JPH11344793A - Silver halide color photographic sensitive material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To prevent color mixing without lowering cyan coloring density by incorporating a specified cyan dye forming coupler selected from specified compds. into at least one cyan color forming photosensitive silver halide emulsion layer. SOLUTION: At least one cyan color forming photosensitive silver halide emulsion layer contains at least one cyan dye forming coupler selected from compds. represented by formula I and a compd. represented by formula II or the like. In the formula I, Z<a> and Z<b> are each -C(R<3> )= or -N=, R<1> and R<2> are each an electron withdrawing group having a Hammett's substituent constant σp of >=0.20, the sum of the constants σp of R<1> and R<2> is >=0.65, R<3> is a substituent and X is H. In the formula II, R<a1> and R<a2> are each H, an alkyl or aryl, R<a3> and R<a4> are each H, an alkyl or aryl and R<a5> is an aryl, but the total number of carbon atoms of R<a1> -R<a5> is not <=13.

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 light-sensitive material,
Further, the present invention relates to a color photographic light-sensitive material having excellent color developing properties, color reproducibility, and rapid processing properties.

[0002]

2. Description of the Related Art A silver halide color photographic light-sensitive material has a red-sensitive emulsion layer (cyan coloring layer), a green-sensitive emulsion layer (magenta coloring layer) and a blue-sensitive emulsion layer (yellow coloring layer) on a support.
One or more layers, and an intermediate layer between these emulsion layers, and the oxidized developing agent reacts with the coupler in each emulsion layer using the exposed silver halide as an oxidizing agent. Then, cyan, magenta, and yellow dyes are formed, and a color image is formed by the color reduction method. As described above, since the silver halide color photographic light-sensitive material has the cyan, magenta, and yellow coloring layers stacked on each other, color mixing may occur even if an intermediate layer exists between them. In order to prevent such color mixing, a compound such as hydroquinone or hydroxyamine is added to the intermediate layer as a color mixing inhibitor. On the other hand, in recent years, pyrrolotriazole-based cyan couplers having excellent hue and coupling activity have been proposed, and the problem that color reproducibility is deteriorated due to unfavorable absorption in the yellow to magenta region which conventional cyan couplers have. (US Pat. No. 5,256,526; EP 0545300). However, these couplers have the disadvantage that they are more susceptible to color mixing than conventional cyan couplers, and it is difficult to prevent color mixing with the above-described color mixing inhibitors, and the appearance of an effective color mixing inhibitor is desired. Was.

[0003]

SUMMARY OF THE INVENTION The present invention has been made in view of the above-mentioned problems, and has as its object to provide a silver halide color display wherein at least one layer of a cyan color-forming emulsion contains a pyrrolotriazole cyan coupler. An object of the present invention is to prevent color mixing without lowering the cyan color density in a photographic light-sensitive material.

[0004]

The object of the present invention has been attained by providing a silver halide color photographic material having the following constitution (1). That is, (1) a support having at least one layer each of a yellow-sensitive photosensitive silver halide emulsion layer, a magenta-sensitive photosensitive silver halide emulsion layer, and a cyan-sensitive photosensitive silver halide emulsion layer on a support; In a silver halide color photographic material having at least one non-color-forming hydrophilic colloid layer having no coloring property, at least one of the cyan color-forming light-sensitive silver halide emulsion layers is a compound represented by the following general formula (I): Silver halide containing at least one cyan dye-forming coupler selected from the group consisting of a compound represented by the following general formula (II) and a compound represented by the following general formula (III) or (IV) Color photographic light-sensitive material.

Embedded image

Embedded image

Embedded image

Embedded image Wherein (I), Z ^a, respectively Z ^b is -C (R ³⁾ = or represents -N =. However, either Z ^a or Z ^b is −
Is N =, the other is -C (R ³⁾ is =. R ¹ and R
² has a Hammett's substituent constant σp value of 0.20
It represents the above electron withdrawing group, and the sum of the σp values of R ¹ and R ² is 0.65 or more. R ³ represents a hydrogen atom or a substituent. X 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. The group of R ¹ , R ² , R ^3, or X may be a divalent group and form a homopolymer or a copolymer by bonding to a dimer or higher polymer or a polymer chain. Formula (II)
In the formula, R ^a1 and R ^a2 each independently represent a hydrogen atom, an alkyl group or an aryl group. R ^a3 and R ^a4 represent a hydrogen atom, an alkyl group or an aryl group. R ^a5 represents an aryl group. However, the total number of carbon atoms of ^{R a1, R a2, R a3} , R a4 and R ^a5 not become 13 or less. In the formula (III),
X ¹ represents a hydroxyl group, an alkoxy group, or an NHR ⁴ group, and Y ¹ represents a group that can be substituted on a benzene ring. l represents an integer of 0 to 4, and when l is 2 or more,
¹ may be the same or different groups. R ⁴
Represents a hydrogen atom, an alkyl group, an aryl group, an acyl group, a sulfonyl group, a carbamoyl group, a sulfamoyl group, or an alkoxycarbonyl group. In the formula (IV), X ² represents a hydroxy group, an alkoxy group or an NHR ⁴ group. Y ² represents a group that can be substituted on a benzene ring. m represents an integer of 0 to 4, and when 1 is 2 or more, a plurality of Y ² may be the same group or different groups. R ⁴ represents a hydrogen atom, an alkyl group, an aryl group, an acyl group, a sulfonyl group, a carbamoyl group, a sulfamoyl group, or an alkoxycarbonyl group.

[0005]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below in detail. First, the cyan coupler represented by formula (I) used in the present invention will be described. Here, the Hammett's substituent constant [sigma] p value used in this specification will be briefly described. Hammett's rule was used to quantitatively discuss the effect of substituents on the reaction or equilibrium of benzene derivatives.
A rule of thumb proposed by LP Hammett for 5 years,
This is widely accepted today. The substituent constants determined by Hammett's rule include σp and σm values, which can be found in many common books,
For example, edited by JADean, "Lange's Handbook of Chemistr
y ”, 12th edition, 1979 (Mc Graw-Hill) and“ Region of Chemistry ”special edition, No. 122, pp. 96-103, 1979 (Nankodo). In the present invention, each substituent is limited or explained by Hammett's substituent constant σp, which means that it is limited only to the substituent having a value known in the literature, which can be found in the above-mentioned book. However, 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 σp value is used as a measure of the electronic effect of the substituent regardless of the substitution position. In the present invention, the σp 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 10% or less.

[0006] In the present specification, the term "aliphatic" means a straight-chain, 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.

Hereinafter, the cyan coupler represented by formula (I) of the present invention will be described in detail. Z ^a and Z ^b each a -C (R ³⁾ = or an -N =. However, Z either ^a and Z ^b are -N =, the other is -C (R ³⁾ =
It is.

R ³ 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 hydrogen atom, halogen atom (for example, chlorine atom, bromine atom), alkyl group (for example, linear or branched alkyl group having 1 to 32 carbon atoms, aralkyl group, alkenyl group, An alkynyl group, a cycloalkyl group or a 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 (for example, methanesulfonamide, hexadecanesulfonamide, benzenesulfonamide, p-toluenesulfonamide, octadecanesulfonamide, 2-methoxy-5-t-butylbenzenesulfonamide), a carbamoyl group (for example, 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 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.

[0011] 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 further 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.

[0012] Cyan couplers of the present invention, both R ¹ and R ² is 0.20 or more electron-withdrawing group, and R ¹
The sum of the σp values of R ² are those which develops as a cyan image by 0.65 or more. The sum of the σp values of R ¹ and R ² is preferably 0.70 or more, and the upper limit is about 2.0.

R ¹ and R ² are Hammett's substituent constant σp
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 ¹ and R ^{2 having} a σp 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, Halogenated alkyl group, halogenated alkoxy group, halogenated aryloxy group, halogenated alkylamino group, halogenated alkylthio group, aryl group substituted with another electron-withdrawing group having a σp value of 0.20 or more, heterocycle Group, halogen atom, azo group, or A selenocyanate group. Among these substituents, the group which can have a substituent may further have a substituent as described for R ³ .

If R ¹ and R ² are described in more detail, σp
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 (e.g., difluoromethylthio, 1,1,
2,2-tetrafluoroethylthio), an aryl group substituted with another electron-withdrawing group having a σp of 0.20 or more (eg, 2,4-dinitrophenyl, 2,4,6-trichlorophenyl, pentachlorophenyl) A heterocyclic group (eg, 2-benzoxazolyl, 2-benzothiazolyl,
1-phenyl-2-benzimidazolyl, 5-chloro-
1-tetrazolyl, 1-pyrrolyl), a halogen atom (for example, a chlorine atom or a bromine atom), an azo group (for example, phenylazo) or a selenocyanate group. Among these substituents, a group which may further have a substituent is R ³
It may further have a substituent as mentioned in the above.

