JPH11271940A - Silver halide color photographic sensitive material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To enable preferable control of the absorption characteristics of a dye produced from a coupler by incorporating a specified compound in the silver halide color photographic sensitive material having a silver halide emulsion layer on a support. SOLUTION: The silver halide color photographic sensitive material having the silver halide emulsion layer on a support contains the compound represented by the formula in which each of R<1> and R<2> is, independently, an H atom or an aliphatic or aryl group, preferably, an H atom or an optionally substituted 1-30C alkyl or 3-30C alkenyl group or the like and each is, preferably, same as each other, and most preferably, an H atom; each of X<1> and X<2> is, independently, a -OR<4> or N(R<5> )R<6> group; each of R<4> -R<6> is, independently, an H atom or an aliphatic or aryl group, preferably, an H atom or a 1-30C alkyl group or the like.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a silver halide photographic material containing a bisurethane or bisureido compound having a specific structure. Also, the present invention relates to a silver halide photosensitive material in which problems such as color image fastness, color reproducibility and hue are improved by using a pyrrolotriazole cyan coupler in combination with a compound having a specific structure.

[0002]

2. Description of the Related Art In a silver halide color photographic light-sensitive material, an oxidized aromatic primary amine color developing agent and a coupler react with an exposed silver halide as an oxidizing agent to form an indophenol or indoaniline. It is well-known that dyes such as indamine, azomethine, phenoxazine, and phenazine are formed, and an image is formed. In this photographic method, a subtractive color method is used, and a color image is formed with three primary colors of yellow, magenta, and cyan. In order to obtain excellent color reproducibility, the absorption spectra of the three primary color dyes need to be ideal.
Dyes formed from couplers do not always have a sufficiently ideal absorption spectrum. For example, there has been a problem that the absorption maximum wavelength is shifted to a shorter wavelength side or a longer wavelength side than the optimum value, and unnecessary side absorption exists. Various dispersion media have been used for the purpose of adjusting the hue of such dyes. By using the dispersion medium, the absorption maximum wavelength of the formed dye can be shifted to the short wavelength side or the long wavelength side. Further, when the formed dye forms a dimer or a multimer and unnecessary side absorption derived therefrom is present, the formation of the dimer or the multimer can be suppressed by using a dispersion medium. However, conventionally known dispersion media, the ability to adjust the hue is not enough, the light or heatfastness of the formed dye, or reduce the color development, or promote the generation of stain,
It has disadvantages such as increasing fog and adversely affecting sensitivity.

On the other hand, in order to form a cyan dye image, a phenol or naphthol coupler has hitherto been used. However, dyes formed from these couplers have an undesirable side absorption in the yellow to magenta region, and thus have a problem of deteriorating color reproducibility. Is desired. As means for solving this problem, US Pat. Nos. 4,728,598 and 4,873,183.
, European Patent Application Publication No. 0249453A2 and the like have been proposed. However, these couplers have fatal drawbacks such as low coupling activity and poor dye fastness. U.S. Pat. No. 5,256,52 discloses a coupler that overcomes these problems.
No. 6, pyrrolotriazole couplers described in EP 0545300 have been proposed. However, there is an absorption originating from an association of a dye formed from a pyrrolotriazole coupler, and it is difficult to adjust the absorption to an ideal value. Further, this coupler is excellent in coupling activity, but the fastness of a color dye image is not always sufficient, and the light fastness particularly in a low color density portion is inferior to that of a conventional coupler, and improvement is desired. Was.
Further, it has been desired that the whiteness of a white background is higher even after a lapse of time.

Further, pyrrolotriazole couplers are p-
Due to the high molecular extinction coefficient of the dye formed by the reaction with the phenylenediamine color developing agent, the oxidized developing agent formed as a result of silver development in the other layer diffuses into the red-sensitive layer and reacts with the cyan coupler in the red-sensitive layer. Increase the cyan density,
There is a disadvantage that color mixing during processing is large. Further, the pyrrolotriazole coupler has a high absorption coefficient of the formed dye, so that various processes caused by the reaction between the color developing agent remaining in the film and the coupler over time after the color development step during the processing and after the processing, and the processing. There is a disadvantage that the cyan stain becomes high.

[0005]

SUMMARY OF THE INVENTION It is a first object of the present invention to provide a silver halide light-sensitive material containing a dispersion medium capable of favorably controlling the absorption characteristics of a dye formed from a coupler. A second object of the present invention is to provide a silver halide color light-sensitive material having excellent color reproducibility and improved storage stability of the light-sensitive material. A third object of the present invention is to provide a silver halide color light-sensitive material having reduced cyan color mixture during processing. A fourth object of the present invention is to provide a silver halide color light-sensitive material having reduced cyan stain. A fifth object of the present invention is to provide a silver halide color light-sensitive material having excellent color development and fastness.

[0006]

It has been found that the above-mentioned object is achieved by a photosensitive material having the following constitution. A silver halide color photographic material having at least one silver halide emulsion on a support, comprising at least one compound represented by the following formula (Ia).

[0007]

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Wherein R ¹ and R ² are each independently a hydrogen atom,
Represents an aliphatic group or an aryl group. X ¹ and X ² each independently represent —OR ⁴ or —N (R ⁵ ) R ⁶ . R ⁴ ,
R ⁵ and R ⁶ represent a hydrogen atom, an aliphatic group, or an aryl group, but none of R ¹ , R ⁵ , and R ⁶ is an alkyl group. In a silver halide color photographic material having at least one silver halide emulsion on a support, at least one compound represented by the following general formula (Ib) and a cyan coupler represented by the following general formula (II) are used. A silver halide photographic light-sensitive material comprising at least one kind.

[0009]

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In the formula (Ib), R ¹ , R ² , R ⁴ , X ¹ , X
² is the same as defined in R ³ represents a hydrogen atom or a substituent. R ⁵ and R ⁶ each independently represent a hydrogen atom, an aliphatic group, or an aryl group. n represents the integer of 0-4. The compound represented by formula (Ib) has no ability to react with an oxidized color developing agent to form a dye. Wherein ^{(II), Z a, Z} b each -C (R ¹³⁾
= Or -N =. However, any of the Z ^a, Z ^b, is -N =, the other is, -C (R ¹³⁾ is =. R
¹¹ and R ¹² each have a Hammett's substituent constant σ _p of 0.2
Represents an electron-withdrawing group of 0 or more, and the sum of the σ _p values of R ¹¹ and R ¹² is 0.65 or more. R ¹³ represents a hydrogen atom or a substituent. X ³ represents a hydrogen atom or a group capable of leaving in a coupling reaction with an oxidized form of an aromatic primary amine developing agent. The group of R ¹¹ , R ¹² , R ¹³ or X ³ may be a divalent group and form a homopolymer or a copolymer by bonding to a dimer or higher polymer or a polymer chain. .

[0011]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below in detail. Here, the Hammett's substituent constant σ _p value used in the present specification will be briefly described. The Hammett's rule is an empirical rule proposed by LP Hammett in 1935 to quantitatively discuss the effect of substituents on the reaction or equilibrium of a benzene derivative, and is widely accepted today. The substituent constant determined by Hammett's rule is σ
There is _p value and sigma _m value and these values can be found in many general books, for example, JADean ed, "Lang
e's Handbook of Chemistry, 12th edition, 1979 (Mc Graw-Hill)
See pages 6-103, 1979 (Nankodo). In addition,
In the present invention, each substituent is defined or described by Hammett's substituent constant σ _p, but this is found in the above-mentioned textbook, in the sense that it is limited only to a substituent having a known value in the literature. In addition, it goes without saying that even if the value is unknown in the literature, it also includes a substituent that will be included in the range when measured based on the Hammett rule. Although the compound represented by the general formula (I) of the present invention is not a benzene derivative, the σ _p value is used as a measure of the electronic effect of the substituent regardless of the substitution position. In the present invention, the σ _p value will be used in this sense in the future. The term “lipophilic” as used in the present invention means that the solubility in water at room temperature is 1%.
It is less than 0%.

In the present specification, the term "aliphatic" means a linear, branched or cyclic, saturated or unsaturated group, for example, alkyl, alkenyl, alkynyl, cycloalkyl or cycloalkenyl. May further have a substituent. Also, aromatic represents aryl,
This may further have a substituent, and a heterocyclic ring (heterocycle) is one having a hetero atom in the ring, including an aromatic group, and further having a substituent. I don't care. The substituents in the present specification and the substituents which may be present on these aliphatic, aromatic, and heterocyclic rings may be any groups that can be substituted unless otherwise specified, and include, for example, an aliphatic group and an aromatic group. Group, heterocyclic group, acyl group, acyloxy group, acylamino group, aliphatic oxy group, aromatic oxy group, heterocyclic oxy group, aliphatic oxycarbonyl group, aromatic oxycarbonyl group, heterocyclic oxycarbonyl group, aliphatic Carbamoyl group, aromatic carbamoyl group, aliphatic sulfonyl group, aromatic sulfonyl group, aliphatic flufamoyl group, aromatic sulfamoyl group, aliphatic sulfonamide group, aromatic sulfonamide group, aliphatic amino group, aromatic amino group, Aliphatic sulfinyl group, aromatic sulfinyl group, aliphatic thio group, aromatic thio group, mercapto group, hydroxy group, cyano group, nitro Group, hydroxyamino group,
Examples include a halogen atom.

The general formulas (Ia) and (Ib) of the present invention are described below.
The compound represented by is described in detail. Where R ¹ ,
R ² each independently represents a hydrogen atom, an aliphatic group, or an aryl group which may be the same or different. Preferably, a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms (eg, methyl, ethyl, i-propyl, n-
Butyl, i-butyl, t-butyl, n-octyl, n-
Hexadecyl, 2-ethylhexyl, 2-chloroethyl, 2-cyanoethyl, 3-chloropropyl, 2-methoxyethyl), a substituted or unsubstituted alkenyl group having 3 to 30 carbon atoms (for example, allyl, homoallyl, prenyl, geranyl, geranylgeranyl) Oleyl), substituted or unsubstituted cycloalkyl group having 3 to 30 carbon atoms (eg, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl), substituted or unsubstituted carbon number 6
To 30 aryl groups (e.g., phenyl, naphthyl, phenanthryl, tolyl, p-methoxyphenyl, o-chlorophenyl, m-acetylaminophenyl).
R ¹ and R ² are preferably a hydrogen atom or a group having 1 to 2 carbon atoms.
It is 0 unsubstituted alkyl group. R ¹ and R ² are preferably the same as each other. Most preferably, R ¹ and R ² are both hydrogen atoms. X ¹ and X ² may be the same or different and represent —OR ⁴ or —N (R ⁵ ) R ⁶ ;
R ⁴ , R ⁵ and R ⁶ may be the same or different and represent a hydrogen atom, an aliphatic group or an aryl group. R ⁴ ,
R ⁵ and R ⁶ are preferably a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted alkenyl group having 3 to 30 carbon atoms, a substituted or unsubstituted alkenyl group having 3 to 30 carbon atoms.
30 cycloalkyl groups, substituted or unsubstituted C6 to C6
30 aryl groups. Specific examples of R ⁴ , R ⁵ and R ⁶ include those described for R ¹ and R ² . R
⁴ is preferably a substituted or unsubstituted alkyl group having 6 to 30 carbon atoms, and more preferably an unsubstituted alkyl group having 6 to 30 carbon atoms. Specific examples of preferred alkyl groups for R ⁴ include n
-Hexyl, n-octyl, n-decyl, n-dodecyl, n-tetradecyl, n-hexadecyl, n-octadecyl, n-eicosyl. Further, a branched alkyl group derived from fine oxocols manufactured by Nissan Chemical Co., Ltd. is also preferable. Fine oxocols are preferably fine oxocols 1400, 1600, 1
80, 180N, 1800, 2000, and 2400. R ⁵ and R ^{6 each} represent a hydrogen atom and a carbon number of ^{6 to 3} ;
A substituted or unsubstituted alkyl group of 0 or a substituted or unsubstituted cycloalkyl group having 5 to 7 carbon atoms is preferred. R ⁵ , R ⁶
Are preferably the same, and more preferably have the same carbon number of 6 to
A 30 unsubstituted alkoxy group or the same unsubstituted cycloalkyl group having 5 to 7 carbon atoms is preferred. The most preferred embodiment of R ^5, R ⁶ are, n- octyl, 2-ethylhexyl, n- dodecyl, n- tetradecyl, n- hexadecyl, n- octadecyl. X ¹ and X ² are preferably the same.

