆ represents a hydrogen atom, an aliphatic group, an aromatic group. Group, heterocyclic group, _{-PO (R 7) 2, -PO} (-OR 2) 2, -CO ₂ R ₇ , -SO ₂ R ₇ , -SO ₂ OR ₇ or an imide group,
U is _{N-R 9, -CO -,} - SO 2 -, - SO- or a single bond. Here, R ₇ represents an aliphatic group, an aromatic group or a heterocyclic group, R ₈ represents a hydrogen atom, an aliphatic group, an aromatic group or a heterocyclic group, and R ₉ and R ₁₀ each independently represent a hydrogen atom , An aliphatic group, an aromatic group, a heterocyclic group, an acyl group, an aliphatic sulfonyl group or an aromatic sulfonyl group.

When 1 ′ is plural, R ₂ may be the same or different, and may combine with each other to form a ring. R ₂ and
R ₃ or R ₃ and T may be bonded to each other to form a ring.

 Hereinafter, the compounds used in the present invention will be described.

Here, the aliphatic group is a linear, branched or cyclic,
Represents an alkyl group, an alkenyl group or an alkynyl group,
It may be substituted or unsubstituted. The aromatic group refers to a substituted or unsubstituted aryl group, and may be a condensed ring. The heterocycle refers to a substituted or unsubstituted monocyclic or fused-ring heterocyclic group. Specific examples of the aliphatic group include methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, t-butyl, cyclopentyl, t-pentyl, cyclohexyl,
n-octyl group, 2-ethylhexyl group, n-decyl group, n-dodecyl group, n-tetradecyl group, n-hexadecyl group, n-octadecyl group, 2-hexyldecyl group, adamantyl group, trifluoromethyl group, carboxy Methyl group, methoxyethyl group, vinyl group, allyl group,
Hydroxyethyl group, heptafluoropropyl group, benzyl group, phenethyl group, phenoxyethyl group, methylsulfonylethyl group, methylsulfonamidoethyl group, 3
-(2-ethylhexyloxy) propyl group, 3-n-
Decyloxypropyl group, 3-n-dodecyloxypropyl group, 3-n-tetradecyloxypropyl group, oleyl group, propargyl group, ethynyl group, 3- (2,4-di-t-pentylphenoxy) propyl group, 4- (2,4-
Di-t-pentylphenoxy) butyl group, 1- (2,4-
Di-t-pentylphenoxy) propyl group, 1- (2,4
-Di-t-pentylphenoxy) pentyl group, 1- (3
-Tetradecylphenoxy) propyl group, 2-n-dodecylthioethyl group and the like.

Specific examples of the aromatic group include a phenyl group, a p-tolyl group, an m-tolyl group, an o-tolyl group, a 4-chlorophenyl group, a 4-nitrophenyl group, a 4-cyanophenyl group,
4-hydroxyphenyl group, 3-hydroxyphenyl group, 1-naphthyl group, 2-naphthyl group, o-biphenylyl group, p-phenylyl group, pentafluorophenyl group,
2-methoxyphenyl group, 2-ethoxyphenyl group, 4
-Methoxyphenyl group, 4-t-butylphenyl group, 4
-T-octylphenyl group, 4-carboxyphenyl group, 4-methylsulfonamidophenyl group, 4- (4-
(Hydroxyphenylsulfonyl) phenyl group, 2-n-
Tetradecyloxyphenyl group, 4-n-tetradecyloxyphenyl group, 2-chloro-5-n-dodecyloxyphenyl group, 3-n-pentadecylphenyl group, 2-
Chlorophenyl group, 4-methoxycarbonylphenyl group, 4-methylsulfonylphenyl group, 2,4-di-t-
And a pentylphenyl group.

Specific examples of the heterocyclic group include a 2-pyridyl group, a 3-pyridyl group, a 4-pyridyl group, a 2-furyl group, a 2-thienyl group, a 3-thienyl group, a 4-quinolyl group, a 2-imidazolyl group, Benzimidazolyl group, 4-pyrazolyl group,
2-benzoxazolyl group, 2-benzothiazolyl group,
1-imidazolyl group, 1-pyrazolyl group, 5-tetrazolyl group, 1,3,4-thiadiazol-2-yl group, 2-prolyl group, 3-triazolyl group, 4-oxazolyl group,
4-thiazolyl group, 2-pyrimidyl group, 2-pyrimidyl group, 1,3,5-triazin-2-yl group, 1,3,4-oxadiazol-2-yl group, 5-pyrazolyl group, 4- Pyrimidyl group, 2-pyrazyl group, succinimide group, phthalimide group, morpholino group, pyrrolidino group, piperidino group,
Imidazolidine-2,4-diole-3-yl group, imidazolidine-2,4-dione-1-yl group, oxazolidine-
There are a 2,4-di-on-3-yl group and the like.

Next, each substituent in the general formula [A] will be described in detail.

In the general formula [A], R ₁ is a halogen atom, an aliphatic group,
Aromatic group, heterocyclic group, amidino group, guanidino group or
COR ₄ , −SO ₂ R ₄ , Represents a group represented by Here, R ₄ and R ₅ are each independently an aliphatic group having 1 to 30 carbon atoms, an aromatic group having 6 to 30 carbon atoms, a heterocyclic group having 1 to 30 carbon atoms, and 0 carbon atoms.
To 30 amino groups [for example, amino group, methylamino group, dimethylamino group, n-butylamino group, anilino group, N
-(2-n-tetradecyloxyphenyl) amino group,
Pyrrolidino group, morpholino group, piperidino group, 2-ethylhexylamino group, n-dodecylamino group, N-methyl-N-dodecylamino group, 3-dodecyloxypropylamino group, 3- (2,4-di-t- Pentylphenoxy) propylamino group, 4- (2,4-di-t-pentylphenoxy) butylamino group and the like], aliphatic oxy group having 1 to 30 carbon atoms [for example, methoxy group, ethoxy group, butoxy group, methoxy group] An ethoxy group, an n-dodecyloxy group,
3- (2,4-di-t-bentylphenoxy) propoxy group or the like] or an aromatic oxy group having 6 to 30 carbon atoms [for example, phenoxy group, 4-n-dodecyloxyphenoxy group, 4-methoxycarbonylphenoxy group] Group etc.]. R ₄ and R ₅ may combine with each other to form a ring.
When R ₁ is a halogen atom, the halogen atom includes a fluorine atom, a chlorine atom, a bromine atom and an iodine atom. When R ₁ is an amidino group or a guanidino group, its total carbon atom number is 1
~ 30, substituted with an aliphatic group, an aromatic group, a hydroxy group, an aliphatic oxy group, an acyl group, an aliphatic sulfonyl group, an aromatic sulfonyl group, an acyloxy group, an aliphatic sulfonyloxy group or an aromatic sulfonyloxy group And two nitrogen atoms may be bonded to each other to form a heterocyclic ring such as imidazole and benzimidazole.

In the general formula [A], R ₂ is a halogen atom (a fluorine atom, a chlorine atom, a bromine atom or an iodine atom), a hydroxy group, a carboxy group, a sulfo group, a cyano group, a nitro group, an amino group having 0 to 30 carbon atoms ( For example, amino group, methylamino group, dimethylamino group, pyrrolidino group, anilino group, etc.), aliphatic group having 1 to 30 carbon atoms, 6 to 30 carbon atoms
An aromatic group, a carbonamide group having 1 to 30 carbon atoms (for example, a formamide group, an acetamido group, a trifluoroacetamido group, a benzamide group, etc.), a carbon atom having 1 to 30 carbon atoms
A sulfonamide group (for example, a methylsulfonamide group,
Trifluoromethylsulfonamide group, n-butylsulfonamide group, p-tolylsulfonamide group, etc., carbamoyl group having 1 to 30 carbon atoms (for example, carbamoyl group, N, N-dimethylcarbamoyl group, N-methylcarbamoyl group) , A pyrrolidinocarbonyl group, a Nn-hexadecylcarbamoyl group, etc.), a sulfamoyl group having 0 to 30 carbon atoms (for example, a sulfamoyl group, an N-methylsulfamoyl group, an N, N-dimethylsulfamoyl group, a morpholino) A sulfonyl group, an N, n-dodecylsulfamoyl group, etc.), a ureido group having 1 to 30 carbon atoms (for example, a ureido group, a 3-methylureido group, a 3-phenylureido group,
An acyl group having 1 to 30 carbon atoms (eg, acetyl group, pivaloyl group, benzoyl group, dodecanoyl group), an acyloxy group having 1 to 30 carbon atoms (eg, acetoxy group, benzoyl) Oxy group, etc.), an aliphatic oxy group having 1 to 30 carbon atoms, an aromatic oxy group having 6 to 30 carbon atoms, an aliphatic thio group having 1 to 30 carbon atoms, an aromatic group having 6 to 30 carbon atoms Thio group, 1 carbon atom
Aliphatic sulfonyl group having up to 30 carbon atoms, aromatic sulfonyl group having 6 to 30 carbon atoms, aliphatic sulfinyl group having 1 to 30 carbon atoms, aromatic sulfinyl group having 6 to 30 carbon atoms, 2 to 30 carbon atoms An aliphatic oxycarbonyl group having 7 carbon atoms
An aliphatic oxycarbonyl group having from 30 to 30 carbon atoms, an aliphatic oxycarbonylamino group having from 2 to 30 carbon atoms, an aromatic oxycarbonylamino group having from 7 to 30 carbon atoms, and a sulfamoylamino group having from 0 to 30 carbon atoms ( For example, a sulfamoylamino group, a 3,3-dimethylsulfamoylamino group, a piperidinosulfonylamino group, etc.), a heterocyclic group having 1 to 30 carbon atoms or an imide group having 4 to 30 carbon atoms (eg, succinimide A maleimide group, a phthalimide group, a diglycolimide group, a 4-nitrophthalimide group, etc.).

