JPH08297351A - Silver halide color photographic sensitive material and color image forming method - Google Patents

Abstract

PURPOSE: To ensure high yellow and cyan developing properties, to prevent the change of a yellow developed part into a cyan part even after storage at a high humidity and to suppress the increase of the cyan stain of an unexposed part by combining a specified yellow coupler with a specified cyan coupler. CONSTITUTION: This photographic sensitive material contains a yellow coupler represented by formula I in a silver halide emulsion layer contg. a yellow dye forming coupler and a cyan coupler represented by formula II in a silver halide emulsion layer contg. a cyan dye forming coupler. In the formula I, R is a tert. alkyl, tert. cycloalkyl, etc., X is a group which is released by a reaction with a color developing agent, Y is a halogen, alkoxy, etc., and Z is a substituent such as -NHCOR<1> or -NHCOR<2> (R<1> is an alkenyl, etc., and R<2> is an alkyl, etc.). In the formula II, R<21> is an aliphatic group, an arom. group, etc., R<22> is an aliphatic group or acylamino, R<23> is H, a halogen, an aliphatic group, etc., and Z<21> is H or a group or atom which can be released at the time of coupling.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a silver halide color photographic light-sensitive material, and more particularly to a silver halide color photographic light-sensitive material excellent in color developability and image stability.

[0002]

The most commonly used color image forming method in silver halide color photographic light-sensitive materials is to oxidize an aromatic primary amine type color developing agent with exposed silver halide as an oxidizing agent. Then, the oxidized aromatic primary amine type color developing agent is reacted with the coupler to form indophenol, indoaniline, indamine, azomethine, phenoxazine, phenazine and dyes similar thereto. In such a method, a method of reproducing a color image by a subtractive color method is used.
Generally, a color image is formed by changing the amount of yellow, magenta, and cyan dyes produced. Of these, pivaloyl-type couplers and benzoyl-type couplers have been conventionally used as yellow couplers. However, these yellow couplers have a lower activity of the coupler and a lower molecular extinction coefficient of the dye molecule produced, as compared with the pyrazolotriazole coupler used as the magenta coupler and the phenol coupler used as the cyan coupler. The amount of couplers used was inevitably high, which was a problem in terms of economy. Furthermore, it becomes difficult to reduce the thickness of the yellow color forming layer, which is an obstacle to further speeding up of processing and low replenishment.

As an attempt to increase the extinction coefficient of the dye molecule produced, for example, European Patent EP04479 is used.
69A1 has an acylacetanilide type coupler having a 3- to 5-membered cyclic acyl group, and European Patent EP 048255.
No. 2A1 proposes a malondianilide type coupler having a cyclic structure. On the other hand, many attempts have been made to increase the color density by increasing the activity of the coupler. Among them, one means is to improve the activity of the coupler by increasing the hydrophilicity of the coupler. For example, a coupler having an oxazolidin-2,4-dione-3-yl group or a 1,2, triazolidin-3,5-dione-4-yl group introduced as a leaving group is disclosed in, for example, JP-A-50-132926. 62-206549, 63-291056 and the like. Further, examples of couplers having an imidazolidin-2,4-dione-3-yl group introduced therein are disclosed in JP-A-3-126939 and JP-A-3-126.
No. 940 and No. 3-126941.

On the other hand, as a cyan coupler, a phenol type coupler has been conventionally used, particularly in a light-sensitive material for observation, from the viewpoints of color forming property, color image fastness of the color forming dye, and spectral absorption property of the color forming dye. When using these cyan couplers and the above-mentioned yellow couplers having increased activity, if the light-sensitive material after color development is stored for a long time in a high humidity condition, the yellow color development part remarkably changes to cyan color. A point arose.

[0005]

The present invention has been made under the circumstances described above. Therefore, an object of the present invention is to use a phenol type cyan coupler excellent in color forming property, color image fastness of the color forming dye, and spectral absorption property of the color forming dye, so that the yellow color forming portion can be obtained even when stored under high humidity conditions. It is an object of the present invention to provide a light-sensitive material which does not discolor to cyan, which suppresses an increase in cyan stain in an uncolored portion, and which is excellent in yellow coloring.

[0006]

The above objects of the present invention have been achieved by the following silver halide color photographic light-sensitive materials. That is, (1) a halogen having at least one yellow dye-forming coupler-containing silver halide emulsion layer, magenta dye-forming coupler-containing silver halide emulsion layer, and cyan dye-forming coupler-containing silver halide emulsion layer on the support. In a silver halide color photographic light-sensitive material, a silver halide emulsion layer containing a yellow dye-forming coupler has the following general formula (Y-
I) containing at least one yellow coupler, and a cyan dye-forming coupler-containing silver halide emulsion layer containing at least one cyan coupler represented by the following general formula (CI). And a silver halide color photographic light-sensitive material. General formula (Y-I)

[0007]

[Chemical 6]

(In the general formula (Y-I), R is a tertiary alkyl group, a tertiary cycloalkyl group, an aliphatic heterocyclic group,
Represents an aromatic group, and X represents a group which leaves upon reaction with a color developing agent. Y represents a halogen atom, an alkoxy group, an aryloxy group, an acyloxy group, a dialkylamino group or an alkyl group, and Z represents a substituent represented by any one of the following general formulas (A) to (H). Substituents (A) to (H)

[0009]

[Chemical 7]

(In the general formula (A), R ¹ represents an alkenyl group, a halogenated alkyl group or a halogenated alkenyl group. In the general formula (B), R ² represents an alkyl group, a cycloalkyl group, an alkenyl group or an aryl group. In the general formula (C), L ₁ represents an alkylene group, R ³ represents an alkyl group, a cycloalkyl group, an alkenyl group or an aryl group.
⁴ and R ⁵ each independently represent an alkyl group, a cycloalkyl group, an aryl group, an alkoxy group, an aryloxy group or an anilino group. In the general formula (E), L ₂
Represents an alkylene group, and R ⁶ represents an alkyl group or an aryl group. In the general formula (F), L ₃ is an alkylene group,
R ⁷ represents an alkyl group or an aryl group. In the general formula (G), L ₄ represents an alkylene group, R ⁸ represents a hydrogen atom, an alkyl group or an aryl group, and R ⁹ represents an alkyl group or an aryl group. In the general formula (H), L
₅ represents an alkylene group, and R ¹⁰ and R ¹¹ each independently represent a hydrogen atom, an alkyl group, or an aryl group. ) General formula (CI)

[0011]

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(In the general formula (CI), R ²¹ represents an aliphatic group, an aromatic group, a heterocyclic group or an aromatic or heterocyclic amino group, and R ²² represents an aliphatic group or an acylamino group, R ²³ represents a hydrogen atom, a halogen atom, an aliphatic group, an aliphatic oxy group or an acylamino group, Z ²¹ represents a hydrogen atom or a group or atom capable of splitting off upon coupling, R ²²
And R ²³ may form a 5- to 7-membered ring. (2) The silver halide color as described in (1), wherein the cyan coupler represented by the general formula (CI) is further represented by the general formula (C-II) or (C-III). Photographic material. General formula (C-II)

[0013]

[Chemical 9]

General formula (C-III)

[0015]

[Chemical 10]

(In the general formula (C-II), R ²⁴ represents an aliphatic group having 2 to 20 carbon atoms. In the general formulas (C-II) and (C-III), R ²¹ represents an aliphatic group. , An aromatic group, a heterocyclic group or an aromatic or heterocyclic amino group, R ²⁵ represents an acylamino group having 1 to 20 carbon atoms, R ²³ represents a hydrogen atom, a halogen atom, an aliphatic group, an aliphatic oxy group. Or an acylamino group, Z ²¹ represents a hydrogen atom or a group or atom capable of splitting off upon coupling, and R ²³ and R ²⁴ or R ²³
And R ²⁵ may form a 5- to 7-membered ring. )

The cyan coupler used in the present invention has a high color forming property, a good color image fastness of a color forming dye, and a good spectral absorption property of the color forming dye. There is a problem that the color changes to a color and cyan stain occurs in the unexposed area. On the other hand, when the yellow coupler used in the present invention is used, it is possible to reduce the cyan discoloration and the cyan stain of the yellow color-developing portion even when the above-mentioned cyan coupler is used, while maintaining the high coloring property of yellow. You can get the unexpected effect that you can. Further, when the cyan coupler represented by the general formula (C-II) or (C-III) is used as the cyan coupler, it is possible to further effectively reduce the cyan discoloration and the cyan stain in the yellow colored portion.

The yellow coupler represented by formula (Y-I) will be described in detail below. General formula (Y-I)
In the formula, R is a tertiary alkyl group having 4 to 28 carbon atoms, a 3 to 7 membered tertiary cycloalkyl group having 4 to 28 carbon atoms, and a fat containing 3 to 7 membered oxygen atom, nitrogen atom, sulfur atom or phosphorus atom. It represents a group heterocyclic group or an aromatic group having 6 to 36 carbon atoms. Specific examples of the group represented by R are shown below.

[0019]

[Chemical 11]

In the general formula (Y-I), X may be any group as long as it is a group capable of splitting off upon coupling with a color developing agent. For example, a group bonded to the active site of the coupling reaction by a nitrogen atom ( Hindantoin group, 1,3-oxazolidine-2,5-dione group, urazole group, parabanic acid group, succinimido group, phthalimido group, pyrazole group, imidazole group, triazole group, etc.); group bonded by oxygen atom (alkoxy group, Aryloxy group, acyloxy group, alkoxycarbonyloxy group, carbamate group and the like); groups bonded by a sulfur atom (alkylthio group, arylthio group, halogen atom and the like). Specific examples of the coupling-off group represented by X are shown below.