R ³ represents a hydrogen atom or a substituent.
As the substituent, a halogen atom, an alkyl group, an aryl group, a heterocyclic group, a cyano group, a hydroxy group, a nitro group,
Carboxy group, sulfo group, amino group, alkoxy group, aryloxy group, acylamino group, alkylamino group,
Anilino group, ureido group, sulfamoylamino group, alkylthio group, arylthio group, alkoxycarbonylamino group, sulfonamide group, carbamoyl group, sulfamoyl group, sulfonyl group, alkoxycarbonyl group,
Examples include a heterocyclic oxy group, an azo group, an acyloxy group, a carbamoyloxy group, a silyloxy group, an aryloxycarbonylamino group, an imide group, a heterocyclic thio group, a sulfinyl group, a phosphonyl group, an aryloxycarbonyl group, and an acyl group.

More specifically, R ³ is a hydrogen atom, a halogen atom (for example, a chlorine atom or a bromine atom), an alkyl group (for example, a linear or branched alkyl group having 1 to 32 carbon atoms, an aralkyl group, an alkenyl group). , Alkynyl, cycloalkyl and cycloalkenyl groups such as methyl, ethyl, propyl, isopropyl, t-butyl, tridecyl, 2-methanesulfonylethyl,
(3-pentadecylphenoxy) propyl, 3- {4-
{2- [4- (4-hydroxyphenylsulfonyl) phenoxy] dodecaneamide} phenyl} propyl, 2-
Ethoxytridecyl, trifluoromethyl, cyclopentyl, 3- (2,4-di-t-amylphenoxy) propyl), aryl group (for example, phenyl, 4-t-butylphenyl, 2,4-di-t-amyl) Phenyl, 4-tetradecanamidophenyl), a heterocyclic group (eg, imidazolyl, pyrazolyl, triazolyl, 2-furyl,
2-thienyl, 2-pyrimidinyl, 2-benzothiazolyl), cyano group, hydroxy group, nitro group, carboxy group, amino group, alkoxy group (for example, methoxy, ethoxy, 2-methoxyethoxy, 2-dodecylethoxy,
2-methanesulfonylethoxy), aryloxy group (for example, phenoxy, 2-methylphenoxy, 4-t
-Butylphenoxy, 3-nitrophenoxy, 3-t-
Butyloxycarbamoylphenoxy, 3-methoxycarbamoyl), acylamino group (for example, acetamido, benzamido, tetradecanamido, 2- (2,4
-Di-t-amylphenoxy) butanamide, 4- (3
-T-butyl-4-hydroxyphenoxy) butanamide, 2- {4- (4-hydroxyphenylsulfonyl)
Phenoxy didecaneamide), an alkylamino group (eg, methylamino, butylamino, dodecylamino, diethylamino, methylbutylamino), an anilino group (eg, phenylamino, 2-chloroanilino, 2-chloro-5-tetradecaneaminoanilino, 2-chloro-5
-Dodecyloxycarbonylanilino, N-acetylanilino, 2-chloro-5- {2- (3-t-butyl-4)
-Hydroxyphenoxy) dodecaneamide {anilino), a ureido group (eg, phenylureido, methylureido, N, N-dibutylureido), a sulfamoylamino group (eg, N, N-dipropylsulfamoylamino, N-methyl) -N-decylsulfamoylamino), an alkylthio group (for example, methylthio, octylthio, tetradecylthio, 2-phenoxyethylthio,
3-phenoxypropylthio, 3- (4-t-butylphenoxy) propylthio), an arylthio group (for example,
Phenylthio, 2-butoxy-5-t-octylphenylthio, 3-pentadecylphenylthio, 2-carboxyphenylthio, 4-tetradecanamidophenylthio), alkoxycarbonylamino group (for example, methoxycarbonylamino, tetradecyloxycarbonyl) Amino), a sulfonamide group (eg, methanesulfonamide, hexadecanesulfonamide, benzenesulfonamide, p-toluenesulfonamide, octadecanesulfonamide, 2-methoxy-5-t-butylbenzenesulfonamide), a carbamoyl group (eg, N-ethylcarbamoyl, N, N-dibutylcarbamoyl, N-
(2-dodecyloxyethyl) carbamoyl, N-methyl-N-dodecylcarbamoyl, N- {3- (2,4-
Di-t-amylphenoxy) propyl @ carbamoyl), a sulfamoyl group (eg, N-ethylsulfamoyl, N, N-dipropylsulfamoyl, N- (2
-Dodecyloxyethyl) sulfamoyl, N-ethyl-N-dodecylsulfamoyl, N, N-diethylsulfamoyl), sulfonyl group (for example, methanesulfonyl, octanesulfonyl, benzenesulfonyl, toluenesulfonyl), alkoxycarbonyl group ( For example, methoxycarbonyl, butyloxycarbonyl, dodecyloxycarbonyl, octadecyloxycarbonyl),
Heterocyclic oxy group (for example, 1-phenyltetrazol-5-oxy, 2-tetrahydropyranyloxy), azo group (for example, phenylazo, 4-methoxyphenylazo, 4-pivaloylaminophenylazo, 2-hydroxy- 4-propanoylphenylazo), an acyloxy group (eg, acetoxy), a carbamoyloxy group (eg, N-methylcarbamoyloxy, N-phenylcarbamoyloxy), a silyloxy group (eg, trimethylsilyloxy, dibutylmethylsilyloxy), aryl An oxycarbonylamino group (for example, phenoxycarbonylamino), an imide group (for example, N-succinimide, N-phthalimide, 3-octadecenylsuccinimide), a heterocyclic thio group (for example, 2-benzothiazolylthio, 2, 4 Di-phenoxy-1,3,5-triazole-6-thio, 2-pyridylthio), a sulfinyl group (eg, dodecanesulfinyl, 3-pentadecylphenylsulfinyl, 3-phenoxypropylsulfinyl), a phosphonyl group (eg, phenoxyphospho) Nyl, octyloxyphosphonyl, phenylphosphonyl), an aryloxycarbonyl group (for example, phenoxycarbonyl), and an acyl group (for example, acetyl, 3-phenylpropanoyl, benzoyl, 4-dodecyloxybenzoyl). R ³ is preferably a hydrogen atom, an unsubstituted alkyl group having 1 to 10 carbon atoms, a chlorine atom, a bromine atom, an alkoxy group having 1 to 10 carbon atoms, a cyano group, a nitro group, an acylamino group having 1 to 10 carbon atoms, Carbon number 1-10
A ureido group, a sulfamoylamino group having 0 to 10 carbon atoms, a carbamoylamino group having 1 to 10 carbon atoms, and a carbon atom having 1 carbon atom
A sulfonamide group having 10 to 10, an alkoxycarbonylamino group having 2 to 10 carbon atoms, and an aminocarbonylamino group having 1 to 10 carbon atoms. R ³ is more preferably a hydrogen atom, a chlorine atom, or an unsubstituted alkyl group having 1 to 10 carbon atoms. Among them, R ³ is most preferably a hydrogen atom. Formulas (Ia), (I
The compound of b) includes R ¹ , R ² , R ³ ,
It is preferable that at least ^{one of} X ¹ and X ² has a so-called ballast group. The molecular weight is preferably at least 200, more preferably at least 250, even more preferably at least 300,
350 or more is most preferable. The molecular weight is preferably 500 or less. The compounds of the general formulas (Ia) and (Ib) are not polymers or oligomers having a plurality of repeating units.
Further, it does not have a hydroquinone structure as a partial structure. −
^{N (R 1) - (C} = O) -X 1 and ^{-N (R 2) - (C} = O)
-X ² is preferably substituted with each other at the m-position. The compounds of the general formulas (Ia) and (Ib) are not dyes having absorption in the visible region.

Hereinafter, a system represented by the general formula (II) of the present invention will be described.
The uncoupler will be described in detail. Z^aAnd Z^bHaso
Each -C (R¹³) = Or -N =. Where Z^aPassing
And Z ^bIs -N = and the other is -C
(R¹³) =.

R ¹³ represents a hydrogen atom or a substituent, and the substituent is a halogen atom, an alkyl group, an aryl group, a heterocyclic group, a cyano group, a hydroxy group, a nitro group, a carboxy group, a sulfo group, an amino group, an alkoxy group. Group, aryloxy group, acylamino group, alkylamino group, anilino group, ureido group, sulfamoylamino group, alkylthio group, arylthio group, alkoxycarbonylamino group, sulfonamide group, carbamoyl group, sulfamoyl group, sulfonyl group, alkoxy Carbonyl group, heterocyclic oxy group, azo group, acyloxy group, carbamoyloxy group, silyloxy group, aryloxycarbonylamino group, imide group, heterocyclic thio group, sulfinyl group,
Examples include a phosphonyl group, an aryloxycarbonyl group, and an acyl group. These groups may be further substituted with substituents as exemplified for R ³ .

More specifically, R ³ is a hydrogen atom, a halogen atom (for example, a chlorine atom or a bromine atom), an alkyl group (for example, a linear or branched alkyl group having 1 to 32 carbon atoms, an aralkyl group, an alkenyl group). Alkynyl group, cycloalkyl group and cycloalkenyl group, specifically, for example, methyl, ethyl, propyl, isopropyl, t-butyl, tridecyl, 2-methanesulfonylethyl, 3-
(3-pentadecylphenoxy) propyl, 3- {4-
{2- [4- (4-hydroxyphenylsulfonyl) phenoxy] dodecaneamide} phenyl} propyl, 2-
Ethoxytridecyl, trifluoromethyl, cyclopentyl, 3- (2,4-di-t-amylphenoxy) propyl), aryl group (for example, phenyl, 4-t-butylphenyl, 2,4-di-t-amyl) Phenyl, 4-tetradecanamidophenyl), a heterocyclic group (eg, imidazolyl, pyrazolyl, triazolyl, 2-furyl,
2-thienyl, 2-pyrimidinyl, 2-benzothiazolyl), cyano group, hydroxy group, nitro group, carboxy group, amino group, alkoxy group (for example, methoxy, ethoxy, 2-methoxyethoxy, 2-dodecylethoxy,
2-methanesulfonylethoxy), aryloxy group (for example, phenoxy, 2-methylphenoxy, 4-t
-Butylphenoxy, 3-nitrophenoxy, 3-t-
Butyloxycarbamoylphenoxy, 3-methoxycarbamoyl), acylamino group (for example, acetamido, benzamido, tetradecanamido, 2- (2,4
-Di-t-amylphenoxy) butanamide, 4- (3
-T-butyl-4-hydroxyphenoxy) butanamide, 2- {4- (4-hydroxyphenylsulfonyl)
Phenoxy didecaneamide), an alkylamino group (eg, methylamino, butylamino, dodecylamino, diethylamino, methylbutylamino), an anilino group (eg, phenylamino, 2-chloroanilino, 2-chloro-5-tetradecaneaminoanilino, 2-chloro-5
-Dodecyloxycarbonylanilino, N-acetylanilino, 2-chloro-5- {2- (3-t-butyl-4)
-Hydroxyphenoxy) dodecaneamide {anilino), a ureido group (eg, phenylureido, methylureido, N, N-dibutylureido), a sulfamoylamino group (eg, N, N-dipropylsulfamoylamino, N-methyl) -N-decylsulfamoylamino), an alkylthio group (for example, methylthio, octylthio, tetradecylthio, 2-phenoxyethylthio,
3-phenoxypropylthio, 3- (4-t-butylphenoxy) propylthio), an arylthio group (for example,
Phenylthio, 2-butoxy-5-t-octylphenylthio, 3-pentadecylphenylthio, 2-carboxyphenylthio, 4-tetradecanamidophenylthio), alkoxycarbonylamino group (for example, methoxycarbonylamino, tetradecyloxycarbonyl) Amino), a sulfonamide group (eg, methanesulfonamide, hexadecanesulfonamide, benzenesulfonamide, p-toluenesulfonamide, octadecanesulfonamide, 2-methoxy-5-t-butylbenzenesulfonamide), a carbamoyl group (eg, N-ethylcarbamoyl, N, N-dibutylcarbamoyl, N-
(2-dodecyloxyethyl) carbamoyl, N-methyl-N-dodecylcarbamoyl, N- {3- (2,4-
Di-t-amylphenoxy) propyl @ carbamoyl), a sulfamoyl group (eg, N-ethylsulfamoyl, N, N-dipropylsulfamoyl, N- (2
-Dodecyloxyethyl) sulfamoyl, N-ethyl-N-dodecylsulfamoyl, N, N-diethylsulfamoyl), sulfonyl group (for example, methanesulfonyl, octanesulfonyl, benzenesulfonyl, toluenesulfonyl), alkoxycarbonyl group ( For example, methoxycarbonyl, butyloxycarbonyl, dodecyloxycarbonyl, octadecyloxycarbonyl),
Heterocyclic oxy group (for example, 1-phenyltetrazol-5-oxy, 2-tetrahydropyranyloxy), azo group (for example, phenylazo, 4-methoxyphenylazo, 4-pivaloylaminophenylazo, 2-hydroxy- 4-propanoylphenylazo), an acyloxy group (eg, acetoxy), a carbamoyloxy group (eg, N-methylcarbamoyloxy, N-phenylcarbamoyloxy), a silyloxy group (eg, trimethylsilyloxy, dibutylmethylsilyloxy), aryl An oxycarbonylamino group (for example, phenoxycarbonylamino), an imide group (for example, N-succinimide, N-phthalimide, 3-octadecenylsuccinimide), a heterocyclic thio group (for example, 2-benzothiazolylthio, 2, 4 Di-phenoxy-1,3,5-triazole-6-thio, 2-pyridylthio), a sulfinyl group (eg, dodecanesulfinyl, 3-pentadecylphenylsulfinyl, 3-phenoxypropylsulfinyl), a phosphonyl group (eg, phenoxyphospho) Nyl, octyloxyphosphonyl, phenylphosphonyl), an aryloxycarbonyl group (for example, phenoxycarbonyl), and an acyl group (for example, acetyl, 3-phenylpropanoyl, benzoyl, 4-dodecyloxybenzoyl).