In the general formula [A], R ₃ represents a hydrogen atom or R ₆ U. Here, R ₆ is a hydrogen atom, an aliphatic group having 1 to 30 carbon atoms, an aromatic group having 6 to 30 carbon atoms, a heterocyclic group having 1 to 30 carbon atoms, -OR ₇ , —SO ₂ OR ₇ or an imide group having 4 to 30 carbon atoms (for example, a succinimide group, a maleimide group, a phthalimide group,
U represents N—R ₉ , —CO
—, —SO ₂ —, —SO— or a single bond, wherein R ₇ is an aliphatic group having 1 to 30 carbon atoms, an aromatic group having 6 to 30 carbon atoms or a heterocyclic ring having 1 to 30 carbon atoms. R ₈ represents a hydrogen atom, an aliphatic group having 1 to 30 carbon atoms, 6 to 30 carbon atoms
Represents an aromatic group or a heterocyclic group having 1 to 30 carbon atoms, wherein R ₉ and R ₁₀ each independently represent a hydrogen atom, an aliphatic group having 1 to 30 carbon atoms, or an aromatic group having 6 to 30 carbon atoms. A heterocyclic group having 1 to 30 carbon atoms, an acyl group having 1 to 30 carbon atoms (such as an acetyl group, a trifluoroacetyl group, a benzoyl group, a p-chlorobenzoyl group) or a group having 1 to 30 carbon atoms. Sulfonyl group (for example, methylsulfonyl group, n
-Butylsulfonyl group, phenylsulfonyl group, p-nitrophenylsulfonyl group, etc.). R ₉ and R ₁₀ may be bonded to each other to form a ring.

In the general formula [A], T represents a hydrogen atom or a group capable of leaving by a coupling reaction with the oxidizing property of an aromatic primary amine developer. Examples of the latter include halogen atoms (fluorine atom, chlorine atom, bromine atom and iodine atom), sulfo group, thiocyanato group, isothiocyanato group, selenocyanato group, resin oxy group having 1 to 30 carbon atoms, carbon An aromatic oxy group having 6 to 30 carbon atoms, an aliphatic thio group having 1 to 30 carbon atoms, an aromatic thio group having 6 to 30 carbon atoms, a heterocyclic thio group having 1 to 30 carbon atoms, and a carbon atom number 1 to
30 heterocyclic oxy groups, aromatic azo groups having 6 to 30 carbon atoms, heterocyclic groups having 1 to 30 carbon atoms, acyloxy groups having 1 to 30 carbon atoms (eg, acetoxy group, benzoyloxy group, etc.), A sulfonyloxy group having 1 to 30 carbon atoms (eg, methylsulfonyloxy group, p-tolylsulfonyloxy group, etc.), a carbamoyloxy group having 1 to 30 carbon atoms (eg, N, N-dimethylcarbamoyloxy group, pyrrolidinocarbonyl An oxy group, an N-ethylcarbamoyloxy group, etc.), a thiocarbonyloxy group having 2 to 30 carbon atoms (for example, a methylthiocarbonyloxy group, a phenylthiocarbonyloxy group, etc.) and a carbonyldioxy group having 2 to 30 carbon atoms ( Examples thereof include a methoxycarbonyloxy group and a phenoxycarbonyloxy group).

In the general formula [A], R ₂ and R ₃ , R ₂ and T or
R ₂ may combine with each other to form a ring. R ₂ and
-CH ₂ CO as an example in which the R ₃ is attached -, - OCO -, - NHCO
_{-, - C (CH 3)} 2 CO -, - there CH = CHCO- like. R ₃ and T
Doo is -CH ₂ C Examples of binding -, - COO- or the like is. Examples of bonding of a plurality of R ₂ include-(CH ₂ ) ₃ -,-(CH ₂ ) ₄
-, -OCO-, -OCONH-, -NHCONH-,-(CH = CH) _{2
-, - OCH 2 O -,} - OCH 2 CH 2 O -, - OC (CH 3) there are ₂ O- and the like.

Next, examples of preferred substituents in the compound represented by the general formula [A] will be described below.

In the general formula [A], R ₁ is preferably a halogen atom, —COR ₄ or —SO ₂ R _{4, and} more preferably R ₄ is an amino group. Examples of -COR ₄ include a carbamoyl group, N-
Ethylcarbamoyl group, Nn-butylcarbamoyl group, N-cyclohexylcarbamoyl group, N- (2-ethylhexyl) carbamoyl group, N-dodecylcarbamoyl group, N-hexadecylcarbamoyl group, N- (3-
Decyloxypropyl) carbamoyl group, N- (3-dodecyloxypropyl) carbamoyl group, N- [3-
(2,4-di-t-pentylphenoxy) propyl] carbamoyl group, N- [4- (2,4-di-t-pentylphenoxy) butyl] carbamoyl group, N, N-dimethylcarbamoyl group, N, N -Dibutylcarbamoyl group, N-methyl-N-dodecylcarbamoyl group, morpholinocarbabonyl group, N-methyl-N-phenylcarbamoyl group, N
-(2-tetradecyloxyphenyl) carbamoyl group, N-phenylcarbamoyl group, N- (4-tetradecyloxyphenyl) carbamoyl group, N- (2-propoxyphenyl) carbamoyl group, N- (2-chloro-
5-dodecyloxyphenyl) carbamoyl group, N-
(2-chlorophenyl) carbamoyl group and the like,
Examples of ₂ R ₄ include a sulfamoyl group, an N-methylsulfamoyl group, an N, N-diethylsulfamoyl group, an N, N-diisopropylsulfamoyl group, an N- (3-dodecyloxypropyl) carbamoyl group, N- [3- (2,4-di-t-pentylphenoxy) propyl] carbamoyl group, N- [4- (2,4-di-t-pentylphenoxy)
Butyl] carbamoyl group, pyrrolidinosulfonyl group, N
-Phenylsulfonyl group, N- (2-butoxyphenyl) carbamoyl group, N- (2-tetradecyloxyphenyl) carbamoyl group and the like. Especially as R _1- COR ₄
(R ₄ is an amino group) is preferred.

In the general formula [A], (R ₂ ) l ′ is preferably l ′
= 0 and then l ′ = 1. R ₂ when l '= 1
Preferable are a halogen atom, an aliphatic group, an aliphatic oxy group, a carbonamide group, a sulfonamide group, a cyano group and the like, and among them, a fluorine atom, a chlorine atom, a trifluoromethyl group, a methoxy group and a cyano group are particularly preferred. The substitution position of R ₂ is 2- or 4-position relative to R ₃ NH- are preferred.

In R ₃ of the general formula [A], R ₆ is preferably an aliphatic group, an aromatic group, —OR ₇ or —SR ₇ , and U is preferably —CO— or —SO ₂ —. Examples of the aliphatic group include a methyl group, a trifluoromethyl group, a trichloromethyl group,
Ethyl group, heptafluoropropyl group, t-butyl group,
1-ethylbentyl group, cyclohexyl group, pendyl group, undecyl group, tridecyl group, 1- (2,4-di-t
-Pentylphenoxy) propyl group, and examples of the aromatic group include a phenyl group, a 1-naphthyl group, a 2-naphthyl group, a 2-chlorophenyl group, a 4-methoxyphenyl group,
4-nitrophenyl group, there are a pentafluorophenyl group, a methoxy group as an example of -OR _7, ethoxy group, isopropoxy group, n- butoxy group, isobutoxy group, t-
Butoxy, n-pentyloxy, n-hexyloxy, n-octyloxy, 2-ethylhexyloxy, n-decyloxy, n-dodecyloxy, 2
-Methoxyethoxy group, benzyloxy group, trichloroethoxy group, trifluoroethoxy group, phenoxy group,
There is p- methylphenoxy group, examples of -SR _7,
Methylthio, ethylthio, allylthio, n-butylthio, benzylthio, n-dodecylthio, phenylthio, pt-octylphenylthio, p-dodecylphenylthio, p-octyloxyphenylthio, etc. is there. R ₃ is more preferably an aliphatic oxycarbonyl group (R ₆ is R ₇ O— and U is —CO—) and an aliphatic or aromatic sulfonyl group (R ₆ is an aliphatic group or an aromatic group;
Is —SO ₂ —), particularly preferably an aliphatic oxycarbonyl group.