[0021]

[Chemical 12]

[0022]

[Chemical 13]

In the general formula (Y-I), Y is a halogen atom (fluorine atom, chlorine atom, bromine atom, iodine atom),
Preferably an alkoxy group having 1 to 24 carbon atoms (eg, methoxy group, ethoxy group, n-butoxy group, i-propoxy group, t-butoxy group, octyloxy group, methoxyethoxy group, butoxyethoxy group, trifluoroethoxy group). , Benzyloxy group, hexadecyloxy group, etc.),
Preferably, an aryloxy group having 6 to 30 carbon atoms (for example, phenoxy group, 4-methylphenoxy group, 3-chlorophenoxy group, 4-tert-butylphenoxy group,
2,4-di-tert-amylphenoxy group, β-naphthoxy group, etc.), preferably an acyloxy group having 2 to 28 carbon atoms (eg, acetyl group, propanoyl group, butanoyl group, benzoyl group, cyclohexanoyl group), Preferably, a dialkylamino group having 2 to 36 carbon atoms (eg, dimethylamino group, diethylamino group, dibutylamino group, dioctylamino group, piperazino group, morpholino group, etc.), preferably alkyl group having 1 to 24 carbon atoms ( For example, a methyl group, an ethyl group, an i-propyl group, a trifluoromethyl group, etc.) are represented. In the substituent (A) in Z, R ₁ preferably represents an alkenyl group having 2 to 25 carbon atoms, a halogenated alkyl group or a halogenated alkenyl group. Specifically, oleyl, linoleic, ricinoleic, undecenyl, linolenic, arachidonic, eicosa Bae Ntaeniru, docosahexaenoyl _{enyl, - (CH 2) 11 -CH} = CH-C
₈ H ₁₇ ,-(CH ₂ ) ₇ -CBr = CH-C ₈ H ₁₇ ,-(CH ₂ ) ₇ CCl = CH-C
₈ H ₁₇ ,-(CH ₂ ) ₇ -CH = CBrC ₈ H ₁₇ ,-(CH ₂ ) ₇ CH = CCl-C ₈ H
_{17, - (CH 2) 7} CCl-CClC 8 H 17, - (CH 2) 7 CBr-CBrC 8 H
_{17 and the} like. In the substituent (B), R ₂
Is preferably an alkyl group having 1 to 28 carbon atoms, a cycloalkyl group, an alkenyl group or preferably 6 to 36 carbon atoms.
Represents an aryl group. Specific examples include methyl, ethyl, heptyl, tridecyl, pentadecyl, heptadecyl, 2-ethylhexyl, 2-hexyldecyl, cyclohexyl, 2-methylcyclohexyl, 4-t-butylcyclohexyl, oleyl, 4-t-butylphenyl,
3-pentadecylphenyl and the like can be mentioned. In the substituent (C), L ₁ preferably has 1 to 10 carbon atoms in the chain portion.
4 represents an alkylene group having a total carbon number of 1 to 28, specifically, methylene group, ethylide group, propylidene group, butylidene group, octylidene group, dodecylidene group, 1,1-dimethylmethylene group, ethylene group, propylene group, Butylene group, 1-methylethylene group, 1-ethylethylene group, 2
-Methylethylene group, 1,1-dimethylethylene group,
Examples include 1,2-dimethylethylene group. R ₃ is preferably an alkyl group having 1 to 25 carbon atoms, an alkenyl group, a cycloalkyl group, or preferably 6 to 2 carbon atoms.
6 represents an aryl group, specifically, methyl group, ethyl group, propyl group, t-butyl group, heptyl group, 1-hexyl-nonyl group, 1- (1,3,3-trimethylbutyl) -4, 6,6-Trimethylheptyl group, cyclohexyl group, 4-t-butylcyclohexyl group, 2,6-dimethylcyclohexyl group, oleyl group, allyl group, benzyl group, 4-t-butylphenyl group, 3-pentadecylphenyl Group, 2,4-dichlorophenyl group, 2-chloro-4-t-amylphenyl group and the like. In the substituent (D), R ⁴ and R ⁵ are each independently preferably an alkyl group or an alkoxy group having 1 to 26 carbon atoms, preferably an aryl group or aryloxy group having 6 to 30 carbon atoms, preferably 1 to 1 carbon atoms. 26 alkylamino groups,
It represents a dialkylamino group or an anilino group. R ⁴ and R ⁵ may be the same or different groups. Specific examples of R ⁴ and R ⁵ include methyl group, ethyl group, propyl group, butyl group, hexyl group, octyl group, dodecyl group, hexadecyl group, 2-ethyl-hexyl group, 2-hexyl-decyl group, 3 , 5,5-trimethylhexyl group, cyclohexyl group, 2-methylcyclohexyl group, oleyl group,
Phenyl group, toluyl group, xylyl group, isopropylphenyl group, butoxy group, hexyloxy group, octyloxy group, 2-ethylhexyloxy group, 2-hexyldecyloxy group, 3,5,5-trimethylhexyloxy group, cyclohexyloxy Group, 2-methylcyclohexyloxy group, methoxyethoxy group, oleyloxy group,
Phenoxy group, 3-methylphenoxy group, 4-methylphenoxy group, 3-isopropylphenoxy group, 4-t-
Examples thereof include a butylphenoxy group, a dodecylamino group, a hexadecylamino group, a diethylamino group, a dibutylamino group, a dioctylamino group, an N-methyldodecylamino group, an anilino group, and an N-methylanilino group. L ₂ in the substituents (E), (F), (G), and (H),
L ₃ , L ₄ and L ₅ have the same meaning as L ₁ of the substituent (C), and specific examples thereof include the same groups as those mentioned for L ₁ . Further, R ⁶ and R ⁷ preferably have 1 to 1 carbon atoms.
It represents an alkyl group having 28 or preferably an aryl group having 6 to 36 carbon atoms, and specific examples thereof include the groups exemplified for R ² of the substituent (B). In the substituent (G), R ⁸ represents a hydrogen atom, preferably an alkyl group having 1 to 28 carbon atoms, or preferably an aryl group having 6 to 36 carbon atoms. Specific examples of the alkyl group include a methyl group, an ethyl group, an isopropyl group, a butyl group, a t-butyl group, an octyl group, a dodecyl group, a hexadecyl group, a 2-ethylhexyl group and a cyclohexyl group. Specific examples of the aryl group include phenyl group, 3-methylphenyl group, 4-methoxyphenyl group, 2,4-dichlorophenyl group, 4-t-
A butylphenyl group and the like can be mentioned. R ⁹ has the same meaning as R ³ of the substituent (C), and specific examples thereof include the groups mentioned for R ³ . In the substituent (H), R ¹⁰ and R ¹¹ each independently represent a hydrogen atom, preferably an alkyl group having 1 to 24 carbon atoms or preferably an aryl group having 6 to 30 carbon atoms. Specific examples thereof include the groups mentioned for R ⁸ of the substituent (G).

The preferred structure of the yellow coupler represented by formula (Y-I) is described in detail below.
In the general formula (Y-I), R preferably has 4 to 4 carbon atoms.
20, more preferably a 4 to 8 tertiary alkyl group, a C 4 to 20 (more preferably 4 to 8) 3- to 6-membered tertiary cycloalkyl group, a 5- to 6-membered oxygen-containing tertiary. An aliphatic heterocyclic group, a heterocyclic group containing a 5- to 6-membered nitrogen atom,
Alternatively, it is a phenyl group which may have a substituent. R
Is more preferably as Pivaloyl group, 1-alkylcyclopropyl group, 1-alkylcyclopentyl group, 1-
Alkylcyclohexyl group, 3-alkyloxolane-
3-yl group, 5-alkyl-1,3-dioxan-5-
An yl group, a pyrrolidin-1-yl group and an indolinyl group. Most preferred as R are pivaloyl group, 1-methylcyclopropyl group, 1-ethylcyclopropyl group,
1-benzylcyclopropyl group, 1-ethylcyclopentyl group and indolinyl group. Y is preferably a halogen atom or an alkoxy group, more preferably a chlorine atom or a methoxy group, and most preferably a chlorine atom. X
Is preferably a coupling-off group bonded to the coupling active position with a nitrogen atom or an oxygen atom, and more preferably a group represented by the following general formula (XI).

[0025]

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In the general formula (X-I), Q is a group of divalent non-metal atoms necessary for forming a 5- or 6-membered ring with an imide residue, and in addition to carbon atoms, oxygen atoms, nitrogen atoms, Heteroatoms such as sulfur and phosphorus atoms can be included in the ring. More preferred as X is the general formula (X-I
Groups represented by I), (X-III), (X-IV) and (X-V).

[0027]

[Chemical 15]

In the general formula (X-II), R ¹ and R ²
Each independently represent a hydrogen atom or an alkyl group.
Each of R ¹ and R ² is preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, more preferably one is a methyl group, and further preferably both are methyl groups. In formula (X-III), R ³ represents a hydrogen atom, an alkyl group, an aryl group, an acyl group, an alkylsulfonyl group or an arylsulfonyl group. R ⁴ and R ⁵ each represent a hydrogen atom, an alkyl group, an alkoxy group, an aryl group, an aryloxy group, an alkylsulfonyl group, or an arylsulfonyl group. R ³ is preferably a hydrogen atom, an alkyl group, an alkylsulfonyl group or an arylsulfonyl group, more preferably a hydrogen atom or an alkyl group. A hydrogen atom is particularly preferred as R ³ . R ⁴ and R ⁵ are preferably a hydrogen atom, an alkyl group or an alkoxy group. R ³ , R ⁴ and R ⁵
When is an alkyl group or an alkoxy group, it preferably has 1 to 4 carbon atoms. Also R ³ , R ⁴ and R
Preferably when the sum of carbon numbers of ⁵ is 5 or less, more preferably when it is 4 or less. In the general formula (X-IV), R ⁶ and R ⁷ represent groups having the same meaning as R ³ in the general formula (X-III). Preferred as R ⁶ and R ⁷ is a hydrogen atom, an alkyl group or an aryl group. In formula (X-V) R ⁸ represents a group having the same meaning as R ³ in the general formula (X-III). R ⁸ is preferably a hydrogen atom, an alkyl group or an aryl group. When X is bonded to the coupling active position by an oxygen atom, X
Is preferably an aryloxy group, an acyloxy group or a sulfonyloxy group, and among them, an aryloxy group is more preferable. Further, the 2- or 4-position of the aryloxy group
An aryloxy group having a polarized group such as a sulfonyl group, a sulfamoyl group, a carbamoyl group, an alkoxycarbonyl group, a sulfonamide group, and an acyl group at the position is more preferable.