R ¹ and R ² 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 σp 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 ¹ is a cyano group. Particularly preferred as R ² is an alkoxycarbonyl group, and most preferred is a branched alkoxycarbonyl group (especially a cycloalkoxycarbonyl group).

X 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 aryloxy group, 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, Examples include 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 ³ .

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 (for example, acetoxy, tetradecanoyloxy, benzoyloxy), alkyl or aryl A sulfonyloxy group (eg, methanesulfonyloxy, toluenesulfonyloxy), an acylamino group (eg, dichloroacetylamino, heptafluorobutyrylamino), an alkyl or aryl sulfonamide group (eg, 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 (eg, N-methylcarbamoylamino, N-phenylcarbamoylamino), carbamoyloxy group (eg, N, N-diethylcarbamoyloxy, N-ethylcarbamoyl) Oxy, N-ethyl-N-phenylcarbamoyloxy),
Heterocyclic carbonyloxy group (eg, morpholinocarbonyloxy, piperidinocarbonyloxy), 5- or 6-membered nitrogen-containing heterocyclic group (eg, 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 is an aldehyde or ketone as a leaving group bonded via a carbon atom.
It may take the form of a bis-type coupler obtained by condensing an equivalent coupler. X may contain a photographically useful group such as a development inhibitor and a development accelerator.

X is preferably 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 nitrogen atom at the coupling active site. A 5- or 6-membered nitrogen-containing heterocyclic group bonded by an atom. More preferred X 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 and a heterocyclic carbonyloxy group. It is.

In the cyan coupler represented by the general formula (I), the group of R ¹ , R ² , R ³ or X becomes a divalent group, and binds to a dimer or higher polymer or a polymer chain. To form a homopolymer or a copolymer. A homopolymer or a copolymer bonded to a polymer chain is a typical example of an addition polymer having a cyan coupler residue represented by the general formula (I), a homopolymer or a 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 (I), and one of the 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 (I) is preferably represented by the following general formula (P).

[0021]

Embedded image

In the formula, R is a hydrogen atom, an alkyl having 1 to 4 carbon atoms.
And A represents -CONH-, -COO-
Or a substituted or unsubstituted phenylene group, and B is
A substituted or unsubstituted alkylene group, a phenylene group or
Represents an aralkylene group, L represents -CONH-, -NHCONH-,
-NHCOO-, -NHCO-, -OCONH-, -NH-, -COO
-, -OCO-, -CO-, -O-, -S-, -SO_Two −,
−NHSO_Two -Or -SO _TwoNH-. a, b, and c are 0
Or 1 is indicated. Q represents a compound represented by the general formula (I)
R¹, R^Two , R^ThreeOr a shear from which a hydrogen atom has been removed from X
Indicate the coupler residue. The polymer of the general formula (I)
Cyan coloring monomer and fragrance represented by coupler unit
Does not couple with oxidation products of aromatic primary amine developers
Copolymers of non-chromogenic ethylene-like monomers are preferred.

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 vinylic monomer corresponding to the above general formula (I) is used to form the copolymer having physical properties and / or Alternatively, it can be selected such that the chemical properties, eg, solubility, compatibility with the binder of the photographic colloid composition, eg, 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 ^1, R ² , at least one of R ³ and X is a so-called ballast group (preferably having a total carbon number of 1).
0 or more), and more preferably 10 to 50 carbon atoms in total. Particularly, it is preferable that R ³ has a ballast group. The cyan coupler represented by the general formula (I) is more preferably a compound having a structure represented by the following general formula (V).

[0027]

Embedded image

In the formula, R ¹¹ , R ¹² , R ¹³ , R ¹⁴ and R ¹⁵ 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 ¹¹ and R ^{12 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 ¹³ , R ¹⁴ and R ¹⁵ represent a hydrogen atom or an aliphatic group. Examples of the aliphatic group include the groups described above for R ¹¹ and R ¹² . R ¹³ , R ¹⁴ , R
¹⁵ 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,
Examples thereof include an oxane ring and a thiane ring, and these rings may be substituted with a substituent represented by R ³ described above. The ring formed by Z is preferably a cyclohexane ring which may be substituted, and particularly preferably an alkyl group having 1 to 24 carbon atoms at the 4-position (substituted by a substituent represented by R ³ described above). A cyclohexane ring substituted with

[0030] formula R ³ of (V) has the same meaning as R ³ of formula (I), 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 ² represents a hydrogen atom or a substituent. The substituent is X ² -C (=
O) Groups which promote the elimination of the O- group are preferred. X ² 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 ^{3 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.

The aryl group preferably has 6 to 36 carbon atoms, and more preferably has a single ring. Specific examples include phenyl, 4-t-butylphenyl, 2-methylphenyl, 2,4,6-trimethylphenyl, 2-methoxyphenyl, 4-methoxyphenyl, 2,6-dichlorophenyl, 2-chlorophenyl, 4-dichlorophenyl and the like. General formula (V) used in the present invention
The cyan coupler represented by has an oil-solubilizing group in the molecule, is easily soluble in a high boiling organic solvent, and is formed by oxidative coupling of the coupler itself and the coupler with a color-forming reducing agent (developer). Preferably, the dye is non-diffusible in the hydrophilic colloid layer. In the coupler represented by the general formula (V), R ³ contains a coupler residue represented by the general formula (V) to form a dimer or higher multimer, or R ³ represents a polymer chain. They may be contained to form a homopolymer or a copolymer. A typical example of the homopolymer or copolymer containing a polymer chain is a homopolymer or copolymer of an addition polymer ethylenically unsaturated compound having a coupler residue represented by the general formula (V). In this case, the polymer may contain one or more cyan coloring repeating units having a coupler residue represented by the general formula (V), and an acrylate, methacrylate, or maleate as a copolymer component. It may be a copolymer containing one or more non-color-forming ethylenic monomers that do not couple with the oxidation product of an aromatic primary amine developer such as phenol. Specific examples of the cyan coupler defined in the present invention are shown below, but the invention is not limited thereto.

[0033]

Embedded image

[0034]

Embedded image

[0035]

Embedded image

[0036]

Embedded image

[0037]

Embedded image

[0038]

Embedded image

[0039]

Embedded image

[0040]

Embedded image

[0041]

Embedded image

[0042]

Embedded image

[0043]

Embedded image

[0044]

Embedded image

[0045]

Embedded image

The compound represented by the formula (I) can be prepared by a known method, for example, as described in JP-A-5-150423 and 5-2.
No. 55333, No. 5-202004, No. 7-4837
No. 6 can be synthesized. Hereinafter, specific synthesis examples of the compound represented by the general formula (I) will be shown. Synthesis Example 1 Synthesis of Exemplified Compound (1) Exemplified Compound (1) was synthesized by the following route.

[0047]

Embedded image

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 (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 crystallization was performed to obtain 6.0 g of the exemplary compound (1). Melting point: 256-257 ° C.

Synthesis Example 2 Synthesis of Exemplified Compound (25) In the synthesis of Compound (1), 4.5 g of diallylcarbamoyl chloride was added instead of morpholinocarbamoyl chloride, and the mixture was stirred at room temperature for 2 hours. After the reaction,
The mixture was poured into 200 ml of diluted hydrochloric acid and extracted with 200 ml of ethyl acetate. After the organic phase was dried over magnesium sulfate, the solvent was distilled off under reduced pressure, hexane was added to the residue, and the residue was crystallized to obtain 5.5 g of the desired exemplary compound. Melting point is 2
19 ° C to 220 ° C. Other compounds can be synthesized similarly.

The preferred coating amount of the cyan coupler of the present invention varies depending on the molar extinction coefficient of the cyan coupler.
In the range of 01~1g / m ^2, preferably 0.05 to 0.
5 g / m ² . When the cyan coupler to be used is a coupler represented by the general formula (V), the preferred amount is in the range of 0.01 to 0.6 g / m ² , more preferably 0.05 to 0.4 g / m ^2. m ² , more preferably 0.1
０．３0.3 g / m ² . The ratio of the amount of the cyan coupler to the amount of the silver halide used depends on the equivalentity of the coupler, and the 2-equivalent coupler has an Ag / coupler ratio of 1.5 to 8,4.
For equivalent couplers, the range is 3-16. In the present invention, 2-equivalent couplers having a low pKa are preferred, in which case the Ag / coupler ratio is in the range 1.5-8, preferably 2-5.
6, more preferably in the range of 2.5-5.