In the general formula [A], T is preferably a hydrogen atom, a halogen atom, an aliphatic oxy group, an aromatic oxy group, an aliphatic thio group or a heterocyclic thio group. Examples of the aliphatic oxy group include a methoxy group, an ethoxy group, a 2-hydroxyethoxy group, a 2-chloroethoxy group, a carboxymethoxy group, a 1-carboxyethoxy group, a methoxyethoxy group,
2- (2-hydroxyethoxy) ethoxy group, 2-methylsulfonylethoxy group, 2-methylsulfonyloxyethoxy group, 2-methylsulfonamidoethyl group, 2-
Carboxyethoxy group, 3-carboxypropoxy group,
2- (carboxymethylthio) ethoxy group, 2- (1-
Carboxytridecylthio) ethoxy group, 1-carboxytridecyl group, N- (2-methoxyethyl) carbamoylmethoxy group, 1-imidazolylmethoxy group, 5-phenoxycarbonylbenzotriazol-1-ylmethoxy group and the like; Examples of the oxy group include a 4-nitrophenoxy group, a 4-acetamidophenoxy group,
Examples include an acetamidophenoxy group, a 4-methylsulfonylphenoxy group, and a 4- (3-carboxypropanamido) phenoxy group. Examples of the aliphatic thio group include a methylthio group, a 2-hydroxyethylthio group, a carboxymethylthio group, -Carboxyethylthio group, 1-carboxyethylthio group, 3-carboxypropylthio group, 2-
There are dimethylaminoethylthio group, benzylthio group, n-dodecylthio group, 1-carboxytridecylthio group and the like.Examples of heterocyclic thio group include 1-phenyl-1,2,3,4
-Tetrazol-5-ylthio group, 1-ethyl-1,2,3,
4-tetrazol-5-ylthio group, 1- (4-hydroxyphenyl) -1,2,3,4-tetrazol-5-ylthio group, 4-phenyl-1,2,4-triazol-3-ylthio group, 5-methyl-1,3,4-oxadiazole-2-
Ylthio group, 1- (2-carboxyethyl) -1,2,3,4
-Tetrazol-5-ylthio group, 5-methylthio-1,
3,4-thiadiazol-2-ylthio group, 5-methyl-
1,3,4-thiadiazol-2-ylthio group, 5-phenyl-1,3,4-oxadiazol-2-ylthio group, 5-
Amino-1,3,4-thiadiazol-2-ylthio group, benzoxazol-2-ylthio group, 1-methylbenzimidazol-2-ylthio group, 1- (2-dimethylaminophenyl) -1,2,3, 4-tetrazol-5-ylthio group, benzothiazol-2-ylthio group, 5- (ethoxycarbonylmethylthio) -1,3,4-thiadiazol-2-ylthio group, 1,2,4-triazol-3-ylthio group , 4-pyridylthio group, 2-pyrimidylthio group and the like. T is more preferably a hydrogen atom, a chlorine atom, an aliphatic oxy group or an aliphatic thio group, and particularly preferably a hydrogen atom or an aliphatic oxy group.

Hereinafter, specific examples of the coupler represented by Formula [I] used in the present invention will be shown, but the present invention is not limited thereto.

In the present invention, two or more cyan couplers of the general formula (A) mixedly used in the same layer may have different substituents for any one of R ₁ , R ₂ , and R ₃ , provided that R ₂ is It is preferred that R ₁ and / or R ₃ be the same and different, and it is particularly preferable that R ₂ and T be the same and R ₁ or R ₃ be different.
The different substituents among R ₁ , R ₂ and R ₃ are 2
It is preferable that they differ by at least two.

The melting points of two or more cyan couplers represented by the general formula [A] mixed and used in the same layer are preferably different by 5 ° C. or more.

In the present invention, two or more cyan couplers of the present invention may be mixed in one silver halide emulsion layer, and the coupler having the lowest mixing ratio is preferably 5 mol% or more.
More preferably, it is used in an amount of at least 10 mol%, further preferably at least 15 mol%.

Examples of the coupler represented by the general formula [A] other than the above used in the present invention are described in JP-A-60-237448 and JP-A-61-153640.
Nos. 61-145557 and 63-208042. The synthesis of these couplers is described in JP-A-62-123157, JP-A-62-123158 and 62-2584 in addition to the above-mentioned patent publications.
The method can be performed by the method described in JP-A-46-46.

The high-boiling organic solvent referred to in the present invention means normal pressure (760 mmHg)
And has a boiling point of 175 ° C. or more.

Examples of the high boiling point organic solvent used in combination with the coupler represented by the general formula [I] include phosphate esters (triphenyl phosphate, tricresyl phosphate, octyl diphenyl phosphate, tri-2-ethylhexyl phosphate). , Tri-n-hexyl phosphate, tri-iso-nonyl phosphate, tris-cyclohexyl phosphate, tributoxyethyl phosphate, tri-
2-chloroethyl phosphate, etc.), benzoic esters (2-ethylhexyl benzoate, 2-ethylhexyl 2,4-dichlorobenzoate, etc.), fatty acid esters (di-2-ethylhexyl succinate, 2-hexyl tetradecanoate) Decyl, tributyl citrate, etc.), amides (N, N
-Diethyldodecaneamide, N-tetradecylpyrrolidone, etc.), dialkylanilines (2-butoxy-5-te
rt-octyl-N, N-dibutylaniline, etc.), chlorinated paraffins (paraffins containing 10% to 80% of chlorine), phenols (2,5-di-tert-amylphenol, 2,5-di- Examples include tert-hexyl-4-methoxyphenol, 2-ethylhexyl p-hydroxybenzoate, and the like, and phthalic acid esters (dibutyl phthalate, dicyclohexyl phthalate, diheptyl phthalate, di-2-ethylhexyl phthalate, didodecyl phthalate, etc.). Phosphates and phthalates are particularly preferred.

The amount of the high-boiling organic solvent used in the present invention is determined based on the total weight of the coupler contained in one layer, and is at most 0.3 g per 1 g of the coupler. Degradation is a problem. The amount used is preferably 0.15 g, more preferably 0.05 g, even more preferably 0.01 g or less per 1 g of the coupler, and may be 0 g.

The total weight of the coupler in this case refers to the total weight of all the cyan couplers contained in the halogenated emulsion layer containing at least one of the cyan couplers represented by the general formula [I].

The silver halide emulsion layer containing a cyan coupler is preferably red-sensitive, and is composed of two or more layers having different sensitivities. Each layer contains at least one cyan coupler represented by the general formula [I]. More preferably, it is contained.

Further, it is preferable that at least one of the above-mentioned two layers having red sensitivity and different sensitivities contains two or more cyan couplers represented by the general formula [I].
In this case, it is preferable that the layer containing two or more kinds of the cyan couplers represented by the general formula [I] does not contain a high boiling organic solvent. The amount of the cyan coupler represented by the general formula [I] within the applicable range of the present invention (high boiling point organic solvent / coupler ratio at most 0.3) is usually 1.0 × 10 ⁻⁵ mol / m ² to 1.0 × 10 ⁻⁵ mol / m ² .
3.0 × 10 ⁻³ / m ² , preferably 5.0 × 10 ⁻⁵ mol / m ² to 1.5
× 10 ⁻³ mol / m ² .

When the same color-sensitive silver halide emulsion layer is divided into two or more layers having different sensitivities, the present invention is preferably applied to a layer other than the highest sensitivity layer.

When the present invention uses a cyan coupler alone and stores a light-sensitive material containing only 0.3 or less by weight of a high-boiling point organic solvent with respect to the coupler at an extremely low temperature (for example, -15 ° C to 50 ° C), the coloring performance is reduced. That was surprising. This is because conventional cyan couplers did not cause such a decrease in color development in a system having a large amount or a small amount of a high-boiling organic solvent, and the coupler of the present invention also used a large amount of a high-boiling organic solvent as commonly used. Sometimes such problems have not occurred.

The present inventors have conducted intensive studies and found that, when the cyan coupler of the present invention is used alone, a high boiling organic solvent is used only in an amount of 0.3 or less with respect to the cyan coupler. Is not crystalline or oily, forms a metastable phase, and after returning to room temperature, even if color developed, this phase remains without disappearing, so that the color developability decreases.
Differential thermal analysis of this metastable coating (eg DTA, DS
C), and the use of a mixture of two types of couplers as in the constitution of the present invention suppresses the formation of a metastable phase even at cryogenic storage and does not cause a decrease in color developability due to color development. It revealed that.

Accordingly, in the cyan couplers represented by the general formula [I] which are used in combination of two or more in the present invention, the peaks observed in the DTA or DSC measurement when used alone according to the above method are weaker due to the combined use of the two. It is preferred to select the syn-an coupler and its mixing ratio so that it becomes or disappears.