In the general formula (Y-I), Y is preferably a halogen atom, an alkoxy group or an aryloxy group, more preferably a chlorine atom or an alkoxy group, still more preferably a chlorine atom or a methoxy group. Most preferred is a chlorine atom. The substituent represented by Z in formula (Y-I) is represented by (A) to (H). Of these, R ¹ of the substituent (A) is preferably a halogenated alkenyl group having 13 to 21 carbon atoms, an alkenyl group, or a halogenated alkyl group, and more preferably 15 to 19 carbon atoms.
The halogenated alkyl and halogenated alkenyl groups preferably have 1 or 2 halogen atoms to be substituted, and the halogen atom is preferably a chlorine atom or a bromine atom, more preferably a chlorine atom. R ¹ is more preferably an alkenyl group, and most preferably an alkenyl group forming an oleic acid amide group as the substituent (A).

In the substituent (B), R ² is preferably an alkyl group having 12 to 22 carbon atoms or an aryl group, and more preferably an alkyl group or aryl group having 14 to 20 carbon atoms. More preferably, R ² has 14 carbon atoms.
-20 straight-chain or branched alkyl groups, with branched alkyl groups being more preferred. Particularly, an alkyl group branched at the β-position is more preferable.

In the substituent (C), L ₁ is preferably a substituted or unsubstituted alkylene group, and a substituted or unsubstituted methylene group, ethylene group, propylene group,
It is a butylene group, more preferably a substituted or unsubstituted methylene group, an ethylene group or a propylene group, and further preferably a substituted or unsubstituted methylene group. Among them, a methylene group substituted with an alkyl group or an ethylene group is more preferable, and a methylene group substituted with an alkyl group having 1 to 18 carbon atoms is further preferable. R ³
Is preferably an alkyl group having 1 to 21 carbon atoms or an aryl group, and more preferably an alkyl group having 1 to 17 carbon atoms. As the alkyl group, a linear alkyl group is preferable in terms of color developability, and a branched alkyl group is preferable in terms of fastness. The total carbon number of L ₁ and R ³ is preferably 1
The range is 2 to 24, more preferably 14 to 22, and further preferably 16 to 20.

In the substituent (D), R ⁴ and R ⁵ are each independently preferably an alkyl group or alkoxy group having 1 to 20 carbon atoms, and an aryl group or aryloxy group having 6 to 20 carbon atoms. The alkyl group may be linear or branched, but linear alkyl is preferable from the viewpoint of color developability, and branched alkyl is preferable from the viewpoint of fastness. The aryl group is preferably a substituted or unsubstituted aryl group, but when it is a substituted aryl, the substituent is preferably a chlorine atom, an alkyl group or an alkoxy group. R ⁴ and R ⁵ may be the same or different, but are preferably the same from the viewpoint of ease of synthesis. The total carbon number of R ⁴ and R ⁵ is preferably 12 to 32, more preferably 14 to 28, and further preferably 16 to 24. Further, R ⁴ and R ⁵ may combine with each other to form a ring.

In the substituent (E), L ₂ is a substituent (C)
Represents the same group as L ₁ and preferred examples are also the same as L ₁ . R ⁶ represents the same group as R ² of the substituent (B), and the preferred group is also the same as R ² . The total carbon number of L ₂ and R ⁶ is preferably 12 to 24, more preferably 14 to 2
2, more preferably 16 to 20.

In the substituent (F), L ₃ is the substituent (C)
Represents the same group as L ₁ and R ⁷ represents the same group as R ² of the substituent (B). Further, preferred groups are L ₁ and R ² respectively.
Is the same group as. The total carbon number of L ₃ and R ⁷ is preferably 12 to 24, more preferably 14 to 22, and further preferably 16 to 20.

In the substituent (G), L ₄ is a substituent (C)
Represents the same group as L ₁ and preferred substituents are the same groups as L ₁ . R ⁸ preferably represents a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, or an aryl group having 6 to 20 carbon atoms, and more preferably a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or an alkyl group having 6 to 12 carbon atoms. It is an aryl group. R ⁸
Is more preferably a hydrogen atom, a methyl group, an ethyl group, a propyl group, a butyl group or a phenyl group, and a hydrogen atom, a methyl group or a phenyl group is most preferable. R ⁹ has the same meaning as R ³ of the substituent (C), and the preferred examples are also the same. The total carbon number of L ₄ , R ⁸ and R ⁹ is preferably in the range of 12 to 28, more preferably 14 to 24, still more preferably 16 to 20.

In the substituent (H), L ₅ is a substituent (C)
Represents the same group as L ₁ and the examples of preferable groups are also the same.
R ¹⁰ is preferably a hydrogen atom, an alkyl group having 1 to 20 carbon atoms or an aryl group, and more preferably a hydrogen atom, an alkyl group having 1 to 12 carbon atoms or a phenyl group.
R ¹¹ is preferably an alkyl group having 8 to 20 carbon atoms.
The total carbon number of L ₅ , R ¹⁰ and R ¹¹ is preferably 12
The range is from 28 to 28, more preferably from 14 to 24, still more preferably from 16 to 20. As the substituent represented by Z, the substituent represented by the substituents (A), (B), (C) or (D) is more preferable, and the substituent represented by (C) or (D) is More preferable. Specific examples of the yellow coupler represented by formula (Y-I) are shown below, but the coupler of the present invention is not limited to these couplers.

[0037]

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[0038]

[Chemical 17]

[0039]

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[0040]

[Chemical 19]

[0041]

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[0042]

[Chemical 21]

[0043]

[Chemical formula 22]

[0044]

[Chemical formula 23]

[0045]

[Chemical formula 24]

[0046]

[Chemical 25]

[0047]

[Chemical formula 26]

[0048]

[Chemical 27]

[0049]

[Chemical 28]

[0050]

[Chemical 29]

[0051]

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[0052]

[Chemical 31]

[0053]

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[0054]

[Chemical 33]

[0055]

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[0056]

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[0057]

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[0058]

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[0059]

[Chemical 38]

[0060]

[Chemical Formula 39]

[0061]

[Chemical 40]

[0062]

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[0063]

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[0064]

[Chemical 43]

The cyan coupler represented by formula (C-1) will be described in detail below. R ²¹ is preferably an aliphatic group having 1 to 36 carbon atoms, preferably an aromatic group having 6 to 36 carbon atoms (eg, phenyl group, naphthyl group, etc.), heterocyclic group (eg, 3-pyridyl group, 2- Furyl group) or an aromatic or heterocyclic amino group (eg, anilino group, naphthylamino group, 2-benzothiazolylamino group, 2-pyridylamino group, etc.), and these groups are each further an alkyl group. , Aryl groups, heterocyclic groups, alkoxy groups (eg, methoxy group, 2-methoxyethoxy group, etc.), aryloxy groups (eg, 2,4-di-t)
ert-amylphenoxy group, 2-chlorophenoxy group, 4-cyanophenoxy group etc.), alkenyloxy group (eg 2-propenyloxy group etc.), acyl group (eg acetyl group, benzoyl group etc.), ester group ( For example, butoxycarbonyl group, phenoxycarbonyl group, acetoxy group, benzoyloxy group, butoxysulfonyl group, toluenesulfonyloxy group, etc.), amide group (for example, acetylamino group, ethylcarbamoyl group, dimethylcarbamoyl group, methanesulfonamide group, Butylsulfamoyl group), a sulfamide group (eg, dipropylsulfamoylamino group),
Imide group (eg, succinimide group, hydantoinyl group, etc.), ureido group (eg, phenylureido group,
Dimethylureido group, etc.), aliphatic or aromatic sulfonyl group (eg, methanesulfonyl group, phenylsulfonyl group, etc.), aliphatic or aromatic thio group (eg, ethylthio group, phenylthio group, etc.), hydroxy group, cyano group, It may be substituted with a group selected from a carboxy group, a nitro group, a sulfo group, a halogen atom and the like.
As used herein, the term "aliphatic group" refers to a linear, branched or cyclic aliphatic hydrocarbon group, and includes saturated and unsaturated groups such as alkyl, alkenyl, and alkynyl groups. Typical examples thereof are methyl group, ethyl group, butyl group, dodecyl group, octadecyl group, eicosenyl group, iso-propyl group, tert-butyl group, t
ert-octyl group, tert-dodecyl group, cyclohexyl group, cyclopentyl group, allyl group, vinyl group, 2
-Hexadecenyl group, propargyl group and the like. R ²² preferably represents an acylamino group having 1 to 20 carbon atoms or an aliphatic group, and may be substituted with a substituent allowed for R ²¹ . R ²³ is a hydrogen atom, a halogen atom (for example, a fluorine atom, a chlorine atom, a bromine atom), preferably an aliphatic group having 1 to 20 carbon atoms, preferably an aliphatic oxy group having 1 to 20 carbon atoms, or preferably An acylamino group having 1 to 20 carbon atoms (eg, acetamide group, benzamide group, tetradecanamide group, etc.), and these aliphatic groups, aliphatic oxy groups, and acylamino groups are substituted with substituents allowed by R ^21. You may have. R ²³ is preferably a halogen atom or an acylamino group, more preferably a halogen atom, and particularly preferably a chlorine atom. Z
²¹ represents a hydrogen atom or a coupling-off group, and examples thereof include a halogen atom (eg, fluorine atom, chlorine atom, bromine atom), an alkoxy group (eg, ethoxy group, dodecyloxy group, methoxyethylcarbamoyl). Methoxy group, carboxypropyloxy group, methylsulfonylethoxy group, etc.), aryloxy group (eg, 4-chlorophenoxy group, 4-methoxyphenoxy group, 4-carboxyphenoxy group, etc.), acyloxy group (eg, acetoxy group, tetra Decanoyloxy group, benzoyloxy group, etc.), sulfonyloxy group (eg, methanesulfonyloxy group, toluenesulfonyloxy group, etc.), amide group (eg, dichloroacetylamino group, heptafluorobutyrylamino group, methanesulfonylamino group) , Ruenesulfonylamino group), alkoxycarbonyloxy group (eg, ethoxycarbonyloxy group, benzyloxycarbonyloxy group, etc.), aryloxycarbonyloxy group (eg, phenoxycarbonyloxy group), aliphatic or aromatic thio group ( For example, ethylthio group, phenylthio group, tetrazolylthio group, etc., imide group (for example,
Succinimide group, hydantoinyl group, etc.), aromatic azo group (eg, phenylazo group, etc.) and the like. These leaving groups may include photographically useful groups. R
A group of any one of ²¹ , R ^{23 and} Z ²¹ may independently or jointly form a dimer or higher multimeric coupler. In the case of a dimer, those groups are used as a mere bond or a divalent linking group (for example, a divalent group such as an alkylene group, an arylene group, an ether group, an ester group, an amide group, or a divalent group combining these groups). (E.g., a valent group) and when forming an oligomer or polymer, those groups are preferably the polymer backbone or are attached to the polymer backbone through a divalent group as described for dimers. . When forming a polymer, even if it is a homopolymer of a coupler derivative, another non-color-forming ethylene-like monomer (for example, acrylic acid, methacrylic acid, methyl n-butyl acrylate acrylate, β-hydroxymethacrylate, vinyl acetate, Acrylonitrile, styrene, crotonic acid, maleic anhydride, N-vinylpyrrolidone, etc.), and one or more of them may form a copolymer. Preferable R ²¹ is a substituted or unsubstituted alkyl group or aryl group, and as the substituent of the alkyl group, a phenoxy group which may be substituted and a halogen atom are particularly preferable (the alkyl group is a substituent of the phenoxy group). , Alkoxy group, halogen atom, sulfonamide group,
The sulfamide group is more preferable), and the aryl group is particularly preferably a phenyl group substituted with at least one halogen atom, an alkyl group, a sulfonamide group or an acylamino group.