R ¹³ is preferably an alkyl group, an aryl group, a heterocyclic group, a cyano group, a nitro group, an acylamino group, an anilino group, a ureido group, a sulfamoylamino group, an alkylthio group, an arylthio group, or an alkoxycarbonylamino group. , Sulfonamide group, carbamoyl group,
Sulfamoyl group, sulfonyl group, alkoxycarbonyl group, heterocyclic oxy group, acyloxy group, carbamoyloxy group, aryloxycarbonylamino group, imide group, heterocyclic thio group, sulfinyl group, phosphonyl group, aryloxycarbonyl group, acyl group Can be mentioned.

More preferably, they are an alkyl group and an aryl group, more preferably an alkyl group and an aryl group having at least one substituent, and still more preferably, at least one alkyl group and an alkoxy group from the viewpoint of cohesiveness. , A sulfonyl group, a sulfamoyl group, a carbamoyl group, an acylamide group or an alkyl group or an aryl group having a sulfonamide group as a substituent. Particularly preferred is an alkyl group or an aryl group having at least one alkyl group, acylamide group or sulfonamide group as a substituent. When these substituents are present in the aryl group, it is more preferable to have them at least in the ortho or para position.

The cyan coupler of the present invention, R ¹¹ and R ¹² are both also 0.20 or more electron-withdrawing groups, and R ¹¹
The sum of sigma _p values of R ¹² is one which colored cyan image by 0.65 or more. The sum of the σ _p values of R ¹¹ and R ¹² is preferably 0.70 or more, and the upper limit is about 1.8.

R ¹¹ and R ¹² are Hammett's substituent constant σ _p
An electron-withdrawing group having a value of 0.20 or more. Preferably,
It is an electron-withdrawing group of 0.30 or more. The upper limit is 1.
It is an electron-withdrawing group of 0 or less.

Specific examples of the electron-withdrawing groups R ¹¹ and R ^{12 having} a σ _p value of 0.20 or more include acyl, acyloxy, carbamoyl, alkoxycarbonyl, aryloxycarbonyl, cyano, Nitro group, dialkylphosphono group, diarylphosphono group, diarylphosphinyl group, alkylsulfinyl, arylsulfinyl group, alkylsulfonyl group, arylsulfonyl group, sulfonyloxy group, acylthio group, sulfamoyl group, thiocyanate group, thiocarbonyl group , a halogenated alkyl group, halogenated alkoxy group, a halogenated aryloxy group, a halogenated alkylamino group, a halogenated alkylthio group, an aryl group which sigma _p value is substituted with 0.20 or more other electron-withdrawing group, Heterocyclic group, halogen atom, azo group, or A selenocyanate group. Among these substituents, the group which can further have a substituent may further have a substituent as described for R ¹³ .

If R ¹¹ and R ¹² are described in more detail, σ _p
Examples of the electron-withdrawing group having a value of 0.20 or more include an acyl group (eg, acetyl, 3-phenylpropanoyl, benzoyl, 4-dodecyloxybenzoyl), an acyloxy group (eg, acetoxy), a carbamoyl group (eg, carbamoyl) , N-ethylcarbamoyl, N-phenylcarbamoyl, N, N-dibutylcarbamoyl, N
-(2-dodecyloxyethyl) carbamoyl, N-
(4-n-pentadecanamido) phenylcarbamoyl, N-methyl-N-dodecylcarbamoyl, N- {3
-(2,4-di-t-amylphenoxy) propyl} carbamoyl), an alkoxycarbonyl group (for example, methoxycarbonyl, ethoxycarbonyl, iso-propyloxycarbonyl, tert-butyloxycarbonyl, iso-
Butyloxycarbonyl, butyloxycarbonyl, dodecyloxycarbonyl, octadecyloxycarbonyl), aryloxycarbonyl group (eg, phenoxycarbonyl), cyano group, nitro group, dialkylphosphono group (eg, dimethylphosphono), diarylphosphono group (E.g., diphenylphosphono), diarylphosphinyl group (e.g., diphenylphosphinyl), alkylsulfinyl group (e.g., 3-phenoxypropylsulfinyl), arylsulfinyl group (e.g.,
3-pentadecylphenylsulfinyl), alkylsulfonyl group (eg, methanesulfonyl, octanesulfonyl), arylsulfonyl group (eg, benzenesulfonyl, toluenesulfonyl), sulfonyloxy group (methanesulfonyloxy, toluenesulfonyloxy), acylthio Groups (eg, acetylthio, benzoylthio), sulfamoyl groups (eg, N-ethylsulfamoyl, N, N-dipropylsulfamoyl, N-
(2-dodecyloxyethyl) sulfamoyl, N-ethyl-N-dodecylsulfamoyl, N, N-diethylsulfamoyl), thiocyanate group, thiocarbonyl group (eg, methylthiocarbonyl, phenylthiocarbonyl), alkyl halide Groups (eg, trifluoromethane, heptafluoropropane), halogenated alkoxy groups (eg, trifluoromethyloxy), halogenated aryloxy groups (eg, pentafluorophenyloxy), halogenated alkylamino groups (eg, N, N-
Di- (trifluoromethyl) amino), a halogenated alkylthio group (for example, difluoromethylthio, 1,1,2,2
2-tetrafluoroethane ethylthiomethyl), an aryl group substituted with sigma _p 0.20 or more other electron withdrawing group (e.g., 2,
4-dinitrophenyl, 2,4,6-trichlorophenyl, pentachlorophenyl), a heterocyclic group (for example, 2-
Benzoxazolyl, 2-benzothiazolyl, 1-phenyl-2-benzimidazolyl, 5-chloro-1-tetrazolyl, 1-pyrrolyl), halogen atom (eg, chlorine atom, bromine atom), azo group (eg, phenylazo)
Or a selenocyanate group. Among these substituents, the group which can further have a substituent may further have a substituent as described for R ¹³ .

R ¹¹ and R ¹² are preferably acyl, acyloxy, carbamoyl, alkoxycarbonyl, aryloxycarbonyl, cyano, nitro, alkylsulfinyl, arylsulfinyl, Alkylsulfonyl group, arylsulfonyl group, sulfamoyl group, halogenated alkyl group, halogenated alkyloxy group, halogenated alkylthio group,
A halogenated aryloxy group, two or more σ _p 0.20
An aryl group substituted with the other electron-withdrawing group and a heterocyclic group can be exemplified. More preferred are an alkoxycarbonyl group, a nitro group, a cyano group, an arylsulfonyl group, a carbamoyl group and a halogenated alkyl group. Most preferred as R ¹¹ is a cyano group. Particularly preferred as R ¹² is an alkoxycarbonyl group, and most preferred is a branched alkoxycarbonyl group (particularly a cycloalkoxycarbonyl group).

X ³ represents a hydrogen atom or a group capable of leaving in a coupling reaction with an oxidized form of an aromatic primary amine color developing agent. If the group capable of leaving is specifically described, a halogen atom, an alkoxy group, an aryl group Oxy group, acyloxy group, alkyl or arylsulfonyloxy group, acylamino group, alkyl or arylsulfonamide group, alkoxycarbonyloxy group, aryloxycarbonyloxy group, alkyl, aryl or heterocyclic thio group, carbamoylamino group, carbamoyloxy group And a heterocyclic carbonyloxy group, a 5- or 6-membered nitrogen-containing heterocyclic group, an imide group, an arylazo group, and the like. These groups may be further substituted with a group permitted as a substituent of R ^13. .

More specifically, halogen atoms (eg, fluorine, chlorine, bromine), alkoxy groups (eg, ethoxy, dodecyloxy, methoxyethylcarbamoylmethoxy, carboxypropyloxy, methanesulfonylethoxy, ethoxycarbonylmethoxy), aryl An oxy group (e.g., 4-methylphenoxy, 4-
Chlorophenoxy, 4-methoxyphenoxy, 4-carboxyphenoxy, 3-ethoxycarbonylphenoxy, 3-acetylaminophenoxy, 2-carboxyphenoxy), acyloxy group (eg, acetoxy, tetradecanoyloxy, benzoyloxy), alkyl or aryl Sulfonyloxy group (for example, methanesulfonyloxy, toluenesulfonyloxy), acylamino group (for example, dichloroacetylamino, heptafluorobutyrylamino), alkyl or arylsulfonamide group (for example, methanesulfonylamino,
Trifluoromethanesulfonylamino, p-toluenesulfonylamino), alkoxycarbonyloxy group (for example, ethoxycarbonyloxy, benzyloxycarbonyloxy), aryloxycarbonyloxy group (for example, phenoxycarbonyloxy), alkyl,
Aryl or heterocyclic thio groups (e.g. dodecylthio, 1-carboxydodecylthio, phenylthio, 2-
Butoxy-5-t-octylphenylthio, tetrazolylthio), carbamoylamino group (for example, N-methylcarbamoylamino, N-phenylcarbamoylamino), carbamoyl group (for example, N, N-diethylcarbamoyl, N-ethylcarbamoyl, N -Ethyl-N-
Phenylcarbamoyl), a heterocyclic carbonyloxy group (for example, morpholinocarbonyloxy, piperidinocarbonyloxy), a 5- or 6-membered nitrogen-containing heterocyclic group (for example, imidazolyl, pyrazolyl, triazolyl, tetrazolyl, 1,2-dihydro -2-oxo-1
-Pyridyl), an imide group (eg, succinimide, hydantoinyl), an arylazo group (eg, phenylazo, 4-methoxyphenylazo) and the like. X ³ may also take the form of a bis-type coupler obtained by condensing a 4-equivalent coupler with an aldehyde or ketone as a leaving group bonded via a carbon atom. X ³ may contain a photographically useful group such as a development inhibitor and a development accelerator.

Preferred X ³ is a halogen atom, an alkoxy group, an aryloxy group, an alkyl or arylthio group, an alkyloxycarbonyloxy group, an aryloxycarbonyloxy group, a carbamoyloxy group, a heterocyclic carbonyloxy group, or a coupling active site. It is a 5- or 6-membered nitrogen-containing heterocyclic group bonded by a nitrogen atom. More preferred X ³ is a halogen atom, an alkyl or arylthio group, an alkyloxycarbonyloxy group, an aryloxycarbonyloxy group, a carbamoyloxy group, a heterocyclic carbonyloxy group, and particularly preferred are a carbamoyloxy group, a heterocyclic carbonyloxy group. Group.