Next, the compounds added for preventing color mixing in the present invention will be described. The above-mentioned general formula (II) is a compound called phenidone, and it has other problems such as cyan fog, cyan stain, and processing color mixing which are remarkably observed when a highly active cyan coupler having a pKa of 8.7 or less is used. Although the photographic performance can be improved without significantly affecting the photographic performance, the cyan coupler of the above general formula (I) has a feature that the pKa is low due to its structure. Is particularly effective for preventing color mixing. The effect is particularly large when the pKa of the cyan coupler of the present invention is 8.0 or less, and even greater when the pKa is 7.5 or less. (The pKa of the coupler can be easily measured by determining the pH at the point where it has been neutralized just half by using a pH titration curve in a THF / water = 6/4 mixed solvent system.) By combining the phenidone compound with the above-mentioned general formula (III) or (IV), particularly in an emulsion layer containing the cyan coupler represented by the above-mentioned general formula (I), color mixing is significantly prevented.

In the compound represented by the general formula (II),
When R ^a1 or R ^a2 is an alkyl group, the total number of carbon atoms including the substituent is preferably in the range of 1 to 30, more preferably 1 to 20. When R ^a1 or R ^a2 is an aryl group, the total number of carbon atoms including the substituent is preferably 6 to 30. When R ^a3 or R ^a4 is an alkyl group, the total number of carbon atoms including the substituent is preferably in the range of 1 to 24, more preferably 1 to 24.
18 range. When R ^a3 or R ^a4 is an aryl group, the sum of the carbon numbers including the substituents is preferably in the range of 6 to 24.

The group which can be substituted with an alkyl group for R ^{a1 to} R ^a4 is not particularly limited. , An alkylthio group, an arylthio group, an acylamino group, a carbamoyl group, a sulfamoyl group, a sulfonamide group, a carbamoylamino group, and an alkoxycarbonylamino group are preferable, and in particular, a halogen atom, an alkoxy group,
Acyloxy, alkoxycarbonyl, aryloxy and acylamino groups are more preferred. The group which can be substituted for the alkyl group may contain an unsaturated bond.

When R ^{a1 to} R ^a4 are an aryl group, the substitutable group may be the same as the above-mentioned examples of the substituent of the alkyl group. Group, acyloxy group and acylamino group.

[0057] In the preferred range of the number range of 6 to 30 carbons of R ^a5, more preferably from 6 to 24. The group that can be substituted for R ^a5 is the same as the group that can be substituted for the aryl group of R ^{a1 to} R ^a4 , and the preferred groups are also the same. The compound of the general formula (II) is used by being fixed in oil droplets and dispersed in a hydrophilic colloid. Therefore, it is necessary to make the compound lipophilic. It is preferable that at least any one lipophilic groups R ^a1 to R ^a5 (oil-solubilizing group) is introduced, the total number of carbon atoms of R ^a1 to R ^a5 is at least 14
It is necessary to be above. The total number of carbon atoms is preferably in the range of 16 to 40, more preferably 18
~ 36.

A preferred range of the number of carbon atoms of R ^a5 in the range of 6 to 0 and more preferably in the range of 6 to 24. The group that can be substituted for R ^a5 is the same as the group that can be substituted for the aryl group of R ^{a1 to} R ^a4 , and the preferred groups are also the same. General formula (I
The compound (I) is used by being fixed in oil droplets and dispersed in a hydrophilic colloid. Therefore, it is necessary to make the compound lipophilic. Either at least one of R ^a1 to R ^a5
Preferably the lipophilic group (oil-solubilizing group) is introduced into One, the total number of carbon atoms of R ^a1 to R ^a5 is required to be at least 14 or more. The total number of carbon atoms is preferably in the range of 16 to 40, more preferably 18 to 40.
36.

Preferred as the group for introducing the oil-solubilizing group is R ^a1 or R ^a5 . If oil-solubilizing group is introduced into R ^a1, as the oil-solubilizing group substituted with an unsubstituted linear or branched alkyl group or an alkoxy group, an aryloxy group, an acyl group or an alkoxycarbonyl group having 12 to 24 carbon atoms The alkyl group having 12 to 36 carbon atoms is preferable, and the alkyl group having 14 to 20 carbon atoms is particularly preferable. At this time, ^Ra5
May or may not have a substituent, but is preferably unsubstituted. When an oil-solubilizing group is introduced into ^Ra5 , the oil-solubilizing group is preferably an alkyl group having 12 to 30 carbon atoms, an alkoxy group, an acyloxy group, or an acylamino group, and particularly preferably an alkoxy group having 12 to 24 carbon atoms. R ^a3 and R ^a4 are preferably hydrogen atoms. Among the compounds of the general formula (II), a compound represented by the following general formula (VI) or (VII) is preferable from the viewpoint of storage stability.

[0060]

Embedded image

[0061]

Embedded image

Next, the compound represented by formula (VI) will be described in detail. R ^a and R ^b each independently represent a substituted or unsubstituted aryl group or a substituted or unsubstituted alkyl group having a total of 1 to 30 carbon atoms including the carbon number of the substituent. When R ^a and R ^b are an aryl group, the substituent that substitutes the aryl group is the substituent described in the description of R ^a1 in the formula (II), and specific examples thereof include those described in the description of R ^a1. Can be Among them, more preferably, an alkyl group, an alkoxy group, an acylamino group, a halogen atom,
An aminocarbonylamino group and an alkoxycarbonylamino group. Most preferably, an alkyl group (having 1 to 1 carbon atoms)
10), a halogen atom (a chlorine atom and a bromine atom), and an alkoxy group (1 to 10 carbon atoms). When R ^a and R ^b are aryl groups, unsubstituted aryl groups are more preferable than those having a substituent. When R ^a and R ^b are an alkyl group, the total number of carbon atoms including the number of carbon atoms of the substituent is
1 to 30. The unsubstituted alkyl group may be linear or branched. As a straight-chain alkyl, it has 1 to 26 carbon atoms.
(Eg, methyl, ethyl, n-propyl, n-butyl,
Those having n-hexyl, n-octyl, n-decyl, n-octadecyl, n-eicosyl) are preferable, and the branched alkyl includes 3 to 26 carbon atoms (for example, i-propyl,
t-butyl, 2-ethylhexyl) are preferred. R ^a ,
When R ^b is a substituted alkyl, the substituent is a group represented by the formula (II):
It is a substituent described in the description of ^a1 , and the total number of carbon atoms including the number of carbon atoms of the substituent is preferably from 1 to 20. Specific examples thereof include those described in the description of ^Ra1 , and specific examples thereof include ethoxymethyl, acetoxymethyl, stearoyloxymethyl, p-phenoxymethyl, 1-
Nitrophenoxymethyl, 1-chlorooctyl and the like.

R ^a3 and R ^a4 represent a hydrogen atom, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted aryl group. When R ^a3 and R ^a4 are a substituted alkyl group or a substituted aryl group, the substituent is the substituent described in the description of R ^{a1 in} the formula (II), and specific examples thereof are also those described in the description of R ^a1. Is mentioned. When R ^a3 or R ^a4 is an alkyl group, it preferably has 1 to 20 carbon atoms. An unsubstituted alkyl group is preferable to an alkyl group having a substituent. When R ^a3 or R ^a4 is an aryl group, it has 6 carbon atoms.
~ 20 is preferred. Preferably, at least one of R ^{a3 and} R ^a4 is a hydrogen atom, and most preferably,
^Ra3 and ^Ra4 are both hydrogen atoms.

R ^a5 is a substituted or unsubstituted aryl group, and the substituent to be substituted on the aryl group is R ^{a1 of the} formula (II)
Are the substituents described above. Specific examples of the substituent include those described in the description of the formula (II). The substituent is preferably an alkyl group (1 to 20 carbon atoms, for example, methyl,
Ethyl, i-propyl, t-butyl, n-octyl),
An alkoxy group (1 to 20 carbon atoms, for example, methoxy, ethoxy, i-propoxy, t-butoxy, n-octyloxy, n-tetradecyloxy, n-hexadecyloxy, n-octadecyloxy), an acylamino group (carbon number 1-20, for example, acetylamino group, propionylamino, stearoylamino), alkoxycarbonylamino (2-20 carbon atoms, such as methoxycarbonylamino, ethoxycarbonylamino, octyloxycarbonylamino), aminocarbonylamino (1-2 carbon atoms)
0, for example, dimethylaminocarbonylamino, dioctylaminocarbonylamino), alkylsulfonylamino group (1 to 20 carbon atoms, for example, methanesulfonylamino, ethanesulfonylamino, butanesulfonylamino, octanesulfonylamino), and arylsulfonylamino (C6) -20, for example, benzenesulfonylamino, toluenesulfonylamino, dodecylbenzenesulfonylamino).