Preferable R ²² has 1 to 1 carbon atoms which may be substituted.
20 acylamino groups or alkyl groups. From the viewpoint of reducing cyan discoloration and cyan stain in the yellow colored portion, an acylamino group having 1 to 20 carbon atoms or 2 carbon atoms
Alkyl groups having 20 to 20 carbon atoms are preferable, and alkyl groups having 2 to 20 carbon atoms are most preferable from the viewpoint that the yellow coupler of the present invention has a large effect of improving cyan discoloration and cyan stain. R ²² when R ²² is an alkyl group is preferably unsubstituted, but a R ²² is an acylamino group, when substituted, the substituent alkyl group, an aryloxy group, an acylamino group, an alkylthio group, An arylthio group, an imide group, a ureido group, an alkylsulfonyl group and an arylsulfonyl group are preferable.

In formula (C-II), R ²⁴ is preferably an alkyl group having 2 to 10 carbon atoms, and particularly preferably an alkyl group having 2 to 4 carbon atoms. In formula (C-III), R ²⁵ is preferably an unsubstituted acylamino group, or an acylamino group substituted with an alkoxy group, an aryloxy group, an alkylthio group, or an arylthio group, and particularly, an unsubstituted acylamino group or an alkoxy group. Alternatively, an acylamino group substituted with an aryloxy group is particularly preferable. Further, in the case of an unsubstituted acylamino group, an alkylcarbonylamino group is preferable, and a group in which this alkyl group is a branched alkyl group is particularly preferable. General formula (C-1)
In, it is also preferable that R ²² is an alkyl group and R ²³ is an acylamino group, and these are linked to form a 5- or 6-membered ring. Specific examples of the cyan coupler represented by formula (C-1) are shown below, but the coupler of the present invention is not limited to these couplers.

[0068]

[Chemical 44]

[0069]

Embedded image

[0070]

Embedded image

[0071]

[Chemical 47]

[0072]

Embedded image

[0073]

[Chemical 49]

[0074]

Embedded image

The preferred amounts of yellow couplers and cyan couplers represented by formulas (Y-I) and (C-1) of the present invention in a silver halide color photographic light-sensitive material are 0.01 to 10 millimolar each. The range is m ² , more preferably 0.05 to 5 mmol / m ² , and most preferably 0.1 to ² mmol / m ² . Of course, the couplers represented by the general formulas (Y-I) and (C-1) may be used in combination of two or more kinds. The coupler used at this time may be a coupler other than the couplers represented by formulas (Y-I) and (C-1). In this case, the usage rate of the coupler of the present invention is preferably 50 mol% or more. If the amount of the yellow coupler or cyan coupler of the present invention used is less than 0.01 mmol / m ^2, it is difficult to obtain the required color density, and if it exceeds 10 mmol / m ² , it is not preferable in terms of cost. The preferred amount of the silver halide emulsion in the silver halide emulsion layer in which the coupler of the present invention is used is the silver mole conversion based on the coupler,
It is 0.5 to 50 times, more preferably 1 to 20 times, and most preferably 2 to 10 times.

The coupler used in the present invention can be introduced into the light-sensitive material by various known dispersion methods. Among them, it is dissolved in a high-boiling organic solvent (a low-boiling organic solvent is optionally used in combination) and emulsified and dispersed in a gelatin aqueous solution. The oil-in-water dispersion method of adding to a silver halide emulsion is preferred. The high boiling organic solvent used in the present invention is a compound immiscible with water having a melting point of 100 ° C. or lower and a boiling point of 140 ° C. or higher, and any solvent that is a good coupler can be used. The melting point of the high boiling point organic solvent is preferably 80 ° C. or lower. The boiling point of the high-boiling organic solvent is preferably 160
℃ or more, more preferably 170 ℃ or more. For details of these high boiling point organic solvents, see JP-A-62-
JP-A-215272, page 137, lower right column to 144
It is described in the upper right column of the page. In the present invention, the amount of the high boiling point organic solvent used may be any amount, but the high boiling point organic solvent / coupler ratio is preferably 20 or less in weight ratio to the coupler, and 0.02 to 5 is preferable. More preferable. A known polymer dispersion method may be used in the present invention. The steps, effects, and specific examples of the latex for impregnation as a latex dispersion method as one of the polymer dispersion methods are described in US Pat. No. 4,199,363 and West German Patent Application (OLS).
No. 2,541,274, No. 2,541,230, Japanese Examined Patent Publication No. 53-41091, and European Patent Publication No. 0291.
No. 04, etc., and the dispersion method using a water-insoluble polymer and an organic solvent-soluble polymer is described in PCT International Publication No. WO88 / 00723.

The average particle size of the lipophilic fine particles containing the coupler used in the present invention is not particularly limited, but it is preferably 0.05 to 0.3 μm from the viewpoint of color developability,
0.05 μm to 0.2 μm is more preferable. Generally, in order to reduce the average particle size of lipophilic fine particles, selection of the type of surfactant, increasing the amount of surfactant used, increasing the viscosity of the hydrophilic colloid solution, and increasing the lipophilic organic layer This can be achieved by lowering the viscosity by using a low boiling point organic solvent in combination, increasing the shearing force such as increasing the rotation of the stirring blade of the emulsifying device, or increasing the emulsification time. The particle size of the lipophilic fine particles can be measured, for example, by a device such as Nanosizer manufactured by Coulter Co. of England. The color light-sensitive material of the present invention is constituted by coating at least one yellow color-forming silver halide emulsion layer, magenta color-forming silver halide emulsion layer and cyan color-forming silver halide emulsion layer on a support. In general color photographic paper, color reproduction by the subtractive method can be performed by including a color coupler which forms a dye having a complementary color relationship with the light to which the silver halide emulsion is exposed. In a general color photographic paper, silver halide emulsion grains are spectrally sensitized by the blue-sensitive, green-sensitive and red-sensitive spectral sensitizing dyes in the order of the color-forming layers described above, and on the support in the order described above. It can be constructed by coating. Further, the light-sensitive layer and the color-developing hue may not have the above correspondence, and at least one infrared-sensitive silver halide emulsion layer can be used.

The support used in the present invention may be any support which can be coated with a photographic emulsion layer such as glass, paper and plastic film, but a reflection type support is most preferred. The "reflective support" used in the present invention refers to one which enhances the reflectivity to make the dye image formed on the silver halide emulsion layer clear, and such a reflective support is a support. Those coated with a hydrophobic resin containing a light-reflecting substance such as titanium oxide, zinc oxide, calcium carbonate, or calcium sulfate dispersed therein, or those using the hydrophobic resin itself containing a dispersed light-reflecting substance as a support. Is included. For example, polyethylene-coated paper, polyethylene-terephthalate-coated paper, polypropylene-based synthetic paper, a transparent support provided with a reflective layer, or using a reflective substance together,
Examples thereof include glass plates, polyethylene terephthalate, polyester films of cellulose triacetate or cellulose nitrate, polyamide films, polycarbonate films, polystyrene films, vinyl chloride resins and the like.

The reflection type support used in the present invention is
A paper support whose both surfaces are coated with a water resistant resin layer, wherein at least one of the water resistant resin layers contains white pigment fine particles is preferable. The white pigment particles are preferably contained at a density of 12% by weight or more, more preferably 14% by weight.
It is more than weight%. As the light-reflecting white pigment particles, it is preferable to sufficiently knead the white pigment in the presence of a surfactant, and it is preferable to use pigment particles whose surfaces are treated with a divalent to tetravalent alcohol. It is preferable that the white pigment fine particles are uniformly dispersed in the reflective layer without forming an aggregate of particles, and the size of the distribution depends on the occupied area ratio (%) (Ri) of the fine particles projected on a unit area. It can be measured and obtained. The variation coefficient of the occupied area ratio (%) can be obtained by the ratio s / R of the standard deviation s of Ri to the average value (R) of Ri. In the present invention,
The coefficient of variation of the occupied area ratio (%) of the fine particles of the pigment is 0.1
It is preferably 5 or less, more preferably 0.12 or less. 0.08 or less is particularly preferable.

In the present invention, a support having a surface of diffuse reflection of the second kind can be preferably used. The second-class diffuse reflectivity was obtained by giving unevenness to a surface having a mirror surface and dividing it into fine mirror surfaces facing different directions, and dispersing the directions of the divided fine surfaces (mirror surface). Refers to diffuse reflectivity. The unevenness of the surface of the second type diffuse reflection has a three-dimensional average roughness of 0.1 to 2 μ relative to the center plane.
m, preferably 0.1 to 1.2 μm. The frequency of unevenness on the surface is 0.1 for unevenness with a roughness of 0.1 μm or more.
It is preferably ˜2000 cycles / mm, more preferably 50-600 cycles / mm.
For details of such a support, see JP-A-2-239.
No. 244.