In the cyan coupler represented by the general formula (II), the group represented by R ¹¹ , R ¹² , R ¹³ or X ³ is a divalent group,
It may form a homopolymer or a copolymer by combining with a polymer or a polymer chain of a dimer or more. The homopolymer or copolymer bonded to the polymer chain is a typical example of an addition polymer having a cyan coupler residue represented by the general formula (II), homo- or copolymer of an ethylenically unsaturated compound. . In this case, the polymer may contain one or more kinds of cyan coloring repeating units having a cyan coupler residue represented by the general formula (II), and one of non-coloring ethylene type monomers as a copolymer component. It may be a copolymer containing one or more species. The cyan coloring repeating unit having a cyan coupler residue represented by the general formula (II) is preferably represented by the following general formula (P).

[0030]

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In the formula, R represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms or a chlorine atom, and A represents -CONH-, -COO-
Or a substituted or unsubstituted phenylene group, B represents a substituted or unsubstituted alkylene group, a phenylene group or an aralkylene group, and L represents -CONH-, -NHCONH-,
-NHCOO-, -NHCO-, -OCONH-, -NH-, -COO
-, - OCO -, - CO -, - O -, - S -, - SO 2 -, -
It represents NHSO ₂ — or —SO ₂ NH—. a, b, and c represent 0 or 1. Q represents a cyan coupler residue in which a hydrogen atom has been removed from R ¹¹ , R ¹² , R ¹³ or X of the compound represented by the general formula (II). As the polymer, a copolymer of a cyan-color-forming monomer represented by a coupler unit of the general formula (II) and a non-color-forming ethylene-like monomer that does not couple with an oxidation product of an aromatic primary amine developer is preferable.

The non-color-forming ethylene type monomer which does not couple with the oxidation product of the aromatic primary amine developer includes:
Acrylic acid, α-chloroacrylic acid, α-alkylacrylic acid (eg, methacrylic acid) Amides or esters derived from these acrylic acids (eg, acrylamide, methacrylamide, n-butylacrylamide, t-butylacrylamide, di- Acetone acrylamide, 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, eg, vinyl Toluene, divinylbenzene, vinylacetophenone and sulfostyrene), itaconic acid, citraconic acid, crotonic acid, vinylidene chloride, vinyl alkyl ether (eg, vinyl ethyl ether), maleic ester, N-vinyl-2-pyrrolidone, N-vinylilipyridine and 2- and -4-
Vinyl pyridine and the like.

Particularly preferred are acrylic esters, methacrylic esters, and maleic esters. The non-color-forming ethylene type monomer used here can be used in combination of two or more kinds. 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 ethylenically unsaturated monomer to be copolymerized with the vinyl monomer corresponding to the above general formula (II) has a physical property of a copolymer to be formed and / or Alternatively, it can be selected such that the chemical properties, such as solubility, the compatibility of the photographic colloid composition with the binder, such as gelatin, its flexibility, thermal stability, etc., are favorably affected.

The silver halide light-sensitive material of the cyan coupler of the present invention, the preferably to be contained in the red-sensitive silver halide emulsion layer, it is preferable to so-called internal type coupler. For this purpose, R ^11, R ^12, R ^13, X ³ of (preferably, a total number of 10 or more carbon atoms) at least one group called a ballast group is preferably, carbon atoms in total 10 to 50
Is more preferable. In particular, it is preferable that R ¹³ has a ballast group. The cyan coupler represented by the general formula (II) is more preferably a compound having a structure represented by the following general formula (III).

[0036]

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In the formula, R ²¹ , R ²² , R ²³ , R ²⁴ and R ²⁵ may be the same or different and each represents a hydrogen atom or a substituent. As the substituent, a substituted or unsubstituted aliphatic group or a substituted or unsubstituted aryl group is preferable, and more preferable ones are described below. R ²¹ and R ^{22 each} preferably represent an aliphatic group, for example, a linear, branched or cyclic alkyl group, aralkyl group, alkenyl group, alkynyl group, or cycloalkenyl group having 1 to 36 carbon atoms. For example, methyl, ethyl, propyl, isopropyl, t-butyl, t
-Represents amyl, t-octyl, tridecyl, cyclopentyl, cyclohexyl. The aliphatic group more preferably has 1 to 12 carbon atoms. R ²³ , R ²⁴ and R ²⁵ represent a hydrogen atom or an aliphatic group. Examples of the aliphatic group include the groups described above for R ²¹ and R ²² . R ²³ , R ²⁴ , R
²⁵ is particularly preferably a hydrogen atom.

Z is necessary for forming a 5- to 8-membered ring,
Represents a group of non-metallic atoms, and this ring may be substituted, may be a saturated ring or may have an unsaturated bond.
Preferred non-metallic atoms include a nitrogen atom, an oxygen atom, a sulfur atom and a carbon atom, and more preferably a carbon atom. Examples of the ring formed by Z include a cyclopentane ring, a cyclohexane ring, a cycloheptane ring,
Cyclooctane ring, cyclohexene ring, piperazine ring,
Oxane ring, thiane ring, these rings may be substituted by a substituent as represented by R ¹³ described above. The ring formed by Z is preferably an optionally substituted cyclohexane ring, particularly preferably an alkyl group having 1 to 24 carbon atoms at the 4-position (substituted by a substituent represented by R ¹³ described above). A cyclohexane ring substituted with

R ¹³ of [0039] Formula (III) has the same meaning as R ¹³ in Formula (II), particularly preferably an alkyl group or an aryl group, more preferably a substituted aryl group. From the viewpoint of carbon number, in the case of an alkyl group, preferably,
1 to 36, and in the case of an aryl group, preferably
6 to 36. Among the aryl groups, those in which the alkoxy group is substituted at the ortho position of the bond position with the coupler mother nucleus are not preferred because the light fastness of the dye derived from the coupler is low. In that regard, the substituents on the aryl group may be substituted or
Unsubstituted alkyl groups are preferred, and among them, unsubstituted alkyl groups are most preferred. Particularly, an unsubstituted alkyl group having 1 to 30 carbon atoms is preferable.

X ⁴ represents a hydrogen atom or a substituent. The substituent is X ⁴ -C (=
O) Groups which promote the elimination of the O- group are preferred. X ⁴ is preferably a heterocyclic ring, a substituted or unsubstituted amino group, or an aryl group. The hetero ring is preferably a 5- to 8-membered ring having a nitrogen atom, an oxygen atom, or a sulfur atom and having 1 to 36 carbon atoms. More preferably,
A 5- or 6-membered ring bonded by a nitrogen atom, of which a 6-membered ring is particularly preferred. These rings may form a condensed ring with a benzene ring or a hetero ring. Specific examples include imidazole, pyrazole, triazole, lactam compounds, piperidine, pyrrolidine, pyrrole, morpholine,
Pyrazolidine, thiazolidine, pyrazoline and the like, preferably, morpholine, piperidine,
Particularly, morpholine is preferred. Examples of the substituent of the substituted amino group include an aliphatic group, an aryl group and a heterocyclic group. Examples of the aliphatic group include the substituents of R ^{13 described} above, and further include a cyano group, an alkoxy group (eg, methoxy), an alkoxycarbonyl group (eg, ethoxycarbonyl), a chlorine atom, a hydroxyl group, a carboxyl group, and the like. May be substituted. As the substituted amino group,
Disubstitution is preferred over monosubstitution. As the substituent, an alkyl group is preferable. As the aryl group, C6 to C6
36 are preferable, and a single ring is more preferable. Specific examples include phenyl, 4-t-butylphenyl, 2-
Methylphenyl, 2,4,6-trimethylphenyl, 2
-Methoxyphenyl, 4-methoxyphenyl, 2,6-
Examples thereof include dichlorophenyl, 2-chlorophenyl, and 2,4-dichlorophenyl. The cyan coupler represented by the general formula (III) used in the present invention has an oil-solubilizing group in the molecule and is easily soluble in a high-boiling organic solvent, and the coupler itself and the coupler and a color-forming reducing agent (developer) ) Is preferably non-diffusible in the hydrophilic colloid layer. General formula (III)
In the coupler represented by, R ¹³ contains a coupler residue represented by the general formula (III) and forms a multimer of dimer or more, or R ¹³ contains a polymer chain and has a simple structure. A polymer or copolymer may be formed. The homopolymer or copolymer containing a polymer chain is represented by the general formula (II
A typical example is a homopolymer or copolymer of an addition polymer ethylenically unsaturated compound having a coupler residue represented by I). In this case, one or more kinds of cyan coloring repeating units having a coupler residue represented by the general formula (III) may be contained in the polymer, and an acrylic acid ester, a methacrylic acid ester, or a maleic acid ester may be used as a copolymer component. It may be a copolymer containing one or more non-color-forming ethylenic monomers which do not couple with the oxidation product of an aromatic primary amine developer such as phenol. Specific examples of the compounds represented by formulas (Ia) and (Ib) are shown below. The present invention is not limited to the following specific examples.

[0041]

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[0042]

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[0043]

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[0044]

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[0045]

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[0046]

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Specific examples of the cyan coupler represented by the general formula (II) are described above. The present invention is not limited to the following specific examples.

[0048]

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[0049]

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[0050]

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[0051]

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[0052]

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[0053]

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[0054]

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[0055]

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[0056]

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[0057]

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[0058]

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A method for synthesizing the compounds represented by formulas (Ia) and (Ib) will be described.

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In Scheme 1, R¹, R^Two, R^Three, N, X
¹Has the same meaning as in general formulas (Ia) and (Ib).
Scheme 1 is based on general formulas (Ia) and (Ib)¹
And X ^TwoAre the same when they are the same. L is a leaving group
It is. L is preferably a halogen atom (chlorine atom, odor
Atom, iodine atom), aryloxy group, alkoxy
Group, an oxygen atom activated by a condensing agent. Condensation
Agents include dicyclohexylcarbodiimide, acid chloride
Products, Mitsunobu reagent and the like. Synthetic raw material A
Synthesis raw material B can be reacted with various solvents.
For example, alcohol solvents (eg, methanol, ethanol
, Isopropanol), alkane solvents (for example,
Sun, pentane, petroleum ether), aromatic solvents (eg
Benzene, toluene, xylene), ester solvents
(Eg, ethyl acetate, butyl acetate), ether solvents
(Eg, diethyl ether, tetrahydrofuran),
Amide solvents (eg, dimethylacetamide, dimethyl
Formamide) ketone solvents (eg acetone, methyl
Ethyl ketone, cyclohexanone), water, acetonitrile
Carboxylic acid solvents (eg, acetic acid, propionic acid)
Is given as an example. The reaction uses 1 equivalent of base
Preferably, the base is a metal hydroxide (eg,
Sodium hydroxide, potassium hydroxide), other inorganic bases
(For example, sodium carbonate, potassium carbonate, hydrogen carbonate
Thorium), organic bases (eg, triethylamine,
Lysine, α-picoline) and the like. or,
Without using a base, HL produced as a by-product is distilled off and the reaction system is removed.
Exclusion methods can also be used. Reaction temperature is -20 ° C
To 200 ° C, more preferably 0 ° C to 100 ° C
No. When using a base, 0 ° C to 40 ° C is most preferable.
No. When no base is used, 40 ° C to 100 ° C is most preferable.
Good. The reaction time is preferably from 5 minutes to 24 hours,
0 minutes to 12 hours are more preferred. 1 to 3 hours
Most preferred. The charge ratio of synthetic raw material A to synthetic raw material B is
1: 1 to 1: 4, preferably 1: 1.5 to 1:
2.5 is more preferred. 1: 1.8-1: 2.2 is the most
preferable.

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Next, a synthesizing method when X ¹ and X ² are different will be described. In Scheme 2, R ¹ , X ¹ , X ² , R ³
Has the same meaning as R ¹ , X ¹ , X ² and R ³ in formulas (Ia) and (Ib). Intermediate A is synthesized by reacting synthesis raw material C with synthesis raw material B. The reaction conditions at this time are preferably those described in Scheme 1. Next, intermediate A is reduced and converted to intermediate B. The reduction is preferably a hydrogenation method or reduction with a metal. Examples of the catalyst in the case of the hydrogenation method include palladium carbon (Pd / C), Raney Ni, platinum oxide, and platinum black. The pressure of hydrogen is
The pressure is preferably from 1 to 100 atm, more preferably from 1 to 20 atm. 1 to 10 atm is most preferred. Any reaction solvent can be used as long as it is not reduced and the intermediate A is dissolved. For example, Scheme 1
And the solvents described in the above. Reaction temperature is 0 ° C
To 100 ° C, more preferably 20 ° C to 60 ° C.