The compound of the formula (VI) preferably has a so-called ballast group in at least one of R ^a , R ^b , R ^a3 , R ^a4 and R ^{a5 from} the viewpoint of diffusion resistance. Molecular weight is 20
0 or more is preferable, 250 or more is preferable, and 300 or more is preferable.
The above is more preferred, and the most preferred is 350 or more. The compound of the formula (VII) will be described in detail. Formula (VII)
R ^a3 , R ^a4 and R ^a5 have the same ^meanings as those of the formula (VI).
The same applies to specific examples and preferable examples. R ^c represents a substituted or unsubstituted alkyl group or a substituted or unsubstituted aryl group. When R ^c is an alkyl group or an aryl group, the substituent is the substituent described in the description of R ^{a1 in} the formula (II). Specific examples thereof include those described in the description of ^Ra1 . R ^c is preferably an alkyl group (1 to 20 carbon atoms, for example, methyl, ethyl, i-propyl, t-butyl, n-octyl, n-dodecyl, n-hexadecyl, n-octadecyl, i-octadecyl,
-Ethylhexyl, 2-methoxyethyl, 2-chloroethyl) and aryl groups (C6-20, for example, phenyl, naphthyl, p-chlorophenyl, m-methoxyphenyl, o-methylphenyl).

The compound of the formula (VII) preferably has a so-called ballast group in at least one of R ^c , R ^a3 , R ^a4 and R ^{a5 from} the viewpoint of diffusion resistance. The molecular weight is preferably 200 or more, more preferably 250 or more, still more preferably 300 or more, and most preferably 350 or more. Among the phenidone compounds represented by formulas (VI) and (VII) of the present invention, when added to the non-photosensitive layer, more preferred are compounds represented by formula (VI). When added to the photosensitive layer, the compound represented by the general formula (VII) is more preferred. Among the compounds represented by the general formula (VII), those in which R ^c is an alkyl group, R ^a3 and R ^a4 are both hydrogen atoms, and R ^a5 is a substituted or unsubstituted aryl group are preferable. Among them, those in which the aryl group of R ^a5 is unsubstituted or those in which the substituent is an alkoxy group, an acylamino group, an alkylsulfonylamino group, or an arylsulfonylamino group are preferable. More preferred. As R ^c , an unsubstituted alkyl group is more preferable than an alkyl group having a substituent. Most preferred of the compounds represented by the general formula (VII) are those wherein R ^c is an unsubstituted alkyl group, R ^a3 and R ^a4 are hydrogen atoms, and R ^a5 is an unsubstituted aryl group. Specific examples of the compound represented by the general formula (VI) or (VII) of the present invention are shown below, but it should not be construed that the invention is limited thereto.

[0067]

Embedded image

[0068]

Embedded image

[0069]

Embedded image

[0070]

Embedded image

[0071]

Embedded image

[0072]

Embedded image

[0073]

Embedded image

[0074]

Embedded image

[0075]

Embedded image

[0076]

Embedded image

A method for synthesizing the compounds represented by formulas (VI) and (VII) will be described. The compound represented by the general formula (VI) of the present invention can be synthesized according to the following synthesis method.

[0078]

Embedded image

Compound (VII) -A is condensed with hydrazine to synthesize a compound represented by formula (VII). In the compound (VII) -A, R ^d is an alkyl group or an aryl group, and R ^c , R ^a3 and R ^a4 are R ^c ,
Have the same meanings as R ^a3, R ^a4. R ^a5 hydrazine has the same meaning as R ^a5 of the formula (VII). In this reaction, it is preferable to cause one or more equivalents of a base to act in a suitable solvent. When a hydrazine salt is used, it is preferable to use two or more equivalents of a base to release hydrazine. The base is preferably an alkoxide, and examples thereof include potassium tert-butoxide and sodium methoxide. Examples of the solvent include n-butanol, t-butanol, dimethylsulfoxide, dimethylacetamide and the like. The reaction temperature is generally -20 ° C to 1
Although it can be performed at 80 ° C., it is preferably 0 ° C. to 120 ° C.,
More preferably, it is 30 ° C to 90 ° C. The reaction time is generally from 5 minutes to 24 hours, but is preferably from 30 minutes to 6 hours, more preferably from 1 hour to 3 hours. The molar ratio of hydrazine to compound (VII) -A is preferably 2: 1 to 1: 2. More preferably, it is 1.2: 1 to 1: 1.2.

The compound represented by the general formula (VI) is synthesized by reacting the general formula (VI) -A with hydrazine. Formula (VI) in ^{-A, R a, R b,} R a3, R a4 is an R ^a of the general Formula (VI), and R ^b, R ^a3, R ^a4 synonymous.
L ¹ and L ² are groups that leave in a nucleophilic reaction. L ¹
Is preferably a halogen atom or an oxygen atom activated by a condensing agent. L ² is preferably a hydroxy group or a halogen atom. Reaction temperature is generally -20 ° C
The reaction can be performed at a temperature of from 180 to 180 ° C, preferably from 0 to 120 ° C, more preferably from 30 to 90 ° C. The reaction time is generally from 5 minutes to 24 hours, but preferably from 1 to 24 hours.
From time to 6 hours. From compound (VI) -B to (VI
In the reaction ()), when L ² is a hydroxyl group, acidic conditions are preferable. When L ² is a halogen atom, the reaction may be performed under any of neutral, acidic and alkaline conditions.

Synthesis of Compound (52) Exemplified Compound 52 was synthesized by the following route.

[0082]

Embedded image

(1) First Step 256 g (1.94 mol) of methyl succinate and 800 ml of methanol were stirred at room temperature, and 375 g (1.94 mol) of sodium methylate (28% by weight) was added dropwise thereto. Then, 592 g of 1-bromohexadecane
(1.94 mol) was added dropwise. After refluxing for 3 hours, methanol was distilled off, and the reaction solution was poured into 1N aqueous hydrochloric acid. After extraction with hexane, washing with brine and drying, the solvent was distilled off to obtain 511 g (1.43 mol) of an intermediate a (yield: 73.7).
%).

(2) Second step 511 g (1.43 mol) of intermediate A and methanol 8
A solution prepared by dissolving 94.6 g (1.43 mol) of potassium hydroxide (85%) in 800 ml of methanol was added dropwise to 00 ml of the solution with stirring at 35 ° C. After reacting at 40 ° C. for 2 hours, a solution obtained by dissolving 130 ml of concentrated hydrochloric acid in 500 ml of water was further added dropwise. The precipitated crystals are collected by filtration, and water and n
-Washing with hexane gave Intermediate b. The intermediate b was used in the next step without drying.

(3) Third step: Intermediate B (total amount: 1.43 mol) and methanol 1.0
Of dimethylamine and stirring at 20 ° C.
15 g (1.57 mol) were added dropwise. Then 3 more
135 g (1.57 mol) of a 5% aqueous folimarin solution was added dropwise and reacted at 20 ° C. for 24 hours. The precipitated crystals were collected by filtration, washed with water and methanol, and then dried to obtain 396 g (1.28 mol) of intermediate C (yield: 89.5).
%).

(4) Fourth step 145 g (1.34 mol) of phenylhydrazine and 1.5 l of toluene were stirred at 140 ° C., and the solvent was distilled off using a Dean-Stark dehydrator until the internal temperature reached 100 ° C. . Subsequently, sodium methylate (28% by weight)
After dropping 272 g (1.41 mol) of methanol and distilling off methanol, a solution of 396 g (1.28 mol) of the intermediate c in 400 ml of toluene was dropped. After refluxing for 30 minutes,
After cooling on ice, 150 ml of concentrated hydrochloric acid was added.
0 ml was added. The insoluble matter was removed by filtration, and the solution was cooled. After the precipitated crystals were collected by filtration, washed with water and n-hexane, and dried, 393 g of compound (51) (1.02
mol) was obtained (yield 79.7%). Other compounds can be synthesized similarly.

The compound represented by the general formula (II) of the present invention is used together with a cyan coupler in a cyan color-forming layer. It is further preferable in that the effect is large and the influence such as a decrease in the color developing property is small. The compound of the general formula (II) can also be used for a non-photosensitive colloid layer. In this case, it is desirable to use in combination with a known color mixing inhibitor such as hydroquinones. When used in the non-photosensitive layer, the compound of the general formula (II) is more preferably a compound of the structure represented by the general formula (VI) from the viewpoint of its effect.