 Hereinafter, the layer structure according to the present invention will be described.

In the present invention, at least one of the emulsion layers having substantially the same color sensitivity is composed of two or more silver halide emulsion layers having different sensitivities. You can choose.

Only one of the two or more color-sensitive layers may have a configuration of two or more layers as described above, or a plurality of layers may be two or more types, and the configuration is arbitrary.

In the present invention, at least one of the color-sensitive emulsion layers composed of two or more silver halide emulsion layers having different sensitivities, the at least one layer closer to the support is farther away from the support. Although the sensitivity is higher than that, the layer configuration is arbitrary. For example, when the color-sensitive emulsion layer is composed of two layers, the layer closer to the support is a high-sensitivity layer. In addition, a middle-speed layer is further provided, and in order from the support side, a high-speed layer, a middle-speed layer, and a low-speed layer, and also a low-speed layer, a high-speed layer, a middle-speed layer, and a middle-speed layer, a low-speed layer Layer, high-sensitivity layer,
And a middle-speed layer, a low-speed layer, a high-speed layer, and the like. It suffices that at least two layers having different sensitivities and at least one layer remote from the support have higher sensitivity than the layer remote from the support.

For example, a typical color photographic light-sensitive material is preferably formed by sequentially forming a red-sensitive layer, a green-sensitive layer, and a blue-sensitive layer in this order from the support. A color-sensitive layer composed of two or more different layers, and at least one of the color-sensitive layers thus formed is constituted such that an emulsion layer closer to the support becomes a high-sensitivity layer;
The color photographic light-sensitive material of the present invention can be obtained. For example, the red-sensitive layer may be composed of a high-sensitivity layer and a low-sensitivity layer, and the layer closer to the support may be configured as a high-sensitivity layer. This is one of the preferred embodiments of the present invention. In this case, a green-sensitive layer is provided on the side farther from the support than the red-sensitive layer, and this green-sensitive layer is also composed of two layers, and the low-sensitive layer of the green-sensitive layer is located closer to the support to obtain a red-sensitive layer. The low-sensitivity layer of the layer and the edge-sensitive layer may be adjacent to each other (an intermediate layer may be interposed).
Alternatively, also for the green-sensitive layer, a layer closer to the support can be a high-sensitivity layer. Also, focusing on the green sensitive layer,
In this regard, a layer closer to the support can be a high-sensitivity layer, which is also a preferred embodiment of the present invention. The same applies to the blue-sensitive layer.

In the practice of the present invention, the same color-sensitive layer may be a single layer, but preferably two to three layers. If there are too many layers, sharpness may be affected in terms of film thickness.

When three layers of the high-sensitivity layer (H), the medium-degree layer (M), and the low-sensitivity layer (L) are provided, the order is M, H, L, or H, M, L in order from the support. Or H,
The order of L and M may be used. As a specific example of a preferred layer constitution, the support is made of BS, and the high- and low-sensitivity red-sensitive layers are each made of R.
GH, GL, high sensitivity,
When the low-sensitivity blue-sensitive layers are BH, BL, IL as an intermediate layer, YC as a yellow filter layer, and Pro as a protective layer, BS, IL, RH, RL, IL, GL, GH, YC, BL, BH, and Pro layer configurations are possible. In the red-sensitive layer, the layer closer to the support was a high-sensitivity layer. Further, similarly, a layer configuration of BS, IL, RH, RL, IL, GH, GL, YC, BL, BH, and Pro can be adopted. In this method, the red-sensitive layer and the green-sensitive layer were those having a high sensitivity layer closer to the support. Furthermore, BS, IL, RL, RH, IL, GH, GL, YC, BL, BH,
Pro layer structure is possible. This is a green sensitive layer in which the one closer to the support is a high-sensitivity layer. As a modification, a configuration in which IL is further provided between RL and RH can be adopted. BS, RH, IL, RL, IL, GL, CH,
The layer structure can be YC, B, or Pro, where B is a single blue-sensitive layer, that is, in this layer configuration example, the blue-sensitive layer is one layer. BS, IL, RM, RH, RL, IL, GH, GL,
YC, BL, BH, Pro layer structure can be used, where RM is a red-sensitive medium-sensitive layer, that is, in the example of layer structure, the red-sensitive layer is three layers, and RM, RH, RL In this order. BS, IL, RH, RL, IL, GL, GM, GH, YC, BL,
The layer structure can be BH or Pro, where GM is a green-sensitive medium-sensitive layer, that is, in this example, the green-sensitive layer has a three-layer structure.

In addition, the present invention can be embodied as a number of layer configurations by appropriately rearranging the above-described respective layer configurations.

In the light-sensitive material of the present invention, the difference in sensitivity between the high-sensitivity emulsion layer and the low-sensitivity emulsion layer preferably has a difference of 0.3 to 2.0 logE. When a medium-speed emulsion layer is provided, it is well known that the difference in sensitivity between the high-speed emulsion layer and the medium-speed emulsion layer and the difference between the medium-speed and low-speed emulsion layers are optimal in consideration of gradation and the like. In general, 0.2 to 1.0 logE (E: exposure fee)
It is preferable to have a difference of

Further, in the present invention, JP-A-61-340541, JP-A-61-340541
In order to express the spectral sensitivity proposed in JP-A-198236 and JP-A-61-160448, it is also preferable to provide an emulsion layer having a fourth spectral sensitivity different from the so-called red, green and blue-sensitive emulsion layers. This fourth spectral sensitivity layer may be provided at any position in the photosensitive material, but is preferably provided between the red photosensitive layer and the green photosensitive layer or between the green photosensitive layer and the blue photosensitive layer. .

Preferred silver halide contained in the photographic emulsion layer of the photographic light-sensitive material used in the present invention is silver iodobromide, silver iodochloride, or silver iodochlorobromide containing about 30 mol% or less of silver iodide. . Particularly preferred is silver iodobromide or silver iodochlorobromide containing from about 2 mol% to about 25 mol% silver iodide.

Silver halide grains in photographic emulsions are cubic, octahedral,
It may be one having regular crystals such as tetradecahedron, one having irregular crystal forms such as spherical or plate-like, one having crystal defects such as twin planes, or a complex form thereof.

The silver halide may be fine grains having a grain size of about 0.2 μm or less or large grains having a projected area diameter of about 10 μm, and may be a polydisperse emulsion or a monodisperse emulsion.

The silver halide photographic emulsion usable in the present invention is described, for example, in Research Disclosure (RD) No. 1763 (Jan.
February, p. 22-23, "I. Emulsion preparation
and types) ”and No. 18716 (November 1979), 648
Page, Grafkid, "Physics and Chemistry of Photography", published by Paul Montell (P. Glafkides, Chemic et Phisique Photographi)
que, Paul Montel, 1967), Duffin's "Photoemulsion Chemistry", Focal Press (GFDujjin, Photograpic)
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 Photo).
graphic Emulsion, Focal Press, 1964).

Monodisperse emulsions described in U.S. Pat. Nos. 3,574,628 and 3,655,394 and British Patent 1,413,748 are also preferable.

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, Photographic Science and Engineerin.
g), Vol. 14, pp. 248-257 (1970); U.S. Patent No. 4,434,2
No. 26, 4,414,310, 4,433,048, 4,439,520 and British Patent No. 2,112,157 can be easily prepared.

The crystal structure may be uniform, the inside and the outside may be composed of different halogen compositions, may have a layered structure, and even if silver halides having different compositions are joined by epitaxial junction. Also, it may be bonded to a compound other than silver halide such as, for example, silver rhodan or lead oxide.

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

As the silver halide emulsion, usually, those subjected to physical ripening, chemical ripening and spectral sensitization are used. The additive used in such a process is Research Disclosure No. 1
7643 and No. 18716, and the relevant portions are summarized in the table below.

Known photographic additives which can be used in the present invention are also described in the above two Research Disclosures, and the relevant portions are shown in the following table.

Also, in order to prevent deterioration of photographic performance due to formaldehyde gas, U.S. Patent Nos. 4,411,987 and 4,435,503
It is preferable to add to the publication material a compound which can react with formaldehyde described in (1) and can be immobilized.

Various color couplers can be used in the present invention, and specific examples thereof are described in the patents described in the aforementioned Research Disclosure (RD) No. 17643, VII-CG.

As a yellow coupler, for example, U.S. Pat.
No. 501, No. 4,022,620, No. 4,326,024, No. 4,40
No. 1,752, No. 4,248,961, Japanese Patent Publication No. 58-10739, British Patent No. 1,425,020, No. 1,476,760, U.S. Pat.
Preferred are those described in 3,968, 4,314,023, 4,511,649, and EP 249,473A.