The reduction of the intermediate A can also be carried out using a metal. As the metal, iron and zinc are preferable. When iron is used, it is preferable to use reduced iron for a reduction reaction. At this time, the solvent is preferably a water-containing solvent. Examples thereof include alcohol solvents, amide solvents, and ether solvents. Among them, alcohol solvents are preferable, and isopropyl alcohol is most preferable. The reaction temperature is preferably from 20C to 100C, more preferably from 40C to 80C.
Is preferred. Iron is preferably used in an amount of 4 to 10 times the equivalent of the intermediate A. When iron is used, ammonium chloride is preferably added as an additive in an amount of 0.05 to 0.5 equivalents of the intermediate A. Next, the compound of the general formula (I) is synthesized by reacting the intermediate B with the synthesis raw material B '. Preferred conditions at this time are the same as in Scheme 1. The present invention will be described in more detail with reference to synthesis examples.

Synthesis Example 1 Synthesis of Compound 18

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While stirring 30.0 g of m-phenylenediamine, 100 ml of dimethylacetamide and 46.08 g of pyridine under cooling with water, 177.6 g of the intermediate a was added.
Was added dropwise. After the reaction for 2 hours, the reaction was further performed at 50 ° C. for 1 hour. After cooling, the reaction solution was poured into 300 ml of water, and the precipitated crystals were collected by filtration. After washing with methanol and drying, 161 g of compound 18 was obtained (yield 90.1%). The structure is NMR ₁
And Mass spectra. The compound represented by the general formula (II) can be prepared by a known method, for example, as described in JP-A-5-15
No. 0423, No. 5-255333, No. 5-20200
No. 4, 7-48376, and 9-189988 can be synthesized. The general formula (II) below
A specific synthesis example of the compound represented by is shown below. Synthesis Example 1 Synthesis of Exemplary Compound (Cp-1) Exemplary Compound (Cp-1) was synthesized by the following route.

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Synthesis of Compound (b) 2,6-Di-tert-butyl-4-methylcyclohexanol, 17 g (75 mmol) of acetonitrile 200 m
trifluoroacetic anhydride at 0 ° C., 10.6 m
1 (75 mmol) was added dropwise, followed by compound (a),
15.6 g (60.4 mmol) were added slowly.
After the reaction solution was stirred at room temperature for 2 hours, 300 ml of water and 300 ml of ethyl acetate were added and extracted. The organic layer was washed with aqueous sodium bicarbonate, water and brine. After the organic layer was dried over magnesium sulfate, the solvent was distilled off under reduced pressure, and the residue was recrystallized from acetonitrile to obtain 19.6 g of (b). Synthesis of Compound (c) 5 ml of pyridine was added to a solution of 19.6 g of (b) in 200 ml of ethyl acetate, and bromine was added dropwise under cooling with water. 1
After stirring for 300 hours, water 300 ml, ethyl acetate 300 ml
Was added and extracted. After extraction, the ethyl acetate layer was dried over magnesium sulfate, the solvent was distilled off, and acetonitrile was added to the residue, followed by recrystallization. 18.0 g of (c) was obtained. Synthesis of Compound (e) Methyl cyanoacetate 2.2 g of dimethylacetamide 20
0.8 g of sodium hydride was slowly added to the ml solution at 0 ° C., and the mixture was stirred at room temperature for 30 minutes. (Solution S) 10.0 g of (c) dissolved in 50 ml of dimethylacetamide was slowly added dropwise to (Solution S) under ice-cooling. 1
After stirring for 4 hours, 4 g of sodium hydroxide and 20 ml of methanol dissolved in 20 ml of water were added to the reaction solution, and the mixture was stirred for 1 hour while maintaining the reaction temperature at 50 ° C. After the reaction, 200 ml of ethyl acetate was added and neutralized with aqueous hydrochloric acid. After washing with water, the ethyl acetate layer was dried over magnesium sulfate, and the solvent was distilled off under reduced pressure to obtain a crude compound (e). Synthesis of Exemplified Compound (Cp-1) 8.0 g of the obtained crude compound (e) was dissolved in 40 ml of dimethylacetamide and 6 ml of pyridine, and 4.3 g of morpholinocarbamoyl chloride was added at 0 ° C. After stirring at room temperature for 2 hours, the mixture was poured into 200 ml of diluted hydrochloric acid,
Extracted with 200 ml of ethyl acetate. After the organic phase was washed with water and dried over magnesium sulfate, the solvent was distilled off under reduced pressure.
Hexane was added to the residue and the mixture was crystallized to obtain 6.0 g of the exemplified compound (Cp-1). Melting point: 256 ° C-257
° C.

In the present invention, formulas (Ia) and (Ia)
The compound represented by b) is cyan which is adjusted in hue,
It is preferably added to the same layer as the magenta or yellow coupler. At this time, the general formulas (Ia) and (Ib)
Is preferably used in an amount of 0.1 to 4.0 equivalents of the coupler, more preferably 0.5 to 2.0 equivalents.

The coupler used in the present invention is preferably contained in a silver halide emulsion layer, and the silver content in the emulsion layer can take any value with respect to the coupler. From the viewpoint of reproducibility, it is preferably 2.0 or more and 8.0 or less, more preferably 2.8 or more and 6.0 or less, and most preferably 2.8 or more and 5.0 or less. Here, the ratio of silver to the coupler is defined by the molar conversion ratio of silver to the coupler. Said couplers are generally on the support at 0.01 to 1 g / m < ² >, preferably 0.1 to 1 g / m < ² >.
05-0.4 g / m ² , more preferably 0.1-0.3
g / m ² .

In order to introduce the coupler into the silver halide light-sensitive material, a known dispersion method such as an oil-in-water dispersion method or a latex dispersion method using a high-boiling organic solvent described later can be used. In the oil-in-water dispersion method, couplers and other photographically useful compounds are dissolved in a high-boiling organic solvent,
Fine particles can be emulsified and dispersed in a hydrophilic colloid, preferably in an aqueous gelatin solution, together with a dispersant such as a surfactant, by a known apparatus such as an ultrasonic wave, a colloid mill, a homogenizer, a Manton-Gaulin, and a high-speed dissolver. In dissolving the coupler, an auxiliary solvent can be further used. The auxiliary solvent referred to here is an organic solvent effective at the time of emulsification and dispersion, and refers to one that is substantially removed from the photosensitive material after the drying step at the time of coating, for example, ethyl acetate, acetate of a lower alcohol such as butyl acetate,
Examples include ethyl propionate, secondary butyl alcohol, methyl ethyl ketone, methyl isobutyl ketone, β-ethoxyethyl acetate, methyl cellosolve acetate, methyl carbitol acetate, methyl carbitol propionate, and cyclohexanone. Further, if necessary, an organic solvent that is completely miscible with water, for example, methyl alcohol, ethyl alcohol, acetone, tetrahydrofuran, dimethylformamide, or the like can be partially used in combination. These organic solvents can be used in combination of two or more kinds. Further, from the viewpoint of improving the aging stability during storage in the emulsified dispersion state, suppressing photographic performance changes and improving the aging stability of the final composition for coating mixed with the emulsion, the emulsified dispersion may be depressurized as necessary. All or a part of the auxiliary solvent can be removed by a method such as distillation, noodle washing or ultrafiltration. The average particle size of the lipophilic fine particle dispersion thus obtained is 0.04 to 0.5.
0 μm is preferable, and more preferably 0.05 to 0.30.
μm, and most preferably 0.08 to 0.20 μm. The average particle size can be measured using a Coulter submicron particle analyzer model N4 (Coulter Electronics).

In the oil-in-water dispersion method using a high-boiling organic solvent, the weight ratio of the high-boiling organic solvent to the total weight of the couplers used can be arbitrarily determined, but is preferably 0.1 or more and 5.0 or less, more preferably It is 0.3 or more and 3.0 or less, most preferably 0.5 or more and 2.5 or less. It is also possible to use a high boiling point organic solvent without using it at all. In the color light-sensitive material of the present invention, among the high boiling organic solvents that can be used together with the coupler,
From the viewpoints of high color development, color reproducibility, and light fastness, compounds represented by the following general formula (IV) can be preferably used.

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In the general formula [IV], R ³¹ , R ³² and R
³³ represents an acyclic alkyl group, a cycloalkyl group or an aryl group, and 1, m and q each represent 1 or 0. The high boiling point organic solvent represented by the general formula [IV] will be described in detail. When R ³¹ , R ³² and R ³³ in the general formula [IV] are a non-cyclic alkyl group,
It may be linear or branched, and may have an unsaturated bond or a substituent on the chain. Examples of the substituent include a halogen atom, an aryl group, an alkoxy group, an aryloxy group, an alkoxycarbonyl group, a hydroxyl group, an acyloxy group, and an epoxy group. Of course, it is not limited to these,
Phosphate general formulas (IV) represented in a form except R ^31, phosphorous acid, hypophosphorous acid ester residue, it is also included in this phosphine oxide residue, and the like.

When R ³¹ , R ³² and R ³³ are a cycloalkyl group or a group containing a cycloalkyl group, the cycloalkyl group may be a 3- to 8-membered ring and may have an unsaturated bond in the ring, Further, it may have a substituent or a crosslinking group. Examples of the substituent include a halogen atom, an alkyl group, a hydroxyl group, an acyl group, an aryl group, an alkoxy group, an aryloxy group, an alkoxycarbonyl group, an acyloxy group, and an epoxy group. Examples of the cross-linking group include methylene, ethylene, and isopropylidene. When R ³¹ , R ³² and R ³³ are an aryl group or a group containing an aryl group, the aryl group is a halogen atom,
It may be substituted with a substituent such as an alkyl group, an alkoxy group, an aryloxy group, an alkoxycarbonyl group, and an acyloxy group.

Next, preferred high boiling organic solvents in the present invention will be described. In the general formula [IV], R ³¹ and R ³²
And R ³³ are the total number of carbon atoms (hereinafter abbreviated as C number)
An acyclic alkyl group having 1 to 24 (more preferably 4 to 18 C atoms), 5 to 24 C atoms (more preferably 6 to 18 C atoms)
Or an aryl group having 6 to 24 (preferably 6 to 18) C atoms. Specific examples of the substituted or unsubstituted acyclic alkyl group include an n-butyl group, 2
-Ethylhexyl, 3,3,5-trimethylhexyl, n-dodecyl, n-octadecyl, benzyl, oleyl, 2-chloroethyl, 2,3-dichloropropyl, 2-butoxyethyl, 2 -Phenoxyethyl group and the like. Specific examples of the cycloalkyl group include a cyclopentyl group, a cyclohexyl group, 4-t
-Butylcyclohexyl group, 4-methylcyclohexyl group, 2-cyclohexenyl group and the like. Specific examples of the aryl group include a phenyl group, a cresyl group, and p
-Nonylphenyl group, xylyl group, cumenyl group, p-methoxyphenyl group, p-methoxycarbonylphenyl group, p-isopropylphenyl group, m-isopropylphenyl group, o-isopropylphenyl group, p, o-diisopropylphenyl group, etc. Is mentioned. In particular, the high-boiling organic solvents represented by the general formula [IV] include R ³¹ , R ³² and R ³³
Is preferably a substituted or unsubstituted aryl group.
Among them, those in which R ³¹ , R ³² and R ³³ are aryl groups substituted with alkyl groups are most preferred.