The amount of the compound represented by formula (II), (VI) or (VII) of the present invention used in the cyan coloring layer is preferably in the range of 0.1 to 100 mol% based on the cyan coupler. It is in the range of 1 to 50 mol%. It is also possible to preferably use a compound of the general formula (II), (VI) or (VII) in a photosensitive layer other than the above, but in this case, the total amount used is 0.1 to 200 to the cyan coupler.
Mol%, more preferably 1 to 100 mol%, still more preferably 2 to 50 mol%. In the present invention, the compound represented by the general formula (II), (VI) or (VII) may be added to a non-photosensitive hydrophilic colloid layer in a high-boiling organic solvent, a color mixing inhibitor, an ultraviolet absorber, or a polymer dispersant. Can be used together with a dispersing aid such as a surfactant together with the organic compound. The amount used is 0.1 mol% to 2 mol based on the cyan coupler to be coated.
It is in the range of 00 mol%, preferably 1 to 100 mol%, more preferably 2 to 50 mol%.

Next, the compounds of the general formulas (III) and (IV) for preventing color mixing in combination with the phenidone compound of the general formula (II)
Will be described. In the formula (III), X ¹ represents a hydroxyl group, an alkoxy group, or an NHR ⁴ group,
When X ¹ is an alkoxy group, those having 1 to 24 carbon atoms are preferred. When X ¹ is an NHR ⁴ group (R ⁴ is a hydrogen atom, an alkyl group, an aryl group, an acyl group, a sulfonyl group, a carbamoyl group, a sulfamoyl group, or an alkoxycarbonyl group), when R ⁴ is an alkyl group Is a group having 1 to 24 carbon atoms, and is a group having 6 to 30 carbon atoms when R ⁴ is an aryl group; and a carbon group when R ⁴ is an acyl group, a sulfonyl group, a carbamoyl group, a sulfamoyl group, or an alkoxycarbonyl group Those having the numbers 1 to 30 are preferred. X ¹ is preferably a hydroxyl group or NHR ⁴ , more preferably a hydroxyl group. R ⁴ is preferably an alkyl group, an acyl group, or a sulfonyl group, and more preferably an acyl group or a sulfonyl group. Y ¹ may be any group as long as it is a group capable of substituting for a benzene ring, preferably an alkyl group having 1 to 24 carbon atoms, an alkoxy group having 1 to 24 carbon atoms, an acyl group having 1 to 24 carbon atoms, Acylamino group having 1 to 24 carbon atoms, 1 to 24 carbon atoms
A sulfonamide group, a sulfonyl group having 1 to 24 carbon atoms,
A carbamoyl group having 1 to 24 carbon atoms, an alkoxycarbonyl group having 1 to 24 carbon atoms, a ureido group having 1 to 24 carbon atoms,
It is a urethane group having 1 to 24 carbon atoms, an aryl group having 6 to 20 carbon atoms, a halogen atom or a sulfo group. More preferred as Y ¹ are an alkyl group, an acyl group, an acylamino group, a sulfonamide group and an alkoxy group, and among them, an alkyl group, an acylamino group and a sulfonamide group are most preferred. As the alkyl group, a branched or linear unsubstituted alkyl group, or an alkyl group substituted with an amide group or an ester group is more preferable. Further, in order to impart oil solubility to the compound, it is preferable that either X ¹ or Y ¹ is a group having 6 or more carbon atoms, and more preferably, either X ¹ or Y ¹ is a group having 8 or more carbon atoms. Further, the sum of the carbon numbers of X ¹ and Y ¹ is preferably 8 or more, more preferably 12 or more, and further preferably 16 or more. Hereinafter, specific examples of the compound represented by formula (III) are shown, but the invention is not limited thereto.

[0090]

Embedded image

[0091]

Embedded image

[0092]

Embedded image

[0093]

Embedded image

[0094]

Embedded image

[0095]

Embedded image

Next, the compound represented by formula (IV) will be described. In the compound represented by the formula (IV), preferred X ² , Y ² and R ⁴ are each represented by the general formula (III)
Is a group having the same meaning as X ¹ , Y ¹ and R ⁴ described as preferred substituents. Hereinafter, specific examples of the compound represented by the general formula (IV) are shown, but the invention is not limited thereto.

[0097]

Embedded image

[0098]

Embedded image

[0099]

Embedded image

The amount of the compound represented by formula (III) or (IV) of the present invention in the cyan coloring layer is preferably in the range of 0.1 mol% to 200 mol% based on the cyan coupler. Is in the range of 1 mol% to 100 mol%, more preferably in the range of 2 mol% to 50 mol%. In the present invention, the compounds represented by the general formulas (II), (III) and (IV) are contained in the cyan coupler-containing emulsion layer, and when preparing the cyan coupler emulsified dispersion, other components ( Together with a cyan coupler, an ultraviolet absorber, a color image stabilizer and the like.

The cyan coupler of the present invention has the following general formula in addition to the above compounds in terms of hue adjustment and promotion of color formation.
It is preferred to use any of the compounds represented by (VIII), (IX), (X) and (XI). These compounds can be used in combination of several types depending on the purpose.

[0102]

Embedded image

In the general formula (VIII), the substituent R ^s represents an alkyl group, an alkoxy group, an acyl group, an alkoxycarbonyl group, an acyloxy group, an acylamino group, a sulfonamide group, a carbamoyl group, a sulfamoyl group or a sulfonyl group. These substituents further include a halogen atom,
It may have a substituent such as a hydroxyl group, an alkyl group, an aryl group, an alkoxy group and an ester group. The substituent R ^s is preferably an alkoxy group or an alkoxycarbonyl group, and most preferably an alkoxy group. The substitution position of the substituent R ^s may be ortho, meta or para to the COOH group, but is preferably ortho to the hue adjusting ability. The benzene ring may further have a substituent such as a halogen atom or an alkyl group.

In the general formula (IX), the substituent R ^t is an alkyl group,
Represents an alkoxy group, an acyl group, an alkoxycarbonyl group, an acyloxy group, an acylamino group, a sulfonamide group, a carbamoyl group, a sulfamoyl group or a sulfonyl group. These substituents may further have a substituent such as a halogen atom, a hydroxyl group, an alkyl group, an aryl group, an alkoxy group, and an ester group. The substituent R ^t is preferably an alkoxy group or an alkoxycarbonyl group, and most preferably an alkoxy group. Ortho substitution position CONH ₂ group substituents R ^t, meta, para -
Either one may be used, but the ortho position is preferred from the viewpoint of hue adjusting ability. Further halogen atoms on the benzene ring,
It may have a substituent such as an alkyl group.

In the general formula (X), the substituents R ^u , R ^v , R ^w and R ^x may be the same or different and each represents a hydrogen atom, an alkyl group, an aryl group, an alkoxycarbonyl group or an acyl group. These substituents may further have a substituent such as a halogen atom, a hydroxyl group, an alkyl group, an aryl group, an alkoxy group, and an ester group. Substituents R ^u, R ^v, preferably as R ^w and R ^x is a hydrogen atom, an alkyl group or an aryl group, an alkyl group or a cycloalkyl group is more preferably a cycloalkyl group branch is most preferred. The substitution position of the two carbamoyl groups may be any of ortho, meta and para-, but it is particularly preferred that the carbamoyl group is meta at the point of hue adjusting ability. The benzene ring may further have a substituent such as a halogen atom or an alkyl group.

In the general formula (XI), the substituent Q represents a> N—R ^y group or a> C (R ^y1 ) R ^y2 group. The substituents R ^y , R ^y1 and R ^y2 each represent a hydrogen atom, an alkyl group, an aryl group,
Represents an alkoxycarbonyl group or an acyl group. Also,
The substituent R ^z represents a hydrogen atom, an alkyl group, an alkoxy group, an aryloxy group or an acyloxy group. These substituents may further have a substituent such as a halogen atom, a hydroxyl group, an alkyl group, an aryl group, an alkoxy group, and an ester group. The substituent R ^y is preferably an alkyl group or an aryl group, and more preferably an alkyl group substituted with a linear or branched alkyl group or an aryl group. The substituent R ^z is preferably an alkyl group or an alkoxy group, more preferably an alkoxy group.
R ^y1 and R ^y2 are preferably a hydrogen atom or an alkyl group.

The following formulas (VIII), (IX) and (X)
Specific examples of the compounds represented by and (XI) are shown below, but the compounds preferably used in the coupler of the present invention are not limited to the following.