As the magenta coupler, 5-pyrazolone-based and pyrazoloazole-based compounds are preferable, and US Patent No. 4,310,
No. 619, No. 4,351,897, European Patent No. 73,636, U.S. Pat. No. 3,061,432, No. 3,725,067, Research Disclosure No. 24220 (June 1984), JP-A-60-3355
No. 2, Research Disclosure No. 24230 (June 1984), JP-A-60-43659, JP-A-61-72238, and JP-A-60-35
No. 370, No. 55118034, No. 60-185951, U.S. Pat.
Particularly preferred are those described in No. 00,630, No. 4,540,654, No. 4,556,630, International Publication W088 / 04795, and the like.

Examples of the cyan coupler other than the general formula (A) of the present invention include phenol-based and naphthol-based couplers, and include U.S. Pat.Nos. 4,052,212, 4,146,396, and 4,
No. 228,233, No. 4,296,200, No. 2,369,929, No.
No. 2,801,171, No. 2,772,162, No. 2,895,826, No. 3,772,002, No. 3,758,308, No. 4,334,011,
No. 4,327,173, West German Patent Publication No. 3,329,729, European Patent No. 121,365A, No. 249,453A, U.S. Patent No. 3,446,622
No. 4,333,999, No. 4,775,616, No. 4,451,55
No. 9, No. 4,427,767, No. 4,254,212, No. 4,296,1
No. 99 and JP-A-61-42658 are preferred.

Colored couplers for correcting unnecessary absorption of generated dyes are described in Research Disclosure No. 17643 VII.
Section G, U.S. Pat.No. 4,163,670, JP-B-57-39413,
U.S. Pat.Nos. 4,004,929 and 4,138,258; British Patent No.
Those described in 1,146,368 are preferred. U.S. Patent No.
A coupler that corrects unnecessary absorption of a coloring dye by a fluorescent dye released at the time of coupling described in 4,774,181,
It is also preferable to use a coupler having a dye precursor group capable of forming a dye by reacting with a developing agent described in US Pat. No. 4,777,120 as a leaving group.

As a coupler in which the coloring dye has an appropriate diffusivity,
Those described in U.S. Pat. No. 4,366,237, British Patent No. 2,125,570, European Patent No. 96,570, and West German Patent Publication (Publication) No. 3,324,533 are preferred.

Typical examples of polymerized dye-forming couplers include U.S. Patent Nos. 3,451,820, 4,080,211 and 4,367,282.
No. 4,409,320, No. 4,576,910, British Patent 2,10
No. 2,173.

Couplers that release a photographically useful residue upon coupling can also be preferably used in the present invention. DIR couplers that release development inhibitors are described in RD17643, VII-F above.
Patents, JP-A-57-151944 and JP-A-57-1542
No. 34, No. 60-184248, No. 63-37346, U.S. Pat.
Preferred are those described in JP-A-8,962 and JP-A-4,782,012.

Examples of couplers that release a nucleating agent or a development accelerator imagewise during development include UK Patent Nos. 2,097,140 and 2,1
No. 31,188, JP-A Nos. 59-157638 and 59-170840 are preferred.

In addition, as couplers that can be used in the light-sensitive material of the present invention, competitive couplers described in U.S. Pat.No. 4,130,427, U.S. Pat.Nos. 4,283,472 and 4,338,393,
No. 4,310,618, a multi-equivalent coupler described in JP-A-60310
185950, DIR redox compound releasing coupler, DIR coupler releasing coupler, DIR described in JP-A-62-24252 and the like.
Coupler-releasing redox compound or DIR redox-releasing redox compound, coupler releasing a dye that recolors after release as described in EP 173,302A, RD No. 1144
9, 24241, bleach accelerator releasing couplers described in JP-A-61-201247, ligand releasing couplers described in U.S. Pat.No. 4,553,477, etc., and leuco dyes described in JP-A-63-75747 are released. Couplers and couplers that release a fluorescent dye described in U.S. Pat. No. 4,774,181 are exemplified.

The coupler used in the present invention can be introduced into a light-sensitive material by various known dispersion methods.

Examples of the high boiling point solvent used in the oil-in-water dispersion method are described in US Pat. No. 2,322,027.

Specific examples of high-boiling organic solvents having a boiling point at normal pressure of 175 ° C. or higher used in the oil-in-water dispersion method include phthalic acid esters (dibutyl phthalate, dicyclohexyl phthalate, di-2-ethylhexyl phthalate, decyl phthalate, bis (2,4-di-t-amylphenyl) phthalate, bis (2,4-di-t-amylphenyl) isophthalate, bis (1,1-diethylpropyl) phthalate, etc., phosphoric acid or phosphonic acid ester (Triphenyl phosphate, tricresyl phosphate, 2-ethylhexyl diphenyl phosphate, tricyclohexyl phosphate, tri-2-ethylhexyl phosphate, tridodecyl phosphate, tributoxyethyl phosphate, trichloropropyl phosphate, di-
2-ethylhexylphenylphosphonate, etc.), benzoic esters (2-ethylhexylbenzoate, dodecylbenzoate, 2-ethylhexyl-p-hydroxybenzoate, etc.), amides (N, N-diethyldodecaneamide, N, N-diethyl) Laurylamide, N-tetradecylpyrrolidone, etc.), alcohols or phenols (isostearyl alcohol, 2,4-di-tert-)
Aliphatic carboxylic acid esters (bis (2-ethylhexyl) sebacate, dioctyl azelate, glycerol tributyrate, isostearyl lactate, trioctyl citrate, etc.), aniline derivatives (N, N-dibutyl-2) -Butoxy-5-tert
-Octylaniline, etc.), hydrocarbons (paraffin,
Dodecylbenzene, diisopropylnaphthalene, etc.). The auxiliary solvent has a boiling point of about 30 ° C.
Above, preferably 50 ° C. or more and about 160 ° C. or less of an organic solvent can be used, typical examples are ethyl acetate, butyl acetate,
Examples include ethyl propionate, methyl ethyl ketone, cyclohexanone, 2-ethoxyethyl acetate, and dimethylformamide.

The process and effect of the latex dispersion method and specific examples of the latex for impregnation are described in U.S. Pat. No. 4,199,363, West German Patent Application (OLS) Nos. 2,541,274 and 2,541,230.

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.

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 the right column of page 647 of No.18716
It is described in the left column on page 648.

In the light-sensitive material of the present invention, the total thickness of all the hydrophilic colloid layers on the side having the emulsion layer is preferably 28 μm or less, and the film swelling speed T _1/2 is preferably 30 seconds or less. The film thickness means a film thickness measured under humidity control at 25 ° C. and a relative humidity of 55% (2 days), and the film swelling rate T _1/2 can be measured according to a method known in the art. For example, Photographic Science and Engineering (Photogr.Sci.Eng.), 19 by A. Green et al.
Vol. 2, No., pp. 124-129, and can be measured by using a serometer (swelling meter). T _1/2 is reached when the color developer is processed at 30 ° C. for 3 minutes 15 seconds. The saturated film thickness is defined as 90% of the maximum swelled film thickness, and the time required to reach the film thickness of T _1/2 is defined.

The film swelling speed T _1/2 can be adjusted by adding a hardening agent to gelatin as a binder or by changing the aging conditions after coating. The swelling ratio is
150-400% is preferred. The swelling ratio is calculated from the maximum swelling film thickness under the above-mentioned conditions by the formula: (maximum swelling film thickness-film thickness).
/ Can be calculated according to the film thickness.

The color photographic light-sensitive material according to the present invention is described in RD.
The development can be carried out by a usual method described in 17643, pp. 28-29, and No. 18716, 615 left column to right column.

The color developer used in the development of the photosensitive material of the present invention is
An alkaline aqueous solution containing an aromatic primary amine color developing agent as a main component is preferred. Aminophenol compounds are also useful as the color developing agent.
Phenylenediamine compounds are preferably used, and typical examples thereof are 3-methyl-4-amino-N, N-diethylaniline and 3-methyl-4-amino-N-ethyl-N-.
β-hydroxyethylaniline, 3-methyl-4-amino-N-ethyl-N-β-methanesulfonamidoethylaniline, 3-methyl-4-amino-N-ethyl-β-
Examples include methoxyethylaniline and their sulfates, hydrochlorides or p-toluenesulfonates. These compounds can be used in combination of two or more depending on the purpose.

Color developing solutions are pH buffers such as alkali metal carbonates, borates or phosphates, bromide salts, iodide salts,
It generally contains a development inhibitor or an antifoggant such as a penimidazole, a benzothiazole or a mercapto compound. If necessary, hydroxylamine, diethylhydroxylamine, sulfite, hydrazines, phenylsemicarbazide, triethanolamine, catecholsulfones, triethylenediamine (1,4-diazabicyclo [2,2,2] octane) Various preservatives, organic solvents such as ethylene glycol and diethylene glycol, benzyl alcohol, polyethylene glycol, quaternary ammonium salts, development accelerators such as amines, dye-forming couplers, competitive couplers,
Kuburase, such as sodium boron hydride, 1
An auxiliary developing agent such as -phenyl-3-pyrazolidone,
Viscosity imparting agents, aminopolycarboxylic acids, aminopolyphosphonic acids, alkylphosphonic acids, various chelating agents represented by phosphonocarboxylic acids, for example, ethylenediaminetetraacetic acid, nitrilotriacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid , Hydroxyethyliminodiacetic acid, 1-hydroxyethylidene-1,1-diphosphonic acid, nitrilo-N, N, N-trimethylenephosphonic acid, ethylenediamine-N, N, N, N-tetramethylenephosphonic acid, ethylenediamine-diene (O-hydroxyphenylacetic acid) and salts thereof can be mentioned as typical examples.