Regarding l, m and q of the high boiling point organic solvent represented by the general formula [IV], it is preferable that all of them are 1 or at least one of them is 0. Particularly preferably, all of l, m, and q are 1. The high-boiling organic solvent mentioned here has a boiling point of about 150 ° C. at normal pressure.
The temperature is preferably 170 ° C. or higher. Also,
The shape at room temperature is not limited to a liquid shape, and may be any shape such as a low melting point crystal, an amorphous solid, or a paste. When the shape at room temperature is crystalline, the melting point is preferably 1
The temperature is not higher than 00 ° C, more preferably not higher than 80 ° C.
These high-boiling organic solvents may be used alone or 2
A mixture of two or more kinds of high-boiling organic solvents may be used. 2
When using a mixture of more than one high boiling organic solvent,
As long as at least one of them is a high-boiling organic solvent of the general formula [IV], any other high-boiling organic solvent may be used. Examples of the type of the organic solvent used as a mixture include esters of aromatic carboxylic acids such as phthalic acid and benzoic acid, esters of aliphatic carboxylic acids such as succinic acid and adipic acid, amide compounds, and epoxy compounds. And aniline-based compounds, phenolic compounds and the like. When the high boiling organic solvent of the general formula [IV] is crystalline and has a melting point of 80 ° C. or more, it is desirable to use a mixture of two or more high boiling organic solvents. When the high-boiling organic solvent of the general formula [IV] is used by being mixed with another high-boiling organic solvent, when the former is a phosphate ester, the mixing ratio is preferably 25% by weight or more, and more preferably 50% by weight or more. More preferred. When the former is a phosphonate, phosphinate or phosphine oxide, the content is preferably at least 10% by weight, more preferably at least 20% by weight. The general formula (I
Specific examples of the high-boiling organic solvent represented by the formula [V] are shown below, but are not limited thereto.

[0079]

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[0080]

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[0081]

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[0082]

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[0083]

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[0084]

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Among these compounds, SS-4, S
Those of S-30 and SS-31 are preferable. Further, in the present invention, the compound represented by the general formula [V] can be preferably used in combination from the viewpoints of high color development and improvement in light fastness. General formula [V]

[0086]

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In the general formula [V], L represents a single bond or an arylene group. R ^a1 , R ^a2 and R ^a3 may be the same or different and each represents an alkyl group, an alkenyl group, an aryl group or a heterocyclic group. R ^a1 further represents a radical (·) when L is a single bond. ^Ra3 further represents a hydrogen atom. ^Ra1 and L, ^Ra2 and L, ^Ra3 and L, ^Ra1 and ^Ra2 , ^Ra1 and ^Ra3, and ^Ra2 and ^Ra3 may combine with each other to form a 5- to 7-membered ring. The compound represented by formula [V] will be described in detail. L represents a single bond or an arylene group (eg, phenylene, naphthylene). R ^a1 , R ^a2 and R ^a3 may be the same or different and each is an alkyl group (linear, branched or cyclic alkyl group such as methyl, ethyl, isopropyl, t-
Butyl, cyclohexyl, octyl, sec-octyl, t-octyl, decyl, dodecyl, i-tridecyl, tetradecyl, hexadecyl, octadecyl), alkenyl group (linear, branched or cyclic alkenyl group;
For example, vinyl, allyl, cyclohexenyl, oleyl), an aryl group (eg, phenyl, naphthyl) or a heterocyclic group (a 5- to 7-membered heterocyclic ring containing at least one of N, O, S, and P as a ring-constituting atom) Represents for example thienyl, furyl, pyranyl, pyrrolyl, imidazolyl, indolyl, chromanyl, piperidinyl). R ^a1 further represents a radical (·) when L is a single bond. ^Ra3 further represents a hydrogen atom. R ^a1 and L, R
^a2 and L, ^Ra3 and L, ^Ra1 and ^Ra2 , ^Ra1 and ^Ra3 and ^Ra2
And R ^a3 may combine with each other to form a 5- to 7-membered ring.

Each group in the general formula [V] may be further substituted with a substituent. Examples of such a substituent include an alkyl group, an alkenyl group, an aryl group, a heterocyclic group, a halogen atom, a cyano group, a nitro group and a nitro group. Group, hydroxyl group, alkoxy group, alkenoxy group, aryloxy group, heterocyclic oxy group, alkylthio group, alkenylthio group, arylthio group, heterocyclic thio group, amino group, alkylamino group, alkenylamino group, arylamino group, Heterocyclic amino group, acylamino group, sulfonamide group, acyl group, acyloxy group, alkoxycarbonyl group, alkenoxycarbonyl group, aryloxycarbonyl group, heterocyclic oxycarbonyl group, sulfonyl group, sulfinyl group, alkoxycarbonylamino group,
Alkenoxycarbonylamino group, aryloxycarbonylamino group, heterocyclic oxycarbonylamino group,
Examples include a carbamoyl group, a sulfamoyl group, a ureido group, a sulfonyloxy group, a carbamoyloxy group, a sulfamoyloxy group, a phosphoryloxy group, and a silyloxy group.

In the general formula [V], L is preferably a single bond or a phenylene group, more preferably a single bond. Preferably, all of R ^a1 , R ^a2 and R ^a3 are an alkyl group or an alkenyl group. Also, R ^a1 ,
The total number of carbon atoms of R ^a2 , R ^a3 and L is preferably 10 or more, and more preferably 15 or more. More preferred in the general formula [V] can be represented by the following general formula [AI].

[0090]

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In the general formula [AI], R ^a1 is the same as in the general formula [V]. Z ^a1 is a divalent group in which both of the two atoms bonding to N are carbon atoms, and
Represents a group of nonmetallic atoms necessary to form a 7-membered ring.
L ^a1 represents a single bond or a phenylene group.

Of the compounds represented by the general formula [AI], most preferably the following general formula [A-II] or [A-I]
III].

[0093]

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In the general formulas [A-II] and [A-III], ^Ra1 is the same as in the general formula [V]. R ^a4 is an alkyl group,
Represents an alkenyl group or a radical (·), and R ^a5 represents a substituent. n represents an integer of 0, 1 to 4. Z ^a2 represents a group of nonmetallic atoms necessary for forming a 6-membered ring. Z
^a1 is the same as in the general formula [AI].

In formula [A-II], it is preferable that Z ^a2 is a group necessary for forming a piperidine ring. In the general formula [A-III], those in which R ^a1 is an alkyl group or an alkenyl group, and those in which the ring composed of R ^a1 and NZ ^a1 are in the para-position to each other are preferred. Hereinafter, specific examples of the compound represented by the general formula [V] that can be used in the present invention are shown, but the scope of the compound is not limited thereto.

[0096]

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[0097]

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[0098]

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[0099]

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[0100]

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[0101]

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[0102]

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[0103]

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[0104]

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The compound represented by the general formula [V] having an effect on improving the image fastness is preferably added in an amount of 0 to 500 mol%, more preferably 2 to 300 mol%, and most preferably 5 to 5 mol% with respect to the coupler. ~ 200 mol%
It is. These compounds may be used alone or in combination of two or more, and may be added to the same silver halide emulsion layer as the coupler, or may be added to an adjacent layer or another layer. Compounds represented by the general formula [V] which can be used in the present invention are described, for example, in JP-A-1-132562, JP-A-1-113368, and U.S. Pat. No. 4,921,96.
No. 2, 4,639, 415, Tokuhei 6-75175
Can be easily synthesized according to the method described in (1).

The silver halide photographic light-sensitive material of the present invention is used for a color negative film, a color positive film, a color reversal film, a color reversal photographic paper, a color photographic paper and the like, and among them, a color photographic paper is preferable.
In the silver halide photographic light-sensitive material of the present invention, other conventionally known photographic materials and additives can be used. For example, a transmissive support or a reflective support can be used as a photographic support. Examples of the transmission type support include transmission films such as cellulose nitrate film and polyethylene terephthalate, and polyesters of 2,6-naphthalenedicarboxylic acid (NDCA) and ethylene glycol (EG) and polyesters of NDCA, terephthalic acid and EG. And the like provided with an information recording layer such as a magnetic layer are preferably used. As the reflective support, a reflective support laminated with a plurality of polyethylene layers or polyester layers, and containing a white pigment such as titanium oxide in at least one of such water-resistant resin layers (laminated layers) is preferable.

It is preferable that the water-resistant resin layer contains a fluorescent whitening agent. The fluorescent whitening agent may be dispersed in the hydrophilic colloid layer of the light-sensitive material. As the fluorescent whitening agent, preferably, benzoxazole type, coumarin type,
Pyrazoline-based fluorescent whitening agents can be used, and more preferred are benzoxazolylnaphthalene-based and benzoxazolylstilbene-based fluorescent whitening agents. The amount used is not particularly limited, but is preferably 1 to 100 mg / m ² . The mixing ratio when mixed with the water-resistant resin is preferably 0.0005 to 3% by weight, more preferably 0.001 to 0.5% by weight, based on the resin. The reflective support may be a transmissive support or a reflective support as described above, on which a hydrophilic colloid layer containing a white pigment is applied. Further, the reflective support may be a support having a mirror-reflective or second-class diffuse-reflective metal surface.

The silver halide emulsion used in the present invention has a silver chloride content of 95 mol% from the viewpoint of rapid processing.
The silver chloride or silver chlorobromide emulsion described above is preferred, and a silver halide emulsion having a silver chloride content of 98 mol% or more is more preferred. Among such silver halide emulsions, those having a silver bromide localized phase on the surface of silver chloride grains are particularly preferable since high sensitivity can be obtained and photographic performance can be stabilized.

The above-mentioned reflection type support comprises a silver halide emulsion,
Further, different metal ion species doped in silver halide grains, storage stabilizers or antifoggants for silver halide emulsions, chemical sensitization (sensitizer), spectral sensitization (spectral sensitizer), Cyan, magenta, yellow couplers and their emulsifying and dispersing methods, color image preservability improvers (anti-stain and anti-fading agents), dyes (colored layers), gelatin species, layer composition of photosensitive material, coating pH of photosensitive material, etc. As described above, those described in the patents of Tables 1 and 2 can be preferably applied to the present invention.

[0110]

[Table 1]

[0111]

[Table 2]

As cyan couplers, magenta and yellow couplers other than the couplers represented by the general formula [II] according to the present invention, other than those described in JP-A-62-215272, page 91, upper right column, line 4 to page 121, upper left column 6, Line 3, page 14 upper right column, line 14 to page 18, upper left column last line, and page 30, upper right column, line 6 to page 35 lower right column 11, of JP-A-2-33144.
Line and from page 0, line 15 of EP 0355,660A2
It is also preferably applicable to the couplers described on line 27, page 30, line 30 to page 28, line 45, line 29 to line 31, page 47, line 23 to page 63, line 50.

As the antibacterial and antifungal agents usable in the present invention, those described in JP-A-63-271247 are useful.
Gelatin is preferred as the hydrophilic colloid used in the photographic layer constituting the light-sensitive material. Particularly, heavy metals contained as impurities such as iron, copper, zinc and manganese are preferably at most 5 ppm, more preferably at most 3 ppm. .

The light-sensitive material of the present invention is suitable for a scanning exposure method using a cathode ray (CRT) in addition to being used for a printing system using a normal negative printer. A cathode ray tube exposure apparatus is simpler, more compact, and lower in cost than an apparatus using a laser. Further, adjustment of the optical axis and color is also easy. Various light emitters that emit light in a spectral region are used as necessary for a cathode ray tube used for image exposure. For example, any one of a red light emitter, a green light emitter, and a blue light emitter, or a mixture of two or more thereof is used. The spectral region is not limited to the above red, green, and blue, and a phosphor that emits light in a yellow, orange, purple, or infrared region is also used. In particular, a cathode ray tube which emits white light by mixing these light emitters is often used.

When the photosensitive material has a plurality of photosensitive layers having different spectral sensitivity distributions and the cathode ray tube also has a phosphor which emits light in a plurality of spectral regions, a plurality of colors are exposed at a time, that is, the cathode ray tube is exposed. The image signals of a plurality of colors may be input to the display unit to emit light from the display screen. A method of sequentially inputting image signals for each color, sequentially emitting light of each color, and exposing through a film that cuts a color other than that color (plane sequential exposure)
In general, plane-sequential exposure is preferable for high image quality because a cathode ray tube with high resolution can be used.

The photosensitive material of the present invention is a gas laser, a light emitting diode, a semiconductor laser, a semiconductor laser, or a second harmonic generation light source (SHG) combining a solid-state laser using a semiconductor laser as an excitation light source and a nonlinear optical crystal.
And the like, and is preferably used for a digital scanning exposure method using monochromatic high density light. In order to make the system compact and inexpensive, it is preferable to use a semiconductor laser, a semiconductor laser or a second harmonic generation light source (SHG) in which a solid-state laser is combined with a nonlinear optical crystal. Particularly, in order to design an apparatus that is compact, inexpensive, and has a long life and high stability, it is preferable to use a semiconductor laser, and it is preferable to use a semiconductor laser as at least one of the exposure light sources.