In the present invention, the silver halide grains are 9
It is preferable to use silver chlorobromide, silver chloroiodobromide, or silver chloride grains in which 5 mol% or more is silver chloride. In particular, in the present invention, in order to accelerate the development processing time, a silver chlorobromide or silver chloride containing substantially no silver iodide can be preferably used. The term "substantially free of silver iodide" as used herein means that the silver iodide content is 1 mol% or less, preferably 0.2 mol% or less. On the other hand, for the purpose of enhancing high illuminance sensitivity, spectral sensitization sensitivity, or enhancing stability over time of a light-sensitive material, 0.01 to 3 mol% on the emulsion surface as described in JP-A-3-84545. In some cases, high silver chloride grains containing silver iodide are preferably used. The halogen composition of the emulsion may be different or the same between grains, but if an emulsion having the same halogen composition among grains is used, it is easy to make the properties of each grain uniform. Regarding the halogen composition distribution inside the silver halide emulsion grains, the so-called uniform structure grains having the same composition in any part of the silver halide grains, or the core inside the silver halide grains and the shell surrounding it. (shell)
Particles having a so-called laminated structure having a different halogen composition with [one or more layers], or a structure having a portion having a different halogen composition in a non-layer form inside or on the surface of the particle (edges, corners or surfaces of the particles when present on the surface of the particle) Particles having a structure in which portions having different compositions are bonded to each other can be appropriately selected and used. In order to obtain high sensitivity, it is advantageous to use either of the latter two rather than the particles having a uniform structure, and it is also preferable from the viewpoint of pressure resistance. When the silver halide grains have the structure as described above, the boundary between different portions in the halogen composition is an unclear boundary because a mixed crystal is formed due to the composition difference even if the boundary is clear. It may also be one that positively has a continuous structural change.

The high silver chloride emulsion used in the present invention preferably has a structure having a localized silver bromide phase in the inside and / or on the surface of the silver halide grain in the form of layer or non-layer as described above. The halogen composition of the localized phase preferably has a silver bromide content of at least 10 mol%, more preferably more than 20 mol%. The silver bromide content of the silver bromide localized layer is analyzed using an X-ray diffraction method (for example, described in “Chemical Society of Japan, New Experimental Chemistry Lecture 6, Structural Analysis” Maruzen). can do. And these localized phases are the inside of the particle, the edge of the particle surface,
It can be on a corner or on a surface, but one preferred example is one that is epitaxially grown on the corner of the grain. It is also effective to further increase the silver chloride content of the silver halide emulsion for the purpose of reducing the replenishment amount of the developing solution. In such a case, an almost pure silver chloride emulsion having a silver chloride content of 98 mol% to 100 mol% is also preferably used.

The average grain size of the silver halide grains contained in the silver halide emulsion used in the present invention (the grain size is defined by the diameter of the circle equivalent to the projected area of the grain and the number average thereof is taken) is 0. 1 μm to 2 μm is preferable. Further, the particle size distribution thereof is preferably a so-called monodisperse coefficient of variation of 20% or less (standard deviation of particle size distribution divided by average particle size), preferably 15% or less, more preferably 10% or less. . At this time, for the purpose of obtaining a wide latitude, it is also preferable to use the above monodispersed emulsion by blending it in the same layer, or to perform multi-layer coating.

The shape of silver halide grains contained in a photographic emulsion is irregular, such as cubic, tetradecahedral or octahedral, having a regular crystal form, spherical, tabular or the like. Those having an irregular crystal form, or those having a composite form thereof can be used.
It may also be a mixture of materials having various crystal forms. In the present invention, it is preferable that 50% or more, preferably 70% or more, and more preferably 90% or more of the particles having the above-mentioned regular crystal form are contained in the present invention. In addition to these, an emulsion in which tabular grains having an average aspect ratio (diameter in terms of circle / thickness) of 5 or more, preferably 8 or more exceeds 50% of all grains as a projected area can also be preferably used.

The silver (bromide) bromide emulsion used in the present invention is described in P. G.
Chimie et Phisique Photographique (Paul by lafkides
Montel, 1967), GF Duffin Photogr
aphic Emulsion Chemistry (Published by Focal Press, 196
6 years), VL Zelikman et al Making and Coating P
hotographic Emulsion (Focal Press, 1964
Year)). That is, any of an acidic method, a neutral method, an ammonia method and the like may be used, and as a form of reacting the soluble silver salt and the soluble halogen salt, any method such as a one-sided mixing method, a simultaneous mixing method, and a combination thereof may be used. You may use. It is also possible to use a method of forming grains in an atmosphere in which silver ions are excessive (so-called reverse mixing method). As one form of the simultaneous mixing method, a method of keeping pAg in a liquid phase where silver halide is formed constant, that is, a so-called controlled double jet method can be used. According to this method, a silver halide emulsion having a regular crystal form and a nearly uniform grain size can be obtained.

The localized phase of the silver halide grain of the present invention or its substrate preferably contains a different metal ion or a complex ion thereof. The preferred metal is selected from metal ions or metal complexes belonging to Group VIII and Group IIb of the Periodic Table, and lead ions and thallium ions. Ions or their complex ions mainly selected from iridium, rhodium, iron etc. in the localized phase, and metal ions selected mainly from osmium, iridium, rhodium, platinum, ruthenium, palladium, cobalt, nickel, iron etc. as the substrate. Alternatively, the complex ions can be used in combination. Further, the type and concentration of the metal ion can be changed depending on the localized phase and the substrate. Plural kinds of these metals may be used. In particular, iron and iridium compounds are preferably present in the silver bromide localized phase.

These metal ion-providing compounds are used in a gelatin aqueous solution which becomes a dispersion medium when silver halide grains are formed,
Of the silver halide grains of the present invention by means such as adding in an aqueous solution of a halide, in an aqueous solution of silver salt or other aqueous solution, or in the form of silver halide fine particles containing metal ions in advance and dissolving the fine particles. It is contained in the localized phase and / or other particle portion (matrix). The metal ions used in the present invention can be contained in the emulsion grains either before, during or immediately after grain formation. This can be changed depending on the position of the metal ion contained in the particle.

The silver halide emulsion used in the present invention is:
Usually, it is chemically and spectrally sensitized. Regarding the chemical sensitization method, chemical sensitization using a chalcogen sensitizer (specifically, sulfur sensitization represented by the addition of an unstable sulfur compound, selenium sensitization with a selenium compound, tellurium sensitization with a tellurium compound is performed. Noble metal sensitization typified by gold sensitization, reduction sensitization and the like can be used alone or in combination. As the compound used for the chemical sensitization, those described in JP-A-62-215272, page 18, lower right column to page 22, upper right column are preferably used. The effect of the constitution of the light-sensitive material of the present invention is more remarkable than when the gold-sensitized high silver chloride emulsion is used. The emulsion used in the present invention is a so-called surface latent image type emulsion in which a latent image is mainly formed on the grain surface.

The silver halide emulsion used in the present invention includes various compounds or precursors thereof for the purpose of preventing fog during the production process of the light-sensitive material, storage or photographic processing, or stabilizing photographic performance. Can be added. Specific examples of these compounds are described in JP-A-62-2.
Those described on pages 39 to 72 of the specification of Japanese Patent No. 15272 are preferably used. Further European patent EP 0447
5-arylamino-1,2,
A 3,4-thiatriazole compound (having at least one electron-withdrawing group in the aryl residue) is also preferably used.

Spectral sensitization is carried out for the purpose of imparting spectral sensitivity in a desired light wavelength region to the emulsion of each layer in the photographic material of the present invention. In the light-sensitive material of the present invention, blue, green,
Examples of spectral sensitizing dyes used for spectral sensitization in the red region include, for example, Heterocyclic compounds-Cyanin by FM Harmer.
e dyes and related compounds (John Wiley & Sons
[New York, London] 1964). As specific examples of compounds and spectral sensitization methods, those described in JP-A-62-215272, page 22, upper right column to page 38 are preferably used. Further, as a red-sensitive spectral sensitizing dye for silver halide emulsion grains having a particularly high silver chloride content, JP-A No. 3/1999
The spectral sensitizing dye described in JP-A-123340 is stable,
It is very preferable from the viewpoint of the strength of adsorption, the temperature dependence of exposure and the like.

When the light-sensitive material of the present invention is efficiently spectrally sensitized in the infrared region, JP-A-3-15049, page 12, upper left column to page 21, lower left column, or JP-A-3-20730, page 4, lower left column to page 15 Lower left column, European patent EP 0,420,
011 page 4, line 21 to page 6, line 54, European patent EP 0,4
20,012, page 4, line 12 to page 10, line 33, European patent E
P0,443,466, US Pat. No. 4,975,3
The sensitizing dye described in No. 62 is preferably used.

To incorporate these spectral sensitizing dyes in a silver halide emulsion, they may be dispersed directly in the emulsion, or water, methanol, ethanol, propanol, methyl cellosolve, 2,2,2. It may be added to the emulsion by dissolving it in a solvent such as 3,3-tetrafluoropropanol alone or in a mixed solvent. Also, Japanese Patent Publication No.
No. 3389, No. 4427555, No. 57-2208
As described in US Pat. No. 3,822,135, US Pat.
As described in No. 5, etc., an aqueous solution or a colloidal dispersion in which a surfactant coexists may be added to the emulsion. Further, after being dissolved in a solvent which is substantially immiscible with water, such as phenoxyethanol, it may be dispersed in water or a hydrophilic colloid and added to the emulsion. JP-A-53-10
Alternatively, the dispersion may be directly dispersed in a hydrophilic colloid as described in Nos. 2733 and 58-105141, and the dispersion may be added to the emulsion. The time of addition to the emulsion may be any stage of emulsion preparation known to be useful so far. In other words, before grain formation of silver halide emulsion,
It can be selected from during grain formation, immediately after grain formation, before entering the washing step, before chemical sensitization, during chemical sensitization, immediately after chemical sensitization, until cooling and solidification of the emulsion, and during preparation of the coating solution. Most commonly, it is performed after the completion of chemical sensitization and before coating. However, as described in US Pat. Nos. 3,628,969 and 4,225,666, the chemical sensitizer is added at the same time as the spectral sensitization. The sensitization can be carried out simultaneously with the chemical sensitization, or can be carried out prior to the chemical sensitization as described in JP-A-58-113928, and it can be added before the completion of silver halide grain precipitation formation. Spectral sensitization can also be started. Furthermore, US Pat. No. 42256
It is also possible to add the spectral sensitizing dyes separately as taught in No. 66, i.e. partly prior to chemical sensitization and the rest after chemical sensitization.
It can be at any time during silver halide grain formation, including the method taught in U.S. Pat. No. 4,183,756. Of these, it is particularly preferable to add a sensitizing dye before the step of washing the emulsion with water or before the chemical sensitization.