When the reversal process is performed, color development is usually performed after black and white development. The black-and-white developer includes dihydroxybenzenes such as hydroquinone, 1-phenyl-3-
Known black-and-white developing agents such as 3-pyrazolidones such as pyrazolidone or aminophenols such as N-methyl-p-aminophenol can be used alone or in combination.

The pH of these color developing solutions and black-and-white developing solutions is generally 9 to 12. The replenishment amount of these developing solutions depends on the color photographic light-sensitive material to be processed, but is generally 3 or less per square meter of the photographic material, and 500 ml by reducing the bromide ion concentration in the replenishing solution.
It can also be: When the replenishment rate is reduced, it is preferable to prevent evaporation of the liquid and air oxidation by reducing the contact area of the processing tank with the air. Further, the amount of replenishment can be reduced by using means for suppressing the accumulation of bromide ions in the developer.

The time for the color development processing is usually set between 2 and 5 minutes, but the processing time can be further shortened by using a high temperature and high pH and using a high concentration of the color developing agent.

The photographic emulsion layer after color development is usually bleached. The bleaching process may be performed simultaneously with the fixing process (bleach-fixing process), or may be performed individually. In order to further speed up the processing, a processing method of performing bleach-fixing after bleaching may be used. Further processing in two successive bleach-fix baths,
Fixing processing before bleach-fixing processing or bleaching processing after bleach-fixing processing can be arbitrarily performed according to the purpose.
Examples of the bleaching agent include iron (III), cobalt (III),
Compounds of polyvalent metals such as chromium (IV) and copper (II) Peroxy acids, quinones, nitro compounds and the like are used. Representative bleaches include ferricyanide; dichromate; iron (II
Organic complex salts of I) or cobalt (III), such as ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, methyliminodiacetic acid, 1,3
-Use of aminopolycarboxylic acids such as diaminopropanetetraacetic acid, glycol ether diaminetetraacetic acid, or complex salts such as citric acid, tartaric acid, and malic acid; persulfates; bromates; permanganates; it can. Among these, iron aminopolycarboxylates (II) including iron (III) complex salts of ethylenediaminetetraacetate
I) Complex salts and persulfates are preferred from the viewpoint of rapid processing and prevention of environmental pollution. In addition, iron (III) aminopolycarboxylate
Complex irons are particularly useful in both bleaching and bleach-fixing solutions. The pH of the bleaching solution or the bleach-fixing solution using these aminopolycarboxylic acid iron (III) complex salts is usually 5.5 to 8, but the processing can be carried out at a lower pH in order to speed up the processing.

In the bleaching agent, the bleach-fixing solution and the prebath thereof, a bleaching accelerator can be used if necessary. Specific examples of useful bleach accelerators are described in the following specification: U.S. Pat. No. 3,893,858, West German Patent 1,290,812, and 2,059,98.
No. 8, JP-A-53-32736, JP-A-53-57831, JP-A-53-37148
No. 53-72623, No. 53-95630, No. 53-95631,
Nos. 53-104232, 53-124424, 53-141623,
53-28426, Research Disclosure No.17129
Having a mercapto group or a disulfide group described in JP-A No. (July 1978); thiazolidine derivatives described in JP-A-50-140129;
No. 20832, No. 53-32735, U.S. Pat. No. 3,706,561; thiourea derivatives; West German Patent No. 1,127,715, JP-A-58
Iodide salts described in -16,235; West German Patent No. 966,410;
Polyoxyethylene compounds described in 2,748,430;
Polyamine compounds described in JP-B-45-8836; and JP-A-429-42,434, JP-A-49-59,644, JP-A-53-94,927, and JP-A-5-94,927.
Compounds described in JP-A Nos. 4-35,727, 55-26,506, and 58-163,940; bromide ions and the like can be used. Among them, compounds having a mercapto group or a disulfide group are preferable in view of a large accelerating effect, and in particular, U.S. Patent No. 3,839,858
Compounds described in JP-A No. 1,290,812 and JP-A-53-95,630 are preferred. Further, the compounds described in U.S. Pat. No. 4,552,834 are also preferable. These bleaching accelerators may be added to the light-sensitive material. These bleaching accelerators are particularly effective when bleach-fixing a color photographic material for photography.

Examples of the fixing agent include thiosulfates, thiocyanates, thioether-based compounds, thioureas, and a large amount of iodide.The use of thiosulfates is common,
In particular, ammonium thiosulfate can be used most widely. As a preservative of the bleach-fix solution, a sulfite, a bisulfite or a carbonyl bisulfite adduct is preferable.

The silver halide color photographic light-sensitive material of the present invention generally undergoes withdrawal processing 5, washing with water and / or stabilization. The amount of water to be washed in the water washing process is determined by the characteristics of the photosensitive material (for example, depending on the material used such as a coupler), the use, the temperature of the water to be washed,
It can be set in a wide range depending on the number of washing tanks (number of stages), a replenishment method such as countercurrent flow, forward flow, and other various conditions. Of these, the relationship between the number of washing tanks and the amount of water in the multi-stage countercurrent method is described in the Journal of the Society of Motion Picture and T
It can be determined by the method described in elevision Eugineers, Vol. 64, pp. 248-253 (May, 1955).

According to the multi-stage countercurrent method described in the above-mentioned document, the amount of washing water can be greatly reduced.However, due to an increase in the residence time of water in the tank, bacteria grow, and the generated suspended matter adheres to the photosensitive material. Problem arises. In the processing of the color light-sensitive material of the present invention, calcium ion described in JP-A-62-288838,
A method for reducing magnesium ions can be used very effectively. Further, isothiazolone compounds and thiabendazoles described in JP-A-57-8542, chlorine-based disinfectants such as chlorinated sodium isocyanurate, and other benzotriazoles, etc., written by Hiroshi Horiguchi, "Bactericidal and Fungicide Chemistry" ,
Sanitizing agents described in “Sterilization, sterilization, and antifungal technology of microorganisms” at the Sanitary Technology Hall, “Encyclopedia of Antifungal and Antifungal Agents” edited by the Japan Society of Antifungals and Fungi can also be used.

In the processing of the light-sensitive material of the present invention, the pH of the washing water is from 4 to
9, preferably 5 to 8. Washing water temperature and washing time can also be variously set depending on the characteristics of the photosensitive material, the use, etc., but in general, 15 to 45 ° C for 20 seconds to 10 minutes, preferably 25 to 40 ° C.
A range of 30 seconds to 5 minutes is selected. Further, the light-sensitive material of the present invention can be processed directly with a stabilizing solution instead of the above-mentioned washing. In such a stabilization process, Japanese Patent Laid-Open No.
Known methods described in JP-A-8543, JP-A-58-14834, and JP-A-60-220345 can all be used.

Further, after the above-mentioned water washing treatment, a stabilization treatment may be further carried out. For example, a stabilizing bath containing formalin and a surfactant used as a final bath of a color light-sensitive material for photography can be mentioned. . Various chelating agents and fungicides can be added to the stabilizing bath.

The overflow solution resulting from the washing and / or replenishment of the stabilizing solution can be reused in another step such as a desilvering step.

The silver halide color light-sensitive material of the present invention may contain a color developing agent for the purpose of simplifying and speeding up the processing.
In order to incorporate the color developing agent, it is preferable to use various precursors of a color developing agent. For example, indoaniline-based compounds described in U.S. Pat. Salt complexes and urethane compounds described in JP-A-53-135628 can be exemplified.

The silver halide color light-sensitive material of the present invention may contain various 1-phenyl-
3-pyrazolidones may be incorporated. Typical compounds are described in JP-A-56-64339, JP-A-57-1444547, and JP-A-58-144547.
No. 15438.

The various processing solutions in the present invention are used at 10 ° C to 50 ° C. Usually, a temperature of 33 ° C to 38 ° C is standard, but a higher temperature promotes the processing and shortens the processing time, and conversely, lowers the temperature to achieve the improvement of the image quality and the stability of the processing solution. be able to. Further, in order to save silver of the light-sensitive material, a process using cobalt intensification or hydrogen peroxide intensification described in West German Patent No. 2,226,770 or US Pat. No. 3,674,499 may be performed.

The silver halide light-sensitive material of the present invention is disclosed in U.S. Pat.
No. 500,626, JP-A-60-133449, JP-A-59-218443, JP-A-6
The present invention can also be applied to photothermographic materials described in 1-238056 and European Patent 210.660A2.