When such a scanning exposure light source is used,
The spectral sensitivity maximum wavelength of the light-sensitive material of the present invention can be arbitrarily set according to the wavelength of the scanning exposure light source used.
In a solid-state laser using a semiconductor laser as an excitation light source or an SHG light source obtained by combining a semiconductor laser and a nonlinear optical crystal, the laser oscillation wavelength can be halved, so that blue light and green light can be obtained. Therefore, the spectral sensitivity maximum of the photosensitive material can be provided in the usual three wavelength ranges of blue, green and red. If the exposure time in such scanning exposure is defined as the exposure time for the pixel size when the pixel density is 400 dpi, the preferred exposure time is 10 ^-4 seconds or less, more preferably 10 ^-6 seconds or less.

Preferred scanning exposure methods applicable to the present invention are described in detail in the patents listed in the above table. Further, for processing the light-sensitive material of the present invention, the lower right column of page 26, lower right column of page 26 to the upper right column of page 34 of JP-A-2-207250, and the upper left column of page 5 of JP-A-4-97355 can be used. The processing materials and processing methods described in line 17 to page 20, lower right column, line 20 can be preferably applied. As the preservative used in this developer, the compounds described in the patents listed in the above table are preferably used.

The method of developing the light-sensitive material of the present invention after exposure is a conventional method of developing with a developer containing an alkali agent and a developing agent, an alkali solution containing a developing agent in the light-sensitive material and containing no developing agent, etc. In addition to a wet method such as a method of developing with an activator solution, a thermal developing method without using a processing solution can be used. In particular, since the activator method does not contain a developing agent in the processing liquid, it is easy to manage and handle the processing liquid, and is a preferable method from the viewpoint of environmental protection because it has a small load when processing the waste liquid. In the activator method, examples of the developing agent or its precursor incorporated in the photosensitive material include, for example, Japanese Patent Application No. 7-6357.
No. 2, 7-334190, 7-334192,
The hydrazine-type compounds described in JP-A-7-334197 and JP-A-7-344396 are preferred.

Further, a developing method in which the amount of silver applied to the light-sensitive material is reduced and image amplification processing (intensification processing) using hydrogen peroxide is used is also preferably used. In particular, it is preferable to use this method for the activator method. Specifically, Japanese Patent Application Hei 7
Image forming methods using an activator solution containing hydrogen peroxide described in JP-A-63587 and JP-A-7-334202 are preferably used. In the activator method,
Desilvering is usually performed after processing with an activator solution.However, in an image amplification processing method using a low silver content photosensitive material, desilvering processing can be omitted and a simple method such as washing or stabilizing processing can be performed. it can. Further, in a method in which image information is read from a photosensitive material by a scanner or the like, a processing mode that does not require desilvering processing can be adopted even when a photosensitive material having a high silver content such as a photosensitive material for photography is used.

As the activator solution, desilvering solution (bleaching / fixing solution), washing and stabilizing solution used in the present invention, known processing materials and processing methods can be used. Preferably, Research Disclosure Item 36544
(September 1994) Pages 536 to 541, Japanese Patent Application No. 7
-63572 can be used.

[0122]

Example 1 After a corona discharge treatment was applied to the surface of a paper support laminated on both sides with polyethylene, a gelatin subbing layer containing sodium dodecylbenzenesulfonate was provided, and various photographic constituent layers were further applied. A multilayer color photographic paper (101) having the following layer configuration was produced. The coating solution was prepared as follows.

Preparation of Coating Solution for Fifth Layer 10 g of a cyan coupler (Cp-1) represented by the general formula [II] is dissolved in 30 g of a solvent (Solv-2) and 50 ml of ethyl acetate. ) Emulsified and dispersed in 400 g of a 12% aqueous gelatin solution containing 1.2 g to prepare an emulsion C having an average particle size of 0.18 µm. On the other hand, silver chlorobromide emulsion C (cubic, average grain size 0.55
μm large size emulsion C and 0.42 μm small size emulsion C
1: 4 mixture with silver (silver molar ratio). The variation coefficients of the particle size distribution are 0.09 and 0.11, respectively. In each size emulsion, 0.8 mol% of silver bromide was locally contained on a part of the surface of a grain based on silver chloride). In this emulsion, the following red-sensitive sensitizing dyes G and H were added in an amount of 5.0 × 10 ⁻⁵ mol per mol of silver per mol of silver, and 5.0 × 10 ⁻⁵ mol per mol of silver. , 8.0 × 10 each
^-5 mol was added. Further, Additive X was added in an amount of 2.6 × 10 ⁻³ mol per mol of silver halide. Chemical ripening of this emulsion was optimally performed by adding a sulfur sensitizer and a gold sensitizer. The emulsified dispersion C and the silver chlorobromide emulsion C were mixed and dissolved to prepare a fifth layer coating solution having the following composition. The emulsion coating amount indicates a coating amount in terms of silver amount.

The coating solutions for the first to seventh layers were prepared in the same manner as the coating solution for the fifth layer. These coating solutions are prepared 1
It was applied in 5 minutes. As a gelatin hardener for each layer, 1-oxy-3,5-dichloro-s-triazine sodium salt was used. In addition, preservatives AS-1, AS-2, A
The total amount of each of S-3 and AS-4 was 15.0 mg / m.
^{2, 6.0mg / m 2, 5.0mg} / m 2 and 10.0
mg / m ² .

[0125]

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The following spectral sensitizing dyes were used for the silver chlorobromide emulsion in each photosensitive emulsion layer. Blue-sensitive emulsion layer

[0127]

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(Per mol of silver halide, 1.4 × 10 ^-4 mol was added to a large-size emulsion, and 1.7 × 10 ^-4 mol was added to a small-size emulsion, respectively. Green sensitive emulsion layer

[0129]

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(Sensitizing dye D was used in an amount of 3.0 × 10 ⁻⁴ mol for a large-sized emulsion, 3.6 × 10 ⁻⁴ mol for a small-sized emulsion, Also,
Sensitizing dye E was used in an amount of 4.0 × 10 ⁻⁵ mol for a large-size emulsion, 7.0 × 10 ⁻⁵ mol for a small-size emulsion, and sensitizing dye per mol of silver halide. F per mole of silver halide, 2.0% for large size emulsions.
× 10 ^-4 mol, and 2.8 × 1 for small size emulsions
^0-4 moles were added. ) Red-sensitive emulsion layer

[0131]

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(Per mol of silver halide, 5.0 × 10 ^-5 mol was added to a large-size emulsion, and 8.0 × 10 ^-5 mol was added to a small-size emulsion. Further, the following additive X was added to the red-sensitive emulsion layer in an amount of 2.6 × 10 ⁻³ mol per mol of silver halide.

[0133]

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[0134] Further, the blue-sensitive emulsion layer, green-sensitive emulsion layer and red-sensitive emulsion layer to, 1- (5-methylureidophenyl) -5-mercaptotetrazole each per mol of silver halide 3.3 × 10 ^{- 4} mol, 1.0 × 10 ^-3
Mol and 5.9 × 10 ^-4 mol. Furthermore, the second layer,
0.2 mg / m for each of the fourth, sixth and seventh layers
² , 0.2 mg / m ² , 0.6 mg / m ² , 0.1 mg
/ M ² . In addition, 4-hydroxy-6-methyl-1, 4-hydroxy-6-methyl-1,
3,3a, 7-Tetrazaindene was added in an amount of 1 × 10 ⁻⁴ mol and 2 × 10 ⁻⁴ mol per mol of silver halide, respectively. The following compounds were added separately as second, fourth, and sixth layers as irradiation prevention water-soluble dyes.

[0135]

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(Layer Structure) The composition of each layer is shown below. The numbers represent the coating amount (g / m ² ). The silver halide emulsion represents a coated amount in terms of silver. Support Polyethylene laminated paper [white pigment in a polyethylene of the first layer side (Ti0 ₂ content 15 wt%) and containing bluing dye (ultramarine)]

First Layer (Blue-Sensitive Emulsion Layer) Silver chlorobromide emulsion A (cubic, 3: 7 mixture of large-size emulsion A with an average grain size of 0.88 μm and small-size emulsion A with a 0.70 μm size (silver mole The coefficient of variation of the grain size distribution was 0.08 and 0.10, respectively, and 0.3 mol% of silver bromide was locally contained in a part of the grain surface based on silver chloride in each size emulsion. 0.26 gelatin 1.4 yellow coupler (ExY) 0.64 color image stabilizer (Cpd-1) 0.078 color image stabilizer (Cpd-2) 0.038 color image stabilizer (Cpd-3) 0 0.085 Color image stabilizer (Cpd-5) 0.020 Color image stabilizer (Cpd-9) 0.0050 Solvent (Solv-1) 0.11 Solvent (Solv-6) 0.11

Second layer (color mixture preventing layer) Gelatin 1.0 Color mixture inhibitor (Cpd-4) 0.11 Solvent (Solv-1) 0.065 Solvent (Solv-2) 0.22 Solvent (Solv-3) 0.080 Solvent (Solv-7) 0.010 Ultraviolet absorber (UV-B) 0.070

Third Layer (Green-Sensitive Emulsion Layer) Silver chlorobromide emulsion (cubic, 1: 3 mixture of large-sized emulsion B having an average grain size of 0.55 μm and small-sized emulsion B of 0.39 μm (silver molar ratio) The coefficient of variation of the grain size distribution was 0.10 and 0.08, respectively, and 0.7 mol% of silver bromide was locally contained in a part of the grain surface based on silver chloride in each size emulsion. 0.1) Gelatin 1.3 Magenta coupler (ExM) 0.13 UV absorber (UV-A) 0.12 Color image stabilizer (Cpd-2) 0.010 Color image stabilizer (Cpd-5) 020 Color image stabilizer (Cpd-6) 0.010 Color image stabilizer (Cpd-7) 0.080 Color image stabilizer (Cpd-8) 0.030 Color image stabilizer (Cpd-10) 0.0020 Solvent (Solv-3) 0.15 Solvent (Solv-4) 2 solvent (Solv-5) 0.11

Fourth layer (color mixture prevention layer) Gelatin 1.0 Color mixture prevention agent (Cpd-4) 0.11 Solvent (Solv-1) 0.065 Solvent (Solv-2) 0.22 Solvent (Solv-3) 0.080 Solvent (Solv-7) 0.010 Ultraviolet absorber (UV-B) 0.070

Fifth Layer (Red-Sensitive Emulsion Layer) Silver chlorobromide emulsion (cubic, 1: 4 mixture of large size emulsion having an average grain size of 0.55 μm and small size emulsion of 0.42 μm (silver molar ratio)) The coefficient of variation of the grain size distribution was 0.09 and 0.11, respectively, and 0.8 mol% of silver bromide was locally contained in a part of the grain surface based on silver chloride in each size emulsion.) 0.086 Surfactant (Cpd12) 0.006 Gelatin 0.99 Cyan coupler of general formula [II] (Cp-1) 0.15 Solvent (Solv-2) 0.45

Sixth layer (ultraviolet absorbing layer) Gelatin 0.63 Ultraviolet absorbing agent (UV-C) 0.35 Color image stabilizer (Cpd-7) 0.050 Solvent (Solv-9) 0.050

Seventh layer (protective layer) Acid-treated gelatin 1.0 Acrylic-modified copolymer of polyvinyl alcohol (degree of modification 17%) 0.043 Liquid paraffin 0.018 Surfactant (Cpd-11) 0.026

[0144]

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[0145]

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[0146]

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[0147]

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[0148]

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[0149]

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[0150]

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[0151]

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The photosensitive material 101 prepared as described above was prepared in exactly the same manner except that the composition of the fifth layer was changed as shown in Tables 3 and 4 below.
0 was produced. For these changes, the couplers of the general formula [II] were changed in equimolar amounts. The average particle size of the coupler-containing lipophilic fine particles prepared when preparing these samples was all in the range of 0.17 to 0.19 μm. The ratio of the compound of the general formula [Ia] or [Ib] to [II] is a molar ratio.

[0153]

[Table 3]

The couplers a and b in the table are as follows.

[0155]

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First, the light-sensitive material 104 is coated with a silver amount of about 30%.
% Of the color developing solution in the following processing step using a paper processing machine after the imagewise exposure so that the
Continuous processing was performed until the double amount was replenished.

