JPH08292529A - Silver halide color photographic sensitive material - Google Patents

Abstract

PURPOSE: To enable a processing small in replenishment and discharge to be executed and to obtain a good color development performance and good color reproduction performance by incorporating a specified reducing agent for color development and a specified dye-forming coupler in a photographic constituent layers including a silver halide emulsion layer. CONSTITUTION: The photographic constituent layers including the emulsion layer contains the reducing agent for color development represented by formula I and the dye-forming coupler represented by formula II. In the formula I, R<11> is an aryl or heterocyclic group which may have a substituent; R<12> is an alkyl, alkenyl, alkynyl, aryl, or heterocyclic group which may have a substituent; and X is a -SO2 - or -CO- group or the like, and in the formula II, R<21> is an aliphatic, aromatic, heterocyclic, aromatic amino, or heterocyclic amino group which may have a substituent; R<22> is an acylamino group which may have a substituent; X is H or a halogen atom or an aliphatic group or the like which may have substituent; and Z is H atom or a group to be released by oxidation coupling with the reducing agent for color development.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a color photographic technique, and more particularly to a silver halide color photographic light-sensitive material excellent in environmental protection and safety, and having good color developability and hue even by simple and rapid processing, and a color image forming method. .

[0002]

2. Description of the Related Art In general color photographic light-sensitive materials,
After exposing the light-sensitive material to color development, the oxidized p-phenylenediamine derivative reacts with the coupler to form an image. In this method, a color reproduction method by a subtractive color method is used, and in order to reproduce blue, green, and red, a coupler that forms color images of yellow, magenta, and cyan, which have complementary colors to each other, is used. Conventional color development is achieved by immersing the exposed color photographic light-sensitive material in an aqueous alkaline solution (color developer) in which a p-phenylenediamine derivative is dissolved. However, the p-phenylenediamine derivative made into an alkaline aqueous solution is unstable and easily deteriorates with time, and there is a problem that it is necessary to replenish the color developing solution frequently in order to maintain stable developing performance. Further, the disposal of the used color developing solution containing the p-phenylenediamine derivative is complicated, and in combination with the frequent replenishment described above, the processing of a large amount of the used color developing solution is a big problem. There is. Thus, there is a strong demand for achieving low replenishment and low discharge of the color developing solution.

As one of effective means for solving low replenishment and low discharge of the color developing solution, there is a method of incorporating an aromatic primary amine or its precursor in a hydrophilic colloid layer.
As the aromatic primary amine developing agent or its precursor which can be incorporated, for example, US Pat. No. 2,507,114 can be used.
Issue No