[0108]

Embedded image

[0109]

Embedded image

[0110]

Embedded image

[0111]

Embedded image

In order to introduce the cyan coupler and the like into the silver halide photosensitive material, known dispersion methods such as an oil-in-water dispersion method and a latex dispersion method using a high-boiling organic solvent described later can be used. In the oil-in-water dispersion method, a cyan coupler or other photographically useful compound is dissolved in a high-boiling organic solvent, and the dispersion is dispersed in a hydrophilic colloid, preferably in an aqueous gelatin solution, together with a dispersing agent such as a surfactant, using an ultrasonic, colloid mill. It can be emulsified and dispersed into fine particles by a known device such as a homogenizer, a Menton-Gaulin, a high-speed dissolver, or the like. 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 which is completely miscible with water, for example, methyl alcohol, ethyl alcohol, acetone, tetrahydrofuran, dimethylformamide and 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 in the final coating composition 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 preferably from 0.04 to 0.50 μm, more preferably from 0.05 to 0.30 μm, and most preferably from 0.08 to 0.20 μm. It is. The average particle size was measured using the Coulter Submicron Particle Analyzer mode.
It can be measured using 1N4 (Coulter Electronics) or the like.

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 cyan coupler used can be arbitrarily determined, but is preferably 0.1.
Or more, and 10.0 or less, more preferably 0.3 or more and 7.0 or less, and most preferably 0.5 or more and 5.0 or less. It is also possible to use a high boiling point organic solvent without using it at all.

With respect to the cyan coupler of the present invention, the conventionally used 2-acylamino-5-alkylphenol-type cyan coupler, 2,5-diacylaminophenol-type cyan coupler and 2-carbamoyl-1-
A naphthol type cyan coupler can be used in combination.
Among them, a combination with a 2-acylamino-5-alkylphenol-type cyan coupler is particularly preferable. In this case, the cyan coupler to be used in combination is 1 to the coupler of the present invention.
It is in the range of 50 mol%, preferably 5 to 40 mol%, more preferably 10 to 30 mol%.

In order to improve the image fastness of the cyan coupler of the present invention, a method of co-dispersing an organic solvent-soluble water-insoluble polymer in oil droplets is also preferably used. In this case, the polymer is preferably a styrene, acrylamide, methacrylamide, acrylate, methacrylate-based polymer or a copolymer thereof, and the number average molecular weight is preferably in the range of 20,000 to 200,000. In order to improve the stability of the emulsion, an oligomer molecule having a molecular weight of about 500 to 5,000 is preferably used, and a styrene oligomer, an α-methylstyrene oligomer and the like are preferable. In particular, styrene and α-
Methylstyrene oligomers are particularly preferred in terms of solubility. It is also preferable to add an amphiphilic polymer to the coating solution to promote color formation. In this case, a copolymer of acrylic acid or methacrylic acid and these esters is more preferred. Particularly, a copolymer of methacrylic acid and butyl acrylate is a particularly preferable compound having a large effect.

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, etc., and among them, a color photographic paper is preferable.
As the photographic support used in the present invention, a transmission type support or a reflection type support can be used. As the transmission type support, a transmission film such as a cellulose triacetate film or polyethylene terephthalate,
A material in which an information recording layer such as a magnetic layer is provided on a polyester of 6-naphthalenedicarboxylic acid (NDCA) and ethylene glycol (EG) or a polyester of NDCA, terephthalic acid and EG is 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,
A pyrazoline-based fluorescent whitening agent can be used, and a benzoxazolylnaphthalene-based or benzooxazolylstilbene-based fluorescent whitening agent is more preferable. Specific examples of the fluorescent whitening agent contained in the water-resistant resin layer include, for example, 4,4 ′
-Bis (benzoxazolyl) stilbene and 4,4'-
Bis (5-methylbenzoxazolyl) stilbene and a mixture thereof are exemplified. 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.

As the silver halide emulsion used in the present invention, silver chloro (iodide), silver chloro (iodo) bromide, silver (iodo) bromide emulsion and the like can be used. A silver chloride or silver chlorobromide emulsion having a silver content of 95 mol% or more is preferable, and a silver halide emulsion having a silver chloride content of 98 mol% or more is preferable. 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 reflective 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.

[0121]

[Table 1]

[0122]

[Table 2]

The cyan, magenta and yellow couplers used in the present invention include those described in
No. 2-215272, page 91, upper right column, line 4 to page 121, upper left column, line 6, JP-A-2-33144, page 3, upper right column, line 14 to page 18, upper left column, last line and page 30, upper right Lines 6 to 35, lower right column, line 11 and EP 0355, 660A2, page 4, lines 15 to 27, page 5, line 30 to page 28, last line, page 45, lines 29 to 31 Eyes, page 47, lines 23-6
The couplers described on page 3, line 50 are also useful.

As the antibacterial and antifungal agents that can be used 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.

In the case where 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 second harmonic generation light source (SHG) in which a gas laser, a light emitting diode, a semiconductor laser, a semiconductor laser or a solid laser using a semiconductor laser as an excitation light source is combined with 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.

In the case of using such a scanning exposure light source,
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. When the exposure time in such scanning exposure is defined as the exposure time for the pixel size when the pixel density is 400 dpi, a preferable 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, JP-A-8-2343.
No. 88, Japanese Patent Application No. 7-334190, 7-33419
The hydrazine-type compounds described in Nos. 2, 7-334197, and 7-344396 are preferable.

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 preferably used. In particular, it is preferable to use this method for the activator method. Specifically, Japanese Patent Application Laid-Open
An image forming method using an activator solution containing hydrogen peroxide described in Japanese Patent Application No. 297354/1997 and Japanese Patent Application No. 7-334202 is preferably used. In the activator method, after processing with an activator solution, usually a desilvering process is performed, but in an image amplification processing method using a low silver content photosensitive material,
The desilvering process can be omitted, and a simple method such as washing with water or stabilizing process can be performed. 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) pp. 536-541, JP-A-8
-234388 can be used.

[0133]

EXAMPLE 1 After a corona discharge treatment was applied to the surface of a support having both sides of a paper covered with polyethylene resin, a gelatin subbing layer containing sodium dodecylbenzenesulfonate was provided. To a seventh layer were sequentially coated to prepare a sample (000) of a silver halide color photographic light-sensitive material having the following layer structure. The coating solution for each photographic constituent layer was prepared as follows.

[Silver halide photographic light-sensitive material (photographic paper)
Preparation of (000)] Preparation of Coating Solution for Fifth Layer (Red-Sensitive Emulsion Layer) Cyan Coupler (Example Compound (1) of General Formula (I)) 1
00 g, cyan coupler (C-1) 12 g, cyan coupler (C-2) 50 g, color image stabilizer (Cpd-6) 62
g, color image stabilizer (Cpd-9) 38 g, color image stabilizer (C
pd-14) 12 g, color image stabilizer (Cpd-15) 11
0 g, 62 g of color image stabilizer (Cpd-16), 74 g of color image stabilizer (Cpd-17), color image stabilizer (Cpd-18)
74 g, 40 g of color image stabilizer (Cpd-19), solvent (S
olv-5) dissolved in 140 g of ethyl acetate and 350 ml of ethyl acetate.
The resulting mixture was emulsified and dispersed in 0 g to prepare an emulsified dispersion C.

[0135]

Embedded image

[0136]

Embedded image

On the other hand, silver chlorobromide emulsion C (cubic, 1: 4 mixture of large-size emulsion C with an average grain size of 0.50 μm and small-size emulsion C with an average grain size of 0.41 μm (silver molar ratio). The coefficients of variation 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).
This emulsion contains red-sensitive sensitizing dyes G and H shown below,
5. For large size emulsion C per mole of silver, respectively.
0 × 10 ^-5 mol and 9.0 × 10 ^-5 mol for small-size emulsion C were added. The 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 composition described below. The emulsion coating amount indicates a coating amount in terms of silver amount.

[0138]

Embedded image

The coating solutions for the first to fourth layers and the sixth to seventh layers were prepared in the same manner as the coating solution for the fifth layer. As a gelatin hardener for each layer, 1-oxy-3,5-dichloro-s-triazine sodium salt was used. Also, Ab-1, Ab-2 , Ab-3 and Ab-4 the total amount respectively 15.0 mg / m ² in each layer, 60.0mg / m ^2,
It was added to a 5.0 mg / m ² and 10.0 mg / m ^2.

[0140]

Embedded image

The following were used as the silver chlorobromide emulsion and the spectral sensitizing dye in each photosensitive emulsion layer. <Blue-sensitive emulsion layer> Silver chlorobromide emulsion A: cubic, average grain size 0.72 μm
3: 7 mixture of large size emulsion A of formula (1) and small size emulsion A of 0.60 μm (silver molar ratio). The coefficient of variation of the particle size distribution was 0.08 and 0.10. In each size emulsion, 0.3 mol% of silver bromide was contained locally on a part of the surface of the grain having silver chloride as a substrate.