Processing process Temperature Time Replenishment amount Tank capacity Color development 38.5 ° C 45 seconds 73ml 500ml Bleaching and fixing 30-35 ° C 45 seconds 60ml 500ml Rinse (1) 30-35 ° C 20 seconds --- 500ml Rinse (2) 30- 35 ° C. 20 seconds --- 500 ml rinse (3) 30~35 ℃ 20 seconds 370 ml 500 ml dry 70 to 80 ° C. 60 seconds * replenishment rate is per photosensitive material 1 m ² (3 tanks rinse to (3) → (1) Countercurrent method)

The composition of each processing solution is as follows. Color developer Tank solution Replenisher Water 700ml 700ml Sodium triisopropylene (β) sulfonate 0.1g 0.1g Ethylenediaminetetraacetic acid 3.0g 3.0g 1,2-Dihydroxybenzene-4,6-disulfonate disodium salt 0.5g 0.5g Triethanolamine 12.0 g 12.0 g Potassium chloride 6.5 g-Potassium bromide 0.03 g-Potassium carbonate 27.0 g 27.0 g Fluorescent whitening agent (WHITEX 4, manufactured by Sumitomo Chemical) 1.0 g 3.0 g Sodium sulfite 0.1 g 0.1 g Diethylhydroxylamine 1.1 g 1.1 g disodium-N, N-bis (sulfonatoethyl) hydroxylamine 10.0 g 13.0 g N-ethyl-N- (β-methanesulfonamidoethyl) -3-methyl-4-aminoaniline sulfate 5.0 g 11.5 g Add water 1000ml 1000ml pH (25 ℃) 10.0 11.0

Bleach-fix solution (same as tank solution and replenisher) Water 600 ml Ammonium thiosulfate (700 g / liter) 100 ml Ammonium sulfite 40 g Ammonium iron (III) ethylenediaminetetraacetate 55 g Disodium ethylenediaminetetraacetate 5 g Ammonium bromide 40 g Nitric acid (67) %) 30 g with water 1000 ml pH (25 ° C) (with acetic acid and aqueous ammonium) 4.8

Rinse solution (tank solution and replenisher are the same) Deionized water (calcium and magnesium are each 3 pp
m or less)

Next, each sample was subjected to gradation exposure using a sensitometer (manufactured by Fuji Photo Film Co., Ltd., FWH type, color temperature of light source: 3200 ° K) with a three-color separation optical wedge for sensitometry. . The exposure at this time was performed such that the exposure amount was 250 CMS with an exposure time of 0.1 second. The following evaluation was performed using these samples.

Evaluation 1 (Coloring property: Dmax) The exposed sample was treated with the above-mentioned running liquid using a paper processor. After the processing, an X-Rite 350 densitometer (T
He X-Rite Company), and the maximum color density (Dmax) of yellow, magenta, and cyan was measured.

Evaluation 2 (Color Reproducibility) The reflection and absorption spectrum of the cyan coloring portion treated in the processing step of Evaluation 1 was measured. The association band existing at the short-wave end of the main absorption band in the cyan region of the absorption spectrum is remarkably large,
A sample having poor hue was evaluated as x, and a sample having a moderate degree of association band at the short-wave end and advantageous in color reproduction was evaluated as Δ. Evaluation 3 (Light Fastness) The sample treated in the processing step of Evaluation 1 was irradiated with light using a 100,000 lux xenon light irradiator for 14 days. At the time of irradiation, a heat ray cut filter and an ultraviolet ray cut filter having a light transmittance of 50% at 370 nm were used. A cyan density residual rate (%) after light irradiation at a point where the cyan density before light irradiation was 0.5 was determined, and light fastness was evaluated. The evaluation results are also shown in Table 3.

As is clear from the results shown in Table 3,
It can be seen that the compounds of the present invention represented by the general formulas (Ia) and (Ib) sharpen the hue of the coupler-derived dye, improve the light fastness, and improve the color developability. The effect of hue improvement is particularly remarkable when a cyan coupler represented by the general formula (II) is used as a coupler.

Example 2 Samples 201 to 221 were prepared in the same manner as in Example 1 except that the composition of the fifth layer in Sample 101 of Example 1 was changed as shown in Table 4 below. Processing and various evaluations were performed. In the evaluation of light fastness,
The data at an initial concentration of 2.0 (Do: 2.0) are described.

[0166]

[Table 4]

According to Table 4, according to the general formula [II] defined in the present invention,
It can be seen that the effect of the present invention can be more effectively exerted by using the cyan coupler of formula (I) in combination with the compound of formula (I) and using the compound represented by [V].

Example 3 A sample 301 was prepared by changing the following points from the sample 101 of Example 1. (Layer Structure) The composition of each layer is shown below. The number is the coating amount (g
/ M ² ). The silver halide emulsion represents a coated amount in terms of silver. Support Polyethylene laminated paper [white pigment in a polyethylene of the first layer side (Ti0 ₂ content 20 wt%) and containing bluing dye (ultramarine)]

First Layer (Blue-Sensitive Emulsion Layer) Silver chlorobromide emulsion A (cubic, 3: 7 mixture of large-size emulsion A with an average grain size of 0.89 μm and small-size emulsion A with a 0.71 μm emulsion (silver mole The coefficient of variation of the grain size distribution was 0.08 and 0.10, respectively, and 0.3 mol% of silver bromide was locally contained in a part of the grain surface based on silver chloride in each size emulsion. 0.25 gelatin 1.4 yellow coupler (ExY) 0.62 color image stabilizer (Cpd-1) 0.040 color image stabilizer (Cpd-2) 0.032 color image stabilizer (Cpd-3) 0 0.086 Color image stabilizer (Cpd-5) 0.015 Color image stabilizer (Cpd-13) 0.035 Solvent (Solv-3) 0.14 Solvent (Solv-6) 0.070 Second layer (color mixture prevention) Layer) Gelatin 1.1 Color mixing inhibitor (Cpd-4) 0 11 Color Image Stabilizer (Cpd-7) 0.17 solvent (Solv-1) 0.070 solvent (Solv-2) 0.28 solvent (Solv-7) 0.011

Third Layer (Green-Sensitive Emulsion Layer) Silver chlorobromide emulsion (cubic, 1: 3 mixture of large-size emulsion B having an average grain size of 0.56 μm and small-size emulsion B having an average grain size of 0.39 μm (silver molar ratio) The coefficient of variation of the grain size distribution was 0.10 and 0.08, respectively, and 0.7 mol% of silver bromide was locally contained in a part of the grain surface based on silver chloride in each size emulsion. 0.1) Gelatin 1.3 Magenta coupler (ExM) 0.14 UV absorber (UV-E) 0.13 Color image stabilizer (Cpd-2) 0.011 Color image stabilizer (Cpd-5) 011 Color image stabilizer (Cpd-6) 0.010 Color image stabilizer (Cpd-7) 0.080 Color image stabilizer (Cpd-8) 0.028 Color image stabilizer (Cpd-10) 0.0022 Solvent (Solv-4) 0.20 Solvent (Solv-5) 0 Solvent (Solv-8) 0.20 Fourth layer (color mixture prevention layer) Gelatin 1.1 Color mixture prevention agent (Cpd-4) 0.11 Color image stabilizer (Cpd-7) 0.17 Solvent (Solv-1) ) 0.070 Solvent (Solv-2) 0.28 Solvent (Solv-7) 0.011

Fifth Layer (Red-Sensitive Emulsion Layer) Silver chlorobromide emulsion (cubic, 1: 4 mixture of large size emulsion having an average grain size of 0.57 μm and small size emulsion of 0.42 μm (silver molar ratio)) The coefficient of variation of the grain size distribution was 0.09 and 0.11, respectively, and 0.7 mol% of silver bromide was locally contained in a part of the grain surface based on silver chloride in each size emulsion.) 0.10 Gelatin 0.91 Cyan coupler (Exemplified compound Cp-1) 0.15 Solvent (Solv-2) 0.38 Sixth layer (ultraviolet absorbing layer) Gelatin 0.75 Ultraviolet absorbing agent (UV-F) 33 Solvent (Solv-10) 0.18 Seventh layer (protective layer) Acid-treated gelatin 1.0 Acrylic modified copolymer of polyvinyl alcohol (degree of modification 17%) 0.043 Liquid paraffin 0.018 Surfactant (Cpd) -11) 0. 26

[0172]

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[0173]

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[0174]

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The following compounds were added to the second, fourth and sixth layers separately as the irradiation-preventing water-soluble dye.

[0176]

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Samples 302 to 321 were made exactly the same as Sample 301 except that the composition of the oil-soluble component containing the coupler in the fifth layer was changed to the same as Samples 202 to 221 of Example 2 with respect to Sample 301. Then, the same evaluation as in Example 1 was performed. As a result, it was found that according to the present invention, a photosensitive material having excellent color developability, processing stability, color reproducibility and light fastness can be obtained.

Example 4 Samples 402 to 430 were prepared in the same manner as in Samples 402 to 430 except that the compound (a-6) represented by the general formula (V) was further added to the fifth layer of Samples 102 to 130 by 150 mol% with respect to the coupler. And make
The same evaluation as in Example 1 was performed. As a result, it was found that the light fastness was further improved.

Example 5 A sample 501 was prepared by changing the following points from the sample 101 of Example 1. Color image stabilizer ADF-1 0.01 Ａ ADF-2 0.01 〃 ADF-3 0.05 Ａ ADF-4 0.06 〃 ADF- instead of 0.45 for the solvent (Solv-2) in the fifth layer 5 0.101 Ａ ADF-6 0.05 Stain inhibitor Cpd-14 0.008 〃 Cpd-15 0.079 Solvent (Solv-8) 0.13

[0180]

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By making similar changes, samples 102-130
Were prepared, and the same evaluations as in Example 1 were performed. As a result, it was found that the light fastness was further increased, and the cyan stain and the cyan color mixture during processing were further reduced.

[0182]

As described in detail above, the use of the specific bisurethane or bisureide compound according to the present invention, particularly the use of this compound in combination with a specific cyan coupler, improves the color development and color reproducibility. A silver halide color photographic light-sensitive material which is excellent, has low cyan color mixture and low cyan stain, and has high fastness can be obtained.

Claims (2)

[Claims] 1. A silver halide color photographic light-sensitive material having at least one silver halide emulsion on a support, characterized by containing at least one compound represented by the following formula (Ia). Silver photographic photosensitive material. Embedded image In the formula, R ¹ and R ² each independently represent a hydrogen atom, an aliphatic group, or an aryl group. X ¹ and X ² are each independently -OR
⁴ or —N (R ⁵ ) R ⁶ . R ⁴ , R ⁵ and R ⁶ represent a hydrogen atom, an aliphatic group or an aryl group,
R ¹ , R ⁵ and R ⁶ are not all alkyl groups. 2. A silver halide color photographic light-sensitive material having at least one silver halide emulsion on a support, wherein at least one compound represented by the following general formula (Ib) and at least one compound represented by the following general formula (II) are represented. A silver halide photographic material comprising at least one cyan coupler to be used. Embedded image In the formula (Ib), R ¹ , R ² , R ⁴ , X ¹ and X ² represent
Is synonymous with that specified in. R ³ represents a hydrogen atom or a substituent. R ⁵ and R ⁶ each independently represent a hydrogen atom, an aliphatic group, or an aryl group. n represents an integer of 0 to 4. The compound represented by formula (Ib) has no ability to react with an oxidized color developing agent to form a dye.
Wherein ^{(II), Z a, Z} b are each -C (R ¹³⁾ = or an -N =. However, either Z ^a or Z ^b is −
Is N =, the other is, -C (R ¹³⁾ is =. R ¹¹ , R
¹² represents an electron-withdrawing group having a Hammett's substituent constant σ _p of 0.20 or more, and the sum of σ _p values of R ¹¹ and R ¹² is 0.65 or more. R ¹³ represents a hydrogen atom or a substituent. X ³ represents a hydrogen atom or a group capable of leaving in a coupling reaction with an oxidized form of an aromatic primary amine developing agent. The group of R ¹¹ , R ¹² , R ¹³ or X ³ may be a divalent group and form a homopolymer or a copolymer by bonding to a dimer or higher polymer or a polymer chain. .