Example 1 An emulsion of the coupler (I-18) of the present invention was prepared as follows. The following oil phase and aqueous phase were each heated and dissolved, mixed, and emulsified and dispersed in a household mixer for 10 minutes.

(Oil phase) Coupler (I-18) of the present invention 60 g Solv-1 60 g Ethyl acetate 150 g (Aqueous phase) Sodium dodecylbenzenesulfonate 2 g Bovine bone gelatin (Ca ²⁺ content) 1000 ppm, average molecular weight 50
10,000g) 100g Water was added and the total amount was 1272g. 30 minutes after preparing 500g of this emulsion, it was chemically sensitized and
Anhydro-5,5'-cyclolo-9-ethyl-3,3'-di- (3-sulfopropyl) thiacarbocyanine hydroxide and anhydro-9-ethyl-3,3'-di- (3-sulfopropyl) -4.5.4 ', 5'-Dibenzothiacarbocyanine hydroxide spectrally sensitized silver iodobromide emulsion (AgI content: 3 mol%, average size: 0.4 µm, monodisperse tetrahedral grains: 7 wt% gelatin , Containing 7 wt% as Ag), and adding 700 g of 4-hydroxy-6-notyl-1,3,3a, 7-tetrazaindene, 0.01 g of these solutions. The photosensitive material 101 as described above was produced.

First layer: coupler as an emulsion layer the emulsions ...... silver 1.4 g / m ² present invention ^{...... 0.674g / m 2 (I-} 18) Solv-1 ...... 0.674g / m 2 gelatin ...... 2.5 g / m ² Second layer: protective layer Gelatin: 1.5 g / m ² polymethyl methacrylate particles (diameter: 2.0 μm): 0.05 g / m ² 2,4-dichloro-6-hydroxy-s-triazine Na
Salt ... 0.09 g / m According to the method for preparing sample 101, as shown in Table 1, sample 1
02 to 130 were produced. The coupler was equimolarly substituted for (I-18), and the mixing ratio was shown by molar ratio.

After storing these photosensitive materials at 0 ° C. and -20 ° C. for 14 days, the following color development was performed to measure the maximum cyan density.

Developed samples obtained by storing at 0 ° C are stored at 60 ° C relative humidity.
After storing for 14 days under 70% conditions, the maximum cyan density was measured.

 Table 1 shows the obtained results.

 The following development processing was carried out at 35 ° C.

1. Color development 3 minutes 15 seconds 2. Bleaching 6 minutes 30 seconds 3. Rinse 3 minutes 15 seconds 4. Fixed 4 minutes 20 seconds 5. Rinse 3 minutes 15 seconds 6. Stabilize 1 minute 5 seconds Is as follows.

Color developer Sodium nitrilotriacetate 1.0 g Sodium sulfite 4.0 g Sodium carbonate 30.0 g Potassium bromide 1.4 g Hydroxyamine sulfate 2.4 g 4- (N-ethyl-N-β-hydroxyethylamino) -2-methylaniline sulfate 4.5g Add water 1 Bleaching solution Ammonium bromide 160.0g Ammonia water (28%) 25.0CC Sodium iron salt of ethylenediamine-tetraacetate 130.0g Glacial acetic acid 14.0CC Add water 1 Fixing solution Sodium tetrapolyphosphate 2.0g Sodium sulfite 4.0g Ammonium thiosulfate (70%) 175.0CC Sodium bisulfite 4.6g Water 1 Add stable water Formalin 8.0CC Add water 1 After preparing emulsion, store in refrigerator at 7 ° C for 7 days After dissolving to prepare the coating solution as described above, and leaving it at 40 ° C. for 8 hours, the state of the sample when applied in the same manner as described above is shown in Table 1 as coatability.

From Table 1, it can be seen from Table 1 that the couplers of the present invention alone, which used only a small amount of the high boiling point organic solvent, had a reduced color density when stored at −20 ° C. Samples 125 to 130 using a combination of couplers other than the present invention have a problem that the color development density is poor. It is apparent that there is a problem that the density of the color image is low under the condition of forced degradation and that the sample of the present invention does not have any of these problems.

Example 2 A sample 201, which is a multilayer color photographic material comprising the following layers, was prepared on an undercoated cellulose triacetate film support.

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. The symbols indicating the additives have the following meanings. However, when there are multiple utilities, only one of them is listed as a representative.

UV; UV absorber, Solv; high boiling organic solvent, ExF; dye,
ExS; sensitizing dye, ExC; cyan coupler, ExM; magenta coupler, ExY; yellow coupler, Cpd; additive First layer (antihalation layer) Black colloidal silver 0.15 gelatin 2.9 UV-1 0.03 UV-2 0.06 UV-3 0.07 Solv-2 0.08 ExF-1 0.01 ExF-2 0.01 Second layer (low-sensitivity red-sensitive emulsion layer) Silver iodobromide emulsion (AgI 4% mol%, uniform AgI type, equivalent sphere diameter 0.4 μm, equivalent sphere diameter) Coefficient of variation 37%, plate-like particles, diameter / thickness ratio 3.0) Silver coating amount 0.4 Gelatin 0.8 ExS-1 2.3 × 10 ^-4 ExS-2 1.4 × 10 ^-4 ExS-5 2.3 × 10 ^-4 ExS-7 8.0 × ^10-6 Illustrative Coupler I-8 0.17 ExC-2 0.03 ExC-3 0.13 Third Layer (Medium Sensitivity Red-Sensitive Emulsion Layer) Silver iodobromide emulsion (AgI 6 mol%, internal high AgI type having core-shell ratio of 2: 1, Sphere equivalent diameter 0.65μm, sphere equivalent diameter variation coefficient 25
%, Tabular grains, diameter / thickness ratio 2.0) Silver coating 0.65 silver iodobromide emulsion (AgI 4 mol%, uniform AgI type, equivalent sphere diameter)
0.4 μm, coefficient of variation of equivalent sphere diameter 37%, plate-like particles, diameter /
Thickness ratio 3.0) Coating silver amount 0.1 Gelatin 1.0 ExS-1 2 × 10 ^-4 ExS-2 1.2 × 10 ^-4 ExS-5 2 × 10 ^-4 ExS-7 7 × 10 ^-6 Illustrative coupler I-8 0.31 ExC- 2 0.01 ExC-3 0.06 4th layer (high-sensitivity red-sensitive emulsion layer) Silver iodobromide emulsion (AgI 6 mol%, internal high AgI type with core-shell ratio 2: 1, equivalent sphere diameter 0.7 μm, variation in equivalent sphere diameter) Coefficient 25
%, Plate-like particles, diameter / thickness ratio 2.5) Silver coating amount 0.9 Gelatin 0.8 ExS-1 1.6 × 10 ^-4 ExS-2 1.6 × 10 ^-4 ExS-5 1.6 × 10 ^-4 ExS-7 6 × 10 ^-4 ExC-1 0.07 Illustrative coupler I-8 0.05 ExC-4 0.05 Solv-1 0.07 Solv-2 0.20 Cpd-7 4.6 × 10 ^-4 Fifth layer (intermediate layer) Gelatin 0.6 Cpd-1 0.04 Polyethyl acrylate latex 0.12 Solv- 1 0.02 6th layer (donor layer of multilayer effect on red-sensitive layer) Silver iodobromide emulsion (AgI 6 mol%, internal high AgI type with core-shell ratio 2: 1, equivalent sphere diameter 0.7 μm, coefficient of variation of equivalent sphere diameter) twenty five
%, Tabular grains, diameter / thickness ratio 2.0) Silver coating amount 0.68 Silver iodobromide emulsion (AgI 4 mol%, uniform AgI type, equivalent sphere diameter)
0.4 μm, coefficient of variation of equivalent sphere diameter 37%, plate-like particles, diameter /
Thickness ratio 3.0) Silver coating 0.19 Gelatin 1.0 ExS-3 6 × 10 ^-4 ExC-2 0.07 ExM-10 0.019 Solv-1 0.20 7th layer (intermediate layer) Gelatin 0.6 UV-4 0.03 UV-5 0.04 Cpd-1 0.1 Polyethyl acrylate latex 0.08 Solv-1 0.05 Eighth layer (low-sensitivity green-sensitive emulsion layer) Silver iodobromide emulsion (AgI 4 mol%, uniform AgI type, equivalent sphere diameter)
0.4 μm, coefficient of variation of equivalent sphere diameter 37%, plate-like particles, diameter /
Thickness ratio 2.0) Silver coating 0.18 Gelatin 0.4 ExS-3 2 × 10 ^-4 ExS-4 7 × 10 ^-4 ExS-5 1 × 10 ^-4 ExM-5 0.11 ExM-7 0.03 ExY-8 0.01 Solv-1 0.09 Solv-4 0.01 Ninth layer (medium-speed green-sensitive emulsion layer) Silver iodobromide emulsion (AgI 4 mol%, surface-high AgI type having a core-shell ratio of 1: 1, equivalent sphere diameter 0.5 μm, coefficient of variation of equivalent sphere diameter 20)
%, Plate-like particles, diameter / thickness ratio 4.0) Coating silver amount 0.27 Gelatin 0.6 ExS-3 2 × 10 ^-4 ExS-4 7 × 10 ^-4 ExS-5 1 × 10 ^-4 ExM-5 0.17 ExM-7 0.04 ExM-8 0.02 Solv-1 0.14 Solv-4 0.02 10th layer (high-sensitivity green-sensitive emulsion layer) Silver iodobromide emulsion (AgI 8.7 mol%, silver 3: 3: 2 multilayer structure grain, AgI content) 24 mol from inside, 0 mol, 3 mol%, sphere-corresponding diameter 0.7 [mu] m, a variation coefficient of 25% equivalent spherical diameter, the plate-like particles, diameter / thickness ratio 1.6) coating silver amount 0.7 gelatin 0.8 ExS-4 5.2 × 10 ^{- 4} ExS-5 1 × 10 ^-4 ExS-8 0.3 × 10 ^-4 ExM-5 0.1 ExM-6 0.03 ExY-8 0.02 ExC-1 0.02 ExC-4 0.01 Solv-1 0.25 Solv-2 0.06 Solv-4 0.01 Cpd -7 1 × 10 ^-4 11th layer (yellow filter layer) Yellow colloidal silver 0.06 gelatin 0.8 Cpd-2 0.13 Solv-1 0.13 Cpd-1 0.07 Cpd-6 0.002 H-1 0.13 12th layer (low-sensitivity blue-sensitive emulsion Layer) Silver iodobromide emulsion (AgI 4.5 mol%, uniform AgI type, spherical 0.7 μm equivalent diameter, coefficient of variation of equivalent sphere diameter 15%, plate-like grains, diameter / thickness ratio 7.0) Coating amount of silver 0.3 Silver iodobromide emulsion (AgI 3 mol%, uniform AgI type, equivalent sphere diameter)
0.3 μm, coefficient of variation of equivalent sphere diameter 30%, plate-like particles, diameter /
Thickness ratio 7.0) Silver coating 0.15 Gelatin 1.8 ExS-6 9 × 10 ^-4 ExC-1 0.06 ExC-4 0.03 ExY-9 0.14 ExY-11 0.89 Solv-1 0.42 Layer 13 (intermediate layer) Gelatin 0.7 ExY-12 0.20 Solv-1 0.34 14th layer (high-sensitivity blue-sensitive emulsion layer) Silver iodobromide emulsion (AgI 10 mol%, internal high AgI type, sphere equivalent diameter 1.0 μm, sphere equivalent diameter variation coefficient 25%, multiple twinning Plate-like particles, diameter / thickness ratio 2.0) Silver coating amount 0.5 Gelatin 0.5 ExS-6 1 × 10 ^-4 ExY-9 0.01 ExY-11 0.20 ExC-1 0.02 Solv-1 0.10 15th layer (first protective layer) Fine particles Silver iodobromide emulsion (AgI 2 mol%, uniform AgI type, equivalent sphere diameter 0.07 μm) Coating silver amount 0.12 Gelatin 0.9 UV-4 0.11 UV-5 0.16 Solv-5 0.02 H-1 0.13 Cpd-5 0.10 Polyethyl acrylate Latex 0.09 Sixteenth layer (Second protective layer) Fine grain silver iodobromide emulsion (AgI 2 mol%, uniform AgI type, equivalent sphere diameter 0.07 μm) Silver coating 0.36 Gelatin 0.55 Polymethylmethac Related particles (1.5 μm in diameter) 0.2 H-1 0.17 In addition to the above components, an emulsion stabilizer Cpd-3 was added to each layer.
(0.07 g / m ² ) and a surfactant Cpd-4 (0.03 g / m ² ) were added as coating aids.