The addition amount of these spectral sensitizing dyes is wide depending on the case and is 0.5 per mol of silver halide.
The range of × 10 ^-6 mol to 1.0 × 10 ^-2 mol is preferable.
More preferably, 1.0 × 10 ^-6 mol to 5.0 × 10 ^-3
It is in the molar range. In the present invention, particularly when a sensitizing dye having a spectral sensitizing sensitivity in the red region to the infrared region is used, the compounds described in JP-A-2-157749, page 13, lower right column to page 22, lower right column, may be used in combination. preferable. By using these compounds, the storability and processing stability of the light-sensitive material and the supersensitizing effect can be specifically enhanced. Above all, it is particularly preferable to use the compounds of the general formulas (IV), (V) and (VI) in the same patent in combination. These compounds are used in an amount of 0.5 × 10 ^-5 mol to 1 mol of silver halide.
5.0 × 10 ⁻² mol, preferably 5.0 × 10 ⁻⁵ mol
An amount of 5.0 × 10 ⁻³ mol is used, and 0.1 times to 10000 times, preferably 0.5 times to 5 times per mol of the sensitizing dye.
There is an advantageous usage amount in the range of 000 times.

The light-sensitive material of the present invention is used not only in a printing system using a general negative printer but also in a solid state laser using a gas laser, a light emitting diode, a semiconductor laser, a semiconductor laser or a semiconductor laser as an excitation light source, and a nonlinear laser. It is preferably used for digital scanning exposure using monochromatic high-density light such as a second harmonic generation light source (SHG) combined with an optical crystal. Compact system,
In order to make it inexpensive, it is preferable to use a semiconductor laser, or a second harmonic generation light source (SHG) that is a combination of a semiconductor laser or a solid-state laser and a nonlinear optical crystal. In particular, in order to design an apparatus which is compact, inexpensive, has a long life and high stability, it is preferable to use a semiconductor laser, and it is desirable to use a semiconductor laser as at least one of the exposure light sources.

When using such a scanning exposure light source,
The spectral sensitivity maximum of the light-sensitive material of the present invention can be arbitrarily set according to the wavelength of the scanning exposure light source used. A solid-state laser using a semiconductor laser as an excitation light source or an SHG obtained by combining a semiconductor laser and a nonlinear optical crystal
In the light source, the oscillation wavelength of the laser can be halved, so that blue light and green light can be obtained. Therefore, the spectral sensitivity maximum of the light-sensitive material can be provided in the normal three regions of blue, green and red. In order to use a semiconductor laser as a light source in order to make the device inexpensive, highly stable and compact, it is preferable that at least two layers have a spectral sensitivity maximum at 670 nm or more. This is because currently available inexpensive and stable III-V semiconductor lasers have emission wavelengths only in the red to infrared regions. However, at the laboratory level, the oscillation of II-VI group semiconductor lasers in the green and blue regions has been confirmed, and if semiconductor laser manufacturing technology is developed, these semiconductor lasers can be used inexpensively and stably. It is fully expected. In such a case, at least two layers are 670 nm
As described above, the necessity of having the maximum spectral sensitivity is reduced.

In such scanning exposure, the time for which the silver halide in the light-sensitive material is exposed is the time required for exposing a certain minute area. As this minute area, the minimum unit for controlling the light quantity from each digital data is generally used and is called a pixel. Therefore, the exposure time per pixel changes depending on the size of this pixel. The size of this pixel depends on the pixel density and is in a practical range of 50 to 2000 dpi. When the exposure time is defined as the time for exposing the pixel size when the pixel density is 400 dpi, the preferable exposure time is 10 ^-4 seconds or less, more preferably 10 ^-6 seconds or less.

In the light-sensitive material of the present invention, a hydrophilic colloid layer is used for the purpose of preventing irradiation and halation and improving safety of safelight. It is preferable to add the dyes described above, which can be decolorized by the treatment (in particular, oxonol dyes and cyanine dyes). Some of these water-soluble dyes deteriorate the color separation and safelight safety when the amount used is increased. As a dye that can be used without deteriorating color separation, Japanese Patent Application No. 03-310
No. 143, Japanese Patent Application No. 03-310189, Japanese Patent Application No. 03-
Water-soluble dyes described in 310139 are preferred.

In the present invention, a colored layer which can be decolorized by treatment is used instead of the water-soluble dye or in combination with the water-soluble dye. The coloring layer that can be decolorized by the treatment used may be in direct contact with the emulsion layer, or may be disposed so as to be in contact with the emulsion layer via an intermediate layer containing a treatment color mixing inhibitor such as gelatin or hydroquinone. This colored layer is preferably provided in the lower layer (support side) of the emulsion layer that develops a primary color of the same kind as the colored color. It is possible to install all the colored layers corresponding to each primary color individually, or to selectively install only a part of them. It is also possible to provide a colored layer that is colored corresponding to a plurality of primary color gamuts. The optical reflection density of the colored layer is in the wavelength range used for exposure (from 400 nm to 70 in normal printer exposure).
In the visible light region of 0 nm, the wavelength of the scanning exposure light source used in the case of scanning exposure), the optical density value at the wavelength having the highest optical density is preferably 0.2 or more and 3.0 or less. It is more preferably 0.5 or more and 2.5 or less, and particularly preferably 0.8 or more and 2.0 or less.

A conventionally known method can be applied to form the colored layer. For example, Japanese Patent Laid-Open No. 2-282244-3
The dyes described on page 8 from the upper right column of the page, and JP-A-3-79
No. 31, page 3, upper right column to page 11, lower left column, a method of incorporating a solid fine particle dispersion in a hydrophilic colloid layer, a method of mordanting an anionic dye with a cationic polymer, a method of halogenating the dye Examples thereof include a method of adsorbing to fine particles such as silver and fixing in a layer, a method of using colloidal silver as described in JP-A-1-239544, and the like. As a method for dispersing a fine powder of a pigment in a solid state, for example, a method of containing a fine powder dye which is substantially water-insoluble at a pH of 6 or lower but is substantially water-soluble at a pH of 8 or higher is disclosed in Japanese Patent Laid-Open No. 2-30824
No. 4, pages 4-13. Also, for example,
A method of mordanting an anionic dye on a cationic polymer is described in JP-A-2-84637, pages 18 to 26. For the preparation method of colloidal silver as a light absorber, see US Pat. Nos. 2,688,601 and 3,45.
No. 9,563. Among these methods, the method of incorporating a fine powder dye and the method of using colloidal silver are preferable.

As the binder or protective colloid that can be used in the light-sensitive material of the present invention, it is advantageous to use gelatin, but other hydrophilic colloids can be used alone or together with gelatin. Preferred gelatin has a calcium content of 800 p
It is preferable to use low calcium gelatin of pm or less, more preferably 200 ppm or less. Further, in order to prevent various molds and bacteria which propagate in the hydrophilic colloid layer and deteriorate the image, it is preferable to add an antifungal agent as described in JP-A-63-271247.

When the light-sensitive material of the present invention is exposed to a printer, it is preferable to use the band stop filter described in US Pat. No. 4,880,726. As a result, light color mixture is removed, and color reproducibility is significantly improved. The exposed light-sensitive material can be subjected to a conventional color development process, but in the case of the color light-sensitive material of the present invention, it is preferable to perform bleach-fixing after color development for the purpose of rapid processing.
Particularly when the above high silver chloride emulsion is used, the pH of the bleach-fixing solution is preferably about 6.5 or less, more preferably about 6 or less for the purpose of promoting desilvering. Silver halide emulsions and other materials (additives etc.) and photographic constituent layers (layer arrangement etc.) applied to the light-sensitive material according to the present invention, and processing methods and processings applied for processing the light-sensitive material. As additives, the following patent publications, particularly European patent EP 0,35
Those described in the specification of 5,660A2 (JP-A-2-139544) are preferably used.

[0102]

[Table 1]

[0103]

[Table 2]

[0104]

[Table 3]

[0105]

[Table 4]

[0106]

[Table 5]

In the light-sensitive material of the present invention, it is preferable to use a color image storability-improving compound as described in European Patent EP 0,277,589A2 together with a coupler. In particular, it is preferably used in combination with a pyrazoloazole coupler, a pyrrolotriazole coupler, or an acylacetamide type yellow coupler. That is, the compound and / or the color development treatment in the above-mentioned European Patent Specification which chemically bonds with an aromatic amine-based developing agent remaining after the color development treatment to form a chemically inactive and substantially colorless compound. Use of the compounds in the above-mentioned European patent specification simultaneously or alone to form a chemically inert and substantially colorless compound by chemically bonding with an oxidized product of an aromatic amine type color developing agent which remains afterwards. However, it is preferable to prevent the occurrence of stains and other side effects due to the formation of a coloring dye due to the reaction of the residual color developing agent in the film or the oxidant thereof with the coupler during storage after processing. Further, as the cyan coupler which can be used in combination with the cyan coupler of the present invention, in addition to the naphthol type couplers described in the above-mentioned publicly known documents, diphenylimidazole type cyan couplers described in JP-A-2-33144. European patent EP 0333185A
2-hydroxypyridine type cyan couplers described in JP-A No. 2-42, cyclic active methylene type cyan couplers described in JP-A-64-32260, and European Patent EP045.
6226A1 specification, pyrrolopyrazole type cyan coupler, European Patent EP 0484909, pyrrolo imidazole type cyan coupler, European Patent EP04
Preference is given to using the pyrrolotriazole type cyan couplers described in 88248 and EP 0491197A1. Of these, use of a pyrrolotriazole type cyan coupler is particularly preferable.

Examples of magenta couplers include 5-pyrazolone type magenta couplers and pyrazoloazole type couplers as described in the above-mentioned table. Examples of 5-pyrazolone magenta couplers include WO92 / 18901 and WO92 / 18902.
5-pyrazolone-based magenta couplers capable of releasing arylthio described in JP-A No. 9/18903 and WO 92/18903 are preferable in terms of image storability and little change in image quality due to processing. As the pyrazoloazole-based magenta coupler, a known pyrazoloazole-type coupler is used in the present invention, and among them, in view of hue, image stability, color developability, etc., JP-A-61-2524.
A pyrazolotriazole coupler in which a secondary or tertiary alkyl group as described in JP-A No. 5 is directly linked to the 2, 3 or 6 position of the pyrazolotriazole ring, JP-A-61-65246.
Pyrazoloazole coupler containing a sulfamide group in the molecule as described in JP-A-61-1425.
Pyrazoloazole couplers having an alkoxyphenyl sulfonamide ballast group as described in JP-A-4, EP-A-226,849A and EP-A-294,785A.
It is preferable to use a pyrazoloazole coupler having an alkoxy group or an aryloxy group at the 6-position as described in No.