Sensitizing dyes A, B and C are silver halide 1
Per mole, 1.4 × 1 for large emulsions
^0-4 moles, 1.7 × 1 each for small size emulsions
^0-4 moles were added.

[0143]

Embedded image

<Green-sensitive emulsion layer> Silver chlorobromide emulsion B: cubic, average grain size 0.45 μm
Of large-size emulsion B and small-size emulsion B of 0.35 μm
1: 3 mixture (silver molar ratio). Coefficient of variation of particle size distribution
Are 0.10 and 0.08, respectively. Brominated with each size emulsion
0.4 mol% of silver on part of the surface of silver chloride-based particles
It was contained locally. 1 mole of sensitizing dye D per silver halide
3.0 × 10 for large emulsions ^-FourMol, small sa
3.6 × 10 for size emulsion^-FourMol, also sensitizing color
Element E per mole of silver halide, per large size emulsion
Is 4.0 × 10^-Five7.0 for mole, small size emulsions
× 10^-FiveMoles of sensitizing dye F and 1 mole of silver halide.
2.0 × 10^-FourMole,
2.8 × 10 for small size emulsions^-FourMole was added.

[0145]

Embedded image

<Red-sensitive emulsion layer> Silver chlorobromide emulsion C: cubic, average grain size 0.50 μm
1: 4 mixture (large silver emulsion) of large size emulsion C and small size emulsion C of 0.41 μm. The variation coefficients of the particle size distribution are 0.09 and 0.11, respectively. In each size emulsion, 0.5 mol% of silver bromide was locally contained on a part of the surface of the silver chloride-based grain. Sensitizing dyes G and H were added to a large emulsion at 6.0 × / mol silver halide, respectively.
^10-5 mol, 9.0 × each for small size emulsions
10 ^-5 mol was added. Further, the following compound I was added to the red-sensitive emulsion layer in an amount of 2.6 × 10 ^-3 mol per mol of silver halide. )

[0147]

Embedded image

Further, a blue-sensitive emulsion layer, a green-sensitive emulsion layer and
1- (3-methylureidophenyl) was added to the red-sensitive emulsion layer.
) -5-mercaptotetrazole
3.3 × 10 per mole of silver halide^-FourMol, 1.0 × 10^-3
Mol and 5.9 × 10^-FourMole was added. Furthermore, the second
Layer (color mixture prevention layer), fourth layer (color mixture prevention layer), sixth layer (purple layer)
The outer line absorbing layer) and the seventh layer (protective layer)
0.2mg / m^Two0.2 mg / m ^Two, 0.6 mg / m
^Two0.1 mg / m^TwoWas added so that Also blue
4-hydroxy-sensitive emulsion layer and green-sensitive emulsion layer
-6-methyl-1,3,3a, 7-tetrazaindene
Of 1 × 10^-FourMo
2 × 10^-FourMole was added. In addition, the red sensitive emulsion layer
Copolymer of tacrylic acid and butyl acrylate (weight ratio 1:
1, average molecular weight 200,000 to 400,000) to 0.0
5g / m^TwoWas added. In addition, the second layer, the fourth layer and the
Catechol-3,5-disulfonate disodium in 6 layers
6 mg / m^Two, 6mg / m^Two, 18mg / m
^TwoWas added so that In addition, prevention of irradiation
For each emulsion layer, the following dyes (
) Was added.

[0149]

Embedded image

(Layer Structure) The structure of each layer is shown below. The numbers represent the coating amount (g / m ² ). The silver halide emulsion is
It represents the silver equivalent coating amount. Support Polyethylene resin laminated paper [A white pigment (TiO ₂ ;
Content 16% by weight, ZnO; content 4% by weight) and optical brighteners (4,4'-bis (benzoxazolyl) stilbene and 4,4'-bis (5-methylbenzoxazolyl)
8/2 mixture of stilbene: content 0.05% by weight),
Blue dye (ultramarine)] First layer (blue-sensitive emulsion layer) Silver chlorobromide emulsion A 0.26 Gelatin 1.35 Yellow coupler (ExY) 0.62 Color image stabilizer (Cpd-1) 08 Color image stabilizer (Cpd-2) 0.04 Color image stabilizer (Cpd-3) 0.08 Solvent (Solv-1) 0.23

[0151]

Embedded image

Second layer (color mixture prevention layer) Gelatin 0.99 Color mixture prevention agent (Cpd-4) 0.09 Color image stabilizer (Cpd-5) 0.018 Color image stabilizer (Cpd-6) 0.13 Color image stabilizer (Cpd-7) 0.01 Solvent (Solv-1) 0.06 Solvent (Solv-2) 0.22

[0153]

Embedded image

Third layer (green-sensitive emulsion layer) Silver chlorobromide emulsion B 0.14 Gelatin 1.36 Magenta coupler (ExM) 0.15 Ultraviolet absorber (UV-1) 0.05 Ultraviolet absorber (UV- 2) 0.03 UV absorber (UV-3) 0.02 UV absorber (UV-4) 0.04 Color image stabilizer (Cpd-2) 0.02 Color image stabilizer (Cpd-4) 002 Color image stabilizer (Cpd-6) 0.09 Color image stabilizer (Cpd-8) 0.02 Color image stabilizer (Cpd-9) 0.03 Color image stabilizer (Cpd-10) 0.01 colors Image stabilizer (Cpd-11) 0.0001 Solvent (Solv-3) 0.11 Solvent (Solv-4) 0.22 Solvent (Solv-5) 0.20

[0155]

Embedded image

[0156]

Embedded image

[0157]

Embedded image

Fourth layer (color mixture prevention layer) Gelatin 0.71 Color mixture prevention agent (Cpd-4) 0.06 Color image stabilizer (Cpd-5) 0.013 Color image stabilizer (Cpd-6) 0.10 Color image stabilizer (Cpd-7) 0.007 Solvent (Solv-1) 0.04 Solvent (Solv-2) 0.16

Fifth layer (red-sensitive emulsion layer) Silver chlorobromide emulsion C 0.11 Gelatin 1.16 Cyan coupler [Exemplary compound (1) of general formula (I)] 0.100 Cyan coupler C-10. 012 Cyan coupler C-2 0.050 Color image stabilizer (Cpd-6) 0.062 Color image stabilizer (Cpd-9) 0.038 Color image stabilizer (Cpd-14) 0.012 Color image stabilizer ( Cpd-15) 0.110 Color image stabilizer (Cpd-16) 0.062 Color image stabilizer (Cpd-17) 0.074 Color image stabilizer (Cpd-18) 0.074 Color image stabilizer (Cpd- 19) 0.040 Solvent (Solv-5) 0.140

Sixth layer (ultraviolet absorbing layer) Gelatin 0.66 Ultraviolet absorbing agent (UV-1) 0.19 Ultraviolet absorbing agent (UV-2) 0.06 Ultraviolet absorbing agent (UV-3) 0.06 Ultraviolet absorbing Agent (UV-4) 0.05 Ultraviolet absorber (UV-5) 0.09 Solvent (Solv-7) 0.25 Seventh layer (protective layer) Gelatin 1.00 Acrylic modified copolymer of polyvinyl alcohol (Modified) Degree 17%) 0.04 liquid paraffin 0.02 surfactant (Cpd-13) 0.01

[0161]

Embedded image

[Silver halide photographic light-sensitive material (photographic paper)
Preparation of (102) to (130)] In the preparation of the photographic paper (101), the cyan coupler of the exemplary compound (1) of the general formula (I) used in the red-sensitive emulsion of the fifth layer was replaced with the following Table 3. Using the described cyan coupler of the general formula (I),
The same as photographic paper (101), except that a red-sensitive emulsion to which a phenidone compound of the general formula (II) and a hydroquinone compound of the general formula (III) or (IV) were further added as shown in Table 3 below was used. And photographic paper (102-130)
Was prepared. The compounds of II-1, III-1 and IV-1 were added together with other additives in the step of dissolving in an organic solvent when preparing the above-mentioned emulsified dispersion of cyan coupler.

[0163]

[Table 3]

[0164]

[Table 4]

The photographic papers (101) to (130) processed into a roll having a width of 127 mm were converted into a minilab printer processor PP125 manufactured by Fuji Photo Film Co., Ltd.
After exposure using 8AR (see the following <Exposure conditions: <Measurement / evaluation method for cyan color density> and <Measurement / evaluation method for color mixture>), using a running liquid prepared as follows, After development, bleaching, fixing and stabilization, the measurement and evaluation of the cyan color density and the cyan mixed color density of the magenta color-developed portion were performed as described below. Processing Step Temperature Time Replenishment amount * Color development 38.5 ° C 45 seconds 45 ml Bleaching and fixing 38.0 ° C 45 seconds 35 ml Rinse (1) 38.0 ° C 20 seconds-Rinse (2) 38.0 ° C 20 seconds - rinse (3) ** 38.0 ℃ 20 seconds - rinse (4) ** 38.0 ℃ 30 seconds 121 ml * phosphorus replenishment rate ** Fuji Photo Film Co., Ltd. rinse cleaning system RC50D per photosensitive material 1 m ² The rinsing liquid is taken out of the rinse (3) and sent to the reverse osmosis membrane module (RC50D) by a pump. The permeated water obtained in the tank is supplied to the rinse (4), and the concentrated water is returned to the rinse (3). The pump pressure was adjusted so that the amount of permeated water to the reverse osmosis module was maintained at 50 to 300 ml / min, and the temperature was circulated for 10 hours a day. (Rinsing was carried out in a tank countercurrent system from (1) to (4).)

The composition of each processing solution is as follows. [Color developer] [Tank solution] [Replenisher] Water 800 ml 800 ml Dimethylpolysiloxane surfactant 0.1 g 0.1 g (Silicone KF351A / Shin-Etsu Chemical Co., Ltd.) Triethanolamine 11.6 g 11.6 g Ethylenediaminetetraacetic acid 4.0 g 4.0 g Sodium 4,5-dihydroxybenzene-1,3-disulfonic acid 0.5 g 0.5 g Potassium chloride 10.0 g-Potassium bromide 0.040 g 0.010 g Triazinylaminostilbene Fluorescence 2.5g 5.0g Brightener (Hakor FWA-SF / Showa Chemical Co., Ltd.) Sodium sulfite 0.1g 0.1g Disodium-N, N-bis (sulfonatoethyl) hydroxylamine 8.5g 11.1g N-ethyl-N- (β-methanesulfonamidoethyl ) -3-Methyl-4-amino-4-aminoaniline / 3/2 sulfuric acid monohydrate 5.0 g 15.7 g Potassium carbonate 26.3 g 26.3 g Water was added to the mixture, and 1000 ml 1000 ml pH (at 25 ° C.) / Adjusted with potassium hydroxide and sulfuric acid) 10.15 12.50

[Bleach-fixing solution] [Tank solution] [Replenisher] 800 ml of water 800 ml of ammonium iron (III) ethylenediaminetetraacetate 47.0 g 94.0 g 1.4 g of ethylenediaminetetraacetic acid 2.8 g m-carboxymethylbenzene full Finic acid 8.3 g 16.5 g Nitric acid (67%) 16.5 g 33.0 g Imidazole 14.6 g 29.2 g Ammonium thiosulfate (750 g / l) 107.0 ml 214.0 ml ammonium sulfite 16.0 g 32.0 g meta Potassium bisulfite 23.1 g 46.2 g Water was added to 1000 ml 1000 ml pH (adjusted at 25 ° C./acetic acid and ammonia) 6.0 6.0

[Rinse solution] [Tank solution] [Replenisher] Deionized water (conductivity of 5 μs / cm or less) 1000 ml 1000 ml pH 6.5 6.5 Chlorinated sodium isocyanurate 0.02 g 0.02 g

The photographic paper was exposed and exposed as follows.
Processing such as development was performed, and the measurement and evaluation of cyan color density and color mixture were performed. <Method for Measuring and Evaluating Cyan Color Density> The photographic paper (10
1) to (130) were subjected to gradation exposure with red light, and then processed with the above-mentioned running liquid. Next, the color density of these photographic papers was measured with red light (645 nm, half-width 30 nm). The maximum color density of each sample was read from the sensitometric curve, and the results are shown in the table. <Method of Measuring and Evaluating Color Mixing> -Cyan Color Mixing in Magenta Coloring Portion- The photographic papers (101) to (130) were subjected to gradation exposure with green light, and then processed with the running liquid. Then, these photographic papers were irradiated with red light (645 nm, half width 3).
0 nm) and green light (545 nm, half-width 30 nm)
And the cyan and magenta color density were measured. The cyan color density (red light density) at the exposure amount where the magenta color density (green light density) was 2.0 was read from the sensitometric curve, and is shown in Table 4 as an evaluation value of color mixing. The lower the color mixture value is, the smaller the cyan color mixture in the magenta coloring portion is, and the higher the color purity is.

[0170]

[Table 5]

[0171]

[Table 6]

As is clear from Table 4, the samples (101), (123) and (127) which do not contain the phenidone compound and the hydroquinone compound of the present invention have a large color mixture and are not preferable in color reproduction. On the other hand, it can be seen from the comparison between the sample and Samples (102) to (105) that the color mixing is greatly improved when the phenidone compound of the present invention is used. However, in the samples (104) and (105) in which the added amount was increased in order to obtain a sufficient effect of preventing color mixture, the color density was reduced. Especially (105)
Then, the decrease in the concentration is large. On the other hand, in (106) and (107) using only the hydroquinone compound of the present invention, the effect of preventing color mixture is observed, but the effect is not so large. However, the sample (108) using both of them together
In (112), a remarkably large effect of preventing color mixing is observed. In addition, in these samples, little decrease in color density is observed. Similar effects are observed in other samples using the phenidone compound and the hydroquinone compound of the present invention in combination. As described above, by using the phenidone compound and the hydroquinone compound of the present invention in combination,
The cyan color mixture in the magenta portion can be reduced without lowering the cyan color density. In addition, this makes it possible to provide a tourist material having excellent color reproducibility and color developability.

Claims (1)

[Claims] 1. A yellow-sensitive photosensitive halogen on a support.
Silver halide emulsion layer, magenta coloring photosensitive silver halide emulsion layer
And cyan-sensitive photosensitive silver halide emulsion layers
A non-color-forming parent that has at least one layer each and is not photosensitive
Silver halide powder having at least one aqueous colloid layer
In the color photographic light-sensitive material, the cyan coloring photosensitive halo is used.
At least one silver halide emulsion layer has the following general formula (I)
A cyan dye-forming coupler selected from the compounds represented by
And at least one compound represented by the following general formula (II)
And a compound represented by the following general formula (III) or (IV)
Silver halide color photograph characterized by containing
Photosensitive material. Embedded imageEmbedded imageEmbedded imageEmbedded imageIn the formula (I), Z^a, Z^bIs -C (R^Three) = Again
Represents -N =. Where Z^a, Z^bIs either-
N = and the other is -C (R^Three) =. R¹And R
^TwoMeans that the Hammett's substituent constant σp value is 0.20, respectively.
Represents the above electron withdrawing group, and¹And R^TwoSum of the σp values of
Is 0.65 or more. R^ThreeRepresents a hydrogen atom or a substituent
Represent. X is a hydrogen atom or an aromatic primary amine color
Decoupled in the coupling reaction of the developing agent with the oxidized form
Represents a group. R¹, R^Two, R^ThreeOr, the group of X is divalent
And bond to multimers and polymer chains
A homopolymer or a copolymer may be formed. Formula (II)
Medium, R^a1, R^a2Are each independently a hydrogen atom, an alkyl group,
Or an aryl group. R^a3, R^a4Is a hydrogen atom,
Represents an aryl group or an aryl group. R^a5Represents an aryl group
You. Where R^a1, R^a2, R^a3, R^a4And R^a5Carbon
The sum of the numbers cannot be less than 13. In the formula (III),
X¹Is a hydroxyl group, an alkoxy group, or NHR^FourBase
Represents Y¹Represents a group that can be substituted on a benzene ring. l is
Represents an integer of 0 to 4, and when l is 2 or more, a plurality of Y
¹May be the same or different groups. R^Four
Represents a hydrogen atom, an alkyl group, an aryl group, an acyl group,
Honyl group, carbamoyl group, sulfamoyl group, or
Represents a alkoxycarbonyl group. In the formula (IV), X ^TwoHa
Droxy group, alkoxy group or NHR^FourRepresents a group. Y^Two
Represents a group that can be substituted on a benzene ring. m is 0 to 4
Represents an integer, and when l is 2 or more, ^TwoIs the same group
Or different groups. R^FourIs a hydrogen atom,
Alkyl group, aryl group, acyl group, sulfonyl group,
Rubamoyl group, sulfamoyl group, or alkoxycal
Represents a bonyl group.