The type of the coupler was variously changed so that the amount of the coupler I-8 of the third layer and the fourth layer of the sample 201 became the same as that of the coating amount, and the amount of the high boiling organic solvent Solv-2 to the coupler was shown in Table 2. Samples 202-225 were fabricated with the changes as shown.

After storing these samples at 25 ° C., -5 ° C., and -25 ° C. for 14 days, they were exposed to sensitometry and subjected to the following color development. Table 2 shows the density difference between the -5 ° C and -25 ° C densities of the sample stored at 25 ° C at which the cyan concentration was 2.00, from 2.00.
(Negative values indicate a decrease in concentration).

Also, the developed sample stored at 25 ° C was scratched with a knife so that it reached the support from the emulsion side, and a commercially available cellophane tape was attached to the emulsion side and a peeling test was performed. (The other samples did not peel, but only the cellophane tape peeled.) This result is also shown in Table 2.
Shown in

 The following processing was performed at 38 ° C. by an automatic developing machine.

Color development 3 minutes 15 seconds Bleaching 1 minute Bleaching and fixing 3 minutes 15 seconds Rinse 40 seconds Rinse 1 minute Stable 40 seconds Drying (50 ° C) 1 minute 15 seconds A running water washing method was used. Next, the composition of each processing solution will be described.

The replenishment amount of each processing solution was 1200 ml for color development per 1 m ² of the color photographic material and 80 ml for all others including washing with water. The pre-bath carry-amount to the water washing step was found to be a color light-sensitive material 1 m ² per 50 ml.

洗 Wash water≫ Calcium ion 32mg /, Magnesium ion 7.3mg
/ Containing tap water was passed through a column filled with H-type strongly acidic cation exchange resin and OH-type strongly basic anion exchange resin, and calcium ion 1.2 mg /, magnesium ion 0.
To water treated to 4 mg /, 20 mg of sodium diisocyanurate was added for use.

{Drying} The drying temperature was 50 ° C.

It is apparent that the sample of the present invention has a high film strength and that the color density does not decrease even when the photographic material is stored at an extremely low temperature.

 ──────────────────────────────────────────────────続 き Continuation of the front page (56) References JP-A-62-269958 (JP, A) JP-A-63-88551 (JP, A) JP-A-64-4743 (JP, A) JP-A 62-26958 91947 (JP, A)

Claims (1)

(57) [Claims] 1. A silver halide color photographic light-sensitive material having at least one silver halide emulsion layer on a support, wherein at least one layer contains at least two cyan couplers represented by the following general formula [A]. And the two couplers are different from each other in at least one substituent of R ₁ , R ₂ and R ₃ , and the high boiling point organic solvent in the layer is large in weight ratio to the total amount of the cyan coupler. A silver halide color photographic light-sensitive material, characterized in that both are 0.3. General formula [A] In the general formula [A], R ₁ is a halogen atom, an aliphatic group,
Aromatic group, heterocyclic group, amidino group, guanidino group, or _{-COR 4, -SO 2 R 4,} -SOR 4, Represents a group represented by, R ₂ is a halogen atom, a hydroxyl group, a carboxyl group, a sulfo group, an amino group, a cyano group, a nitro group, an aliphatic group, an aromatic group, a carboxamide group, a sulfonamide group, a carbamoyl group, Sulfamoyl group, ureido group, acyl group, acyloxy group, aliphatic oxy group, aromatic oxy group, aliphatic sulfonyl group, aromatic sulfonyl group, aliphatic sulfinyl group, aromatic sulfinyl group, aliphatic oxycarbonyl group, aromatic Oxycarbonyl group, aliphatic oxycarbonylamino group, aromatic oxycarbonylamino group, sulfamoylamino group,
Represents a heterocyclic group or an imido group, l 'is 0 to an integer of 3, a coupling with R ₃ represents a hydrogen atom or R ₆ U, T is hydrogen atom or an aromatic primary amine developing agent oxidized form Represents a group which can be removed by a reaction. However, R ₄ and R ₅ each independently represent an aliphatic group, an aromatic group, a heterocyclic group, an amino group, an aliphatic oxy group, or an aromatic oxy group, and R ₆ represents a hydrogen atom, an aliphatic group, an aromatic group. Group, heterocyclic group, -OR ₇ , -SR ₇ , -COR ₈ , -CO ₂ R ₇ , -SO ₂ R ₇ , -SO ₂ OR ₇ or an imide group,
U is _{N-R 9, -CO -,} - SO 2 -, represents a SO- or a single bond. Here, R ₇ represents an aliphatic group, an aromatic group or a heterocyclic group, R ₈ represents a hydrogen atom, an aliphatic group, an aromatic group or a heterocyclic group, and R ₉ and R ₁₀ each independently represent a hydrogen atom , An aliphatic group, an aromatic group, a heterocyclic group, an acyl group, an aliphatic sulfonyl group or an aromatic sulfonyl group. When l ′ is plural, R ₂ may be the same or different,
Further, they may combine with each other to form a ring. R ₂ and R ₃ or R ₃ and T may be bonded to each other to form a ring.