Known acylacetanilide type couplers are preferably used as the yellow coupler which can be used in combination with the yellow coupler of the present invention. Among them, a pivaloylacetanilide type coupler having a halogen atom or an alkoxy group at the ortho position of the anilide ring is preferably used. Coupler, European Patent EP0
447969A, JP-A-5-107701, JP-A-5-113642 and the like, acylacetanilide type couplers in which the acyl group is a cycloalkanecarbonyl group substituted at the 1-position, European Patent EP-0482552A and EP E
The malondianilide type couplers described in P-0524540A and the like are preferably used. As the method for processing the color light-sensitive material of the present invention, in addition to the method described in the above table, JP-A-2-207250, page 26, lower right column, line 1 to page 34, upper right column, line 9 and JP-A-4-207250. 97355, page 5, upper left column 17
The processing materials and processing methods described in line 20 to the lower right column, line 20 on page 18 are preferable.

[0110]

EXAMPLES The present invention will be specifically described below with reference to examples, but of course the present invention is not limited thereto. Example 1 A surface of a paper support laminated on both sides with polyethylene was subjected to a corona discharge treatment, and then a gelatin subbing layer containing sodium dodecylbenzenesulfonate was provided, and various photographic constituent layers were further coated to form the layers shown below. A multilayer color photographic paper (100) having the constitution was produced. The coating liquid was prepared as follows.

Preparation of coating solution for first layer Yellow coupler (ExY-1) 122.0 g, color image stabilizer (Cpd-1) 15.4 g, color image stabilizer (Cpd-
2) 7.5 g, color image stabilizer (Cpd-3) 16.7 g
Of the solvent (Solv-1) 44 g and ethyl acetate 180
10% sodium dodecylbenzenesulfonate (86 cc) and citric acid (10 g)
Emulsified dispersion A was prepared by emulsifying and dispersing in 1000 g of gelatin aqueous solution. On the other hand, a silver chlorobromide emulsion A (cubic, 3: 7 mixture of a large size emulsion having an average grain size of 0.88 μm and a small size emulsion of 0.70 μm (silver molar ratio). The variation coefficient of grain size distribution is 0. .08 and 0.10, 0.3 mol% of silver bromide was locally contained in a part of the surface of the grain based on silver chloride, and hexachloroiridium was contained in the grain and in the silver bromide localized phase. 0.1 mg of potassium (IV) was combined, and 1.0 mg of potassium ferrocyanide was combined. This emulsion is
The blue-sensitive sensitizing dyes A, B and C shown below are each 8.0 × 10 ⁻⁵ for a large size emulsion per mol of silver.
1.0 × for moles and small emulsions
10 ⁻⁴ mol is added. The chemical ripening of this emulsion was optimally performed by adding a sulfur sensitizer and a gold sensitizer.
The above emulsified dispersion A and this silver chlorobromide emulsion A were mixed and dissolved to prepare a coating solution for the first layer having the following composition. The emulsion coating amount indicates a coating amount equivalent to silver.

Coating solutions for the second to seventh layers were prepared in the same manner as the coating solution for the first layer. 1-Oxy-3,5-dichloro-s-triazine sodium salt was used as a gelatin hardening agent for each layer. In addition, Cpd-12 and Cp are added to each layer.
the total amount d-13, Cpd-14 and Cpd-15, respectively is ^{15.0mg / m 2, 60.0mg / m} 2, was added to a 5.0 mg / m ² and 10.0 mg / m ^2. The size of the silver chlorobromide emulsion in each light-sensitive emulsion layer was adjusted by the same preparation method as for the silver chlorobromide emulsion A, and the following spectral sensitizing dyes were used. Blue-sensitive emulsion layer

[0113]

[Chemical 51]

Green-sensitive emulsion layer

[0115]

Embedded image

(Sensitizing dye D per mol of silver halide was 3.0 × 10 ^-4 mol for a large-sized emulsion, 3.6 × 10 ^-4 mol for a small-sized emulsion, and Sensitizing dye E per mol of silver halide is 4.0 × 10 ⁻⁵ mol for large-sized emulsion, 7.0 × 10 ⁻⁵ mol for small-sized emulsion, and sensitized. Dye F is 2.0 × 1 per mol of silver halide for a large-sized emulsion.
0 ^-4 mol, or 2.8 x 10 ^-4 for small size emulsions
Mole was added. ) Red-sensitive emulsion layer

[0117]

Embedded image

(1 mol of silver halide was added to the large-sized emulsion at 5.0 × 10 ^-5 mol, and to the small-sized emulsion at 8.0 × 10 ^-5 mol. Further, the following compounds were added to the red-sensitive emulsion layer in an amount of 2.6 × 10 ⁻³ mol per mol of silver halide.

[0119]

[Chemical 54]

Also, 1- (5-methylureidophenyl) -5-mercaptotetrazole was added to the blue-sensitive emulsion layer, the green-sensitive emulsion layer and the red-sensitive emulsion layer in an amount of 3.3 × per mol of silver halide. 10 ^-4 mol, 1.0 x 10 ^-3
Mol and 5.9 × 10 ⁻⁴ mol. Furthermore, 0.2 mg each in the second, fourth, sixth and seventh layers.
/ M ² , 0.2 mg / m ² , 0.6 mg / m ² , and 0.1 mg / m ² . For the blue-sensitive emulsion layer and the green-sensitive emulsion layer, 4-hydroxy-6-methyl-1,3,3a, 7
-Tetrazaindene was added in an amount of 1 x 10 ^-4 mol and 2 x 10 ^-4 mol per mol of silver halide, respectively. Also,
In order to prevent irradiation, the following dyes were added to each emulsion layer (the coating amount in parentheses represents the coating amount) (these dyes are water-soluble and therefore diffuse into all photographic constituent layers).

[0121]

[Chemical 55]

(Layer Structure) The composition of each layer is shown below. The numbers represent the coating amount (g / m ² ). The silver halide emulsion represents the coating amount in terms of silver.

Support Polyethylene Laminated Paper [White pigment (TiO ₂ ; content 15
% By weight) and bluish dye (ultra-blue). ]

First Layer (Blue Sensitive Emulsion Layer) The Silver Chlorobromide Emulsion A 0.24 Gelatin 1.29 Yellow Coupler (ExY-1) 0.55 Color Image Stabilizer (Cpd-1) 0.07 Color Image Stabilizer (Cpd-2) 0.04 Color image stabilizer (Cpd-3) 0.07 Solvent (Solv-1) 0.20

Second layer (color mixing prevention layer) Gelatin 0.99 Color mixing inhibitor (Cpd-4) 0.10 Solvent (Solv-1) 0.07 Solvent (Solv-2) 0.20 Solvent (Solv-3) 0.15 Solvent (Solv-7) 0.12

Third Layer (Green Sensitive Emulsion Layer) Silver Chlorobromide Emulsion B (Cubic, 1: 3 Mixture of Large Size Emulsion with Average Grain Size 0.55 μm and Small Size Emulsion with 0.39 μm (Silver Molar Ratio) The coefficient of variation of the grain size distribution was 0.10 and 0.08, respectively, and 0.8 mol% of silver bromide was locally contained in a part of the grain surface based on silver chloride in each size emulsion. 0.1 mg of potassium hexachloroiridium (IV) in total and 1 mg of potassium ferrocyanide in total were contained in the inside of the grain and in the silver bromide local phase per 1 mol of silver.) 0.13 Gelatin 1.35 Magenta coupler (ExM) 0.12 Ultraviolet absorber (UV-1) 0.12 Color image stabilizer (Cpd-2) 0.01 Color image stabilizer (Cpd-5) 0.01 Color image stabilizer (Cpd-6) 0.01 Color image stabilizer (Cp -7) 0.08 Color Image Stabilizer (Cpd-8) 0.01 solvent (Solv-4) 0.30 solvent (Solv-5) 0.15

Fourth Layer (Color Mixing Prevention Layer) Gelatin 0.72 Color mixing inhibitor (Cpd-4) 0.07 Solvent (Solv-1) 0.05 Solvent (Solv-2) 0.15 Solvent (Solv-3) 0.12 Solvent (Solv-7) 0.09

Fifth layer (red-sensitive emulsion layer) Silver chlorobromide emulsion C (cubic, 1: 4 mixture of large size emulsion with average grain size 0.50 μm and small size emulsion with 0.41 μm (silver molar ratio) The coefficient of variation of the grain size distribution was 0.09 and 0.11, respectively, and in each size emulsion, 0.8 mol% of silver bromide was locally contained in a part of the grain surface based on silver chloride. Further, 0.3 mg of potassium hexachloroiridium (IV) ate was added per mol of silver to the inside of the grain and the silver bromide local phase, and 1.5 mg of potassium ferrocyanide was added together.) 0.18 Gelatin 0. 80 Cyan Coupler (Exemplified Compound C-1) 0.28 Ultraviolet Absorber (UV-3) 0.19 Color Image Stabilizer (Cpd-1) 0.24 Color Image Stabilizer (Cpd-6) 0.01 Color image stabilizer (Cpd-8) 0. 1 Color Image Stabilizer (Cpd-9) 0.04 Color Image Stabilizer (Cpd-10) 0.01 solvent (Solv-1) 0.01 solvent (Solv-6) 0.21

Sixth Layer (UV Absorbing Layer) Gelatin 0.64 UV Absorber (UV-2) 0.39 Color Image Stabilizer (Cpd-7) 0.05 Color Image Stabilizer (Solv-8) 0.05

Seventh Layer (Protective Layer) Gelatin 1.01 Polyvinyl alcohol acrylic modified copolymer (modification degree 17%) 0.04 Liquid paraffin 0.02 Surfactant (Cpd-11) 0.01

[0131]

[Chemical 56]

[0132]

[Chemical 57]

[0133]

Embedded image

[0134]

Embedded image

[0135]

Embedded image

[0136]

[Chemical formula 61]

[0137]

Embedded image

[0138]

[Chemical formula 63]

[0139]

[Chemical 64]

With respect to the sample 100 prepared as described above, the yellow coupler of the first layer (blue sensitive layer) and the cyan coupler of the fifth layer (red sensitive layer) were used as the couplers shown in Tables 6 to 11 below. Sample 100, except replaced to molar
Samples 101 to 189 similar to the above were prepared.

[0141]

[Table 6]

[0142]

[Table 7]

[0143]

[Table 8]

[0144]

[Table 9]

[0145]

[Table 10]

[0146]

[Table 11]

The sample 100 produced as described above was subjected to solid exposure with white light to an area of 30% in area ratio, and then continuous treatment (running) was performed by the following processing steps until the tank capacity for color development was doubled. ) Was carried out. Treatment process Temperature Time Replenisher * Tank capacity Color development 40 ° C 45 seconds 40ml 5 liters Bleach fixing 35 ° C 45 seconds 30 5 liters Rinse 35 ° C 20 seconds-2 liters rinse 35 ° C 20 seconds-2 liters rinse 35 ° C 20 seconds -2 liters Rinse 35 ° C 30 seconds 90 3 liters Dry 70-80 ° C 60 seconds * Replenishment amount per 1 m ² of light-sensitive material (rinse is a 3-tank countercurrent method to →)

The composition of each processing liquid is as follows. Color developer Tank solution Replenisher Water 800ml 800ml Sodium triisopropylnaphthalene (β) sulfonate 0.1g 0.1g Triethanolamine 14.5g 14.5g Potassium hydroxide 3.0g 18.0g Ethylenediaminetetraacetic acid 4.5g 4.5g 4,5-dihydroxybenzene Sodium 1,3-disulfonate 0.5g 0.5g Potassium chloride 15.8g-Sodium bromide 0.045g-Potassium carbonate 26.3g 26.3g Sodium sulfite 0.1g 0.2g Disodium-N, N-bis (sulfonate ethyl) hydroxylamine 8.5g 12.0g N-ethyl-N- (β-methanesulfonamidoethyl) -3-methyl-4-aminoaniline ・ 3/2 sulfuric acid / 1 hydrate 5.0g 17.0g optical brightener Fw1 2.0g 5.0g Add water and add 1000ml 1000ml pH (25 ℃ / with potassium hydroxide and sulfuric acid) 10.15 12.6

[0149]

Embedded image

Bleach-fixing solution Tank solution Replenishing solution Water 800ml 600ml Ammonium thiosulfate (750g / l) 120ml 240ml Ammonium sulfite 30g 65g Ethylenediaminetetraacetic acid Ferric ammonium salt 0.11mol 0.24mol Ethylenediaminetetraacetic acid 0.11g 0.024mol 3-carboxyphenylsulfin Acid 0.1 mol 0.2 mol Maleic acid 0.1 mol 0.2 mol Add water to 1000 ml pH (25 ℃ / nitric acid and ammonia water) 6.5 5.8

Rinse solution (same as tank solution and replenisher solution) Sodium chlorinated isocyanurate 0.02 g Deionized water (conductivity 5 μS / cm or less) 1000 ml pH 6.5

The following evaluations were carried out using the prepared samples after the dura mater reaction was completed. Samples 101-123
For the sensitometer (FWH, manufactured by Fuji Photo Film Co., Ltd.
Using a mold and a color temperature of a light source of 3200K, gradation exposure was performed through a blue filter. Separately, using the above-described sensitometer, the samples 100 to 189 were uniformly exposed with a light amount of blue light such that the yellow color density of the photographic material was 1.5.

Each of the exposed samples and the unexposed samples of Samples 100 to 189 were treated with the above running liquid in the above treatment step.

The maximum color density (Dmax) of the gradation-exposed sample was measured using blue light. The results are shown in Table 6.

The treated sample having a concentration of 1.5 was heated to 70
After standing at 80 ° C. and 80% humidity for 4 weeks, measurement was performed using red light (Dn). In addition, the unexposed sample has a temperature of 60 ° C and a humidity of 70%.
After leaving it for 1 week, it was measured using red light (D
s). The respective results are shown in Tables 7 to 11.

As is clear from Table 6, from the comparison of Sample 100, Samples 101 to 103, Samples 106 to 117, etc.,
Compared with a sample using ExY-1, which is a yellow coupler having a substituent other than the present invention and a hydrophobic leaving group, it has a substituent other than the present invention and a hydrophilic leaving group. Yellow coupler ExY-2, ExY-3, ExY
It can be seen that when -4 is used, the value of Dmax increases and the color developability increases. On the other hand, in the coupler of the present invention, the difference due to such a leaving group is similarly observed, but the coupler Y-having the substituent of the present invention and having a hydrophobic leaving group is
It can be seen that even when 1, Y-49, Y-18 or the like is used, a high color-forming property is exhibited with respect to the coupler for comparison. Further, among the couplers of the present invention, the yellow couplers Y-2, Y-20, Y-44, Y-50 and the like, whose substituents are represented by the general formulas (A), (B), (C) and (D), may be used. It can be seen that the coloring property is particularly improved when used. The same can be said when comparing the samples 118 to 123.

On the other hand, as is clear from Tables 7 to 11, when the yellow coupler ExY-1 having a substituent other than the present invention and having a hydrophobic leaving group such as Sample 100 is used, It can be seen that the value of Dn is relatively small and the cyan discoloration after processing is relatively small, but the value of Ds is very large and the cyan stain in the unexposed area is high.
When yellow couplers ExY-2, ExY-3, and ExY-4 having a substituent other than the present invention and having a hydrophilic leaving group such as Samples 101 to 103 are used, D
The value of n is small and the cyan stain in the unexposed area is low,
It can be seen that the value of Ds is still large and the cyan discoloration after processing is large. On the other hand, the yellow couplers Y-73, Y-75, and Y of the present invention such as Samples 106 to 117 are used.
-82, Y-105, Y-2, Y-32, Y-42, Y
It can be seen that when −50 or the like is used, both Ds and Dn are small, and both the cyan discoloration after processing and the cyan stain in the unexposed area are small. Among the yellow couplers of the present invention, the substituents (A), (B),
(C), (D) yellow coupler Y-2, Y-2
The samples using 0, Y-44, and Y-50 are especially Dn and Ds.
It can be seen that the value of is small and the cyan discoloration after processing and the cyan stain in the unexposed area are both small.

Among the cyan couplers of the present invention, such as Sample 130 and Sample 154, those represented by the general formulas C-II and C
It can be seen that when the couplers C-19 and C-5 represented by -III are used, the values of Ds and Dn both become small, and the cyan discoloration after processing and the cyan stain in the unexposed area become small.

[0159]

The combination of the yellow coupler of the present invention and the cyan coupler of the present invention has high yellow and cyan color-forming properties, and the yellow color-developing portion does not turn into a cyan color even when stored under high humidity conditions. Further, it was possible to provide a light-sensitive material in which cyan stain in the unexposed area was reduced.

Claims (2)

[Claims] 1. A halogen having at least one silver halide emulsion layer containing a yellow dye forming coupler, at least one silver halide emulsion layer containing a magenta dye forming coupler, and at least one silver halide emulsion layer containing a cyan dye forming coupler on a support. In the silver halide color photographic light-sensitive material, the yellow dye forming coupler-containing silver halide emulsion layer contains at least one yellow coupler represented by the following general formula (YI), and a cyan dye forming coupler-containing silver halide. A silver halide color photographic light-sensitive material comprising an emulsion layer containing at least one cyan coupler represented by the following general formula (CI). General formula (Y-I): (In the general formula (Y-I), R is a tertiary alkyl group, 3
Represents a primary cycloalkyl group, an aliphatic heterocyclic group, or an aromatic group, and X represents a group which leaves upon reaction with a color developing agent. Y represents a halogen atom, an alkoxy group, an aryloxy group, an acyloxy group, a dialkylamino group or an alkyl group, and Z represents a substituent represented by any one of the following general formulas (A) to (H). Substituents (A) to (H) embedded image (In the general formula (A), R ¹ represents an alkenyl group, a halogenated alkyl group or a halogenated alkenyl group.
In the general formula (B), R ² represents an alkyl group, a cycloalkyl group, an alkenyl group or an aryl group. In formula (C), L ₁ represents an alkylene group, and R ³ represents an alkyl group, a cycloalkyl group, an alkenyl group or an aryl group. In formula (D), R ⁴ and R ⁵ each independently represent an alkyl group, a cycloalkyl group, an aryl group, an alkoxy group, an aryloxy group or an anilino group. In the general formula (E), L ₂ represents an alkylene group and R ⁶ represents an alkyl group or an aryl group. In the general formula (F), L ₃ represents an alkylene group and R ⁷ represents an alkyl group or an aryl group. In the general formula (G), L
₄ represents an alkylene group, R ⁸ represents a hydrogen atom, an alkyl group or an aryl group, and R ⁹ represents an alkyl group or an aryl group. In formula (H), L ₅ represents an alkylene group, and R ¹⁰ and R ¹¹ each independently represent a hydrogen atom, an alkyl group, or an aryl group. ) General formula (C-I) (In the general formula (CI), R ²¹ represents an aliphatic group, an aromatic group, a heterocyclic group or an aromatic or heterocyclic amino group, R ²² represents an aliphatic group or an acylamino group, and R ²³ represents Represents a hydrogen atom, a halogen atom, an aliphatic group, an aliphatic oxy group or an acylamino group, Z ²¹ represents a hydrogen atom or a group or an atom capable of splitting off upon coupling, and R ²² and R ²³ are 5
To 7-membered ring may be formed. ) 2. The silver halide according to claim 1, wherein the cyan coupler represented by the general formula (CI) is further represented by the general formula (C-II) or (C-III). Color photographic light-sensitive material. General formula (C-II) General formula (C-III) (In the general formula (C-II), R ²⁴ represents an aliphatic group having 2 to 20 carbon atoms, and in the general formulas (C-II) and (C-III), R ²¹ represents an aliphatic group or an aromatic group. Represents a group, a heterocyclic group or an aromatic or heterocyclic amino group, and R ²⁵ has 1 to 2 carbon atoms.
0 represents an acylamino group, R ²³ represents a hydrogen atom, a halogen atom, an aliphatic group, an aliphatic oxy group or an acylamino group, Z ²¹ represents a hydrogen atom or a group or atom capable of splitting off upon coupling, R ²³ And R ²⁴ or R ²³ and R ²⁵ may form a 5- to 7-membered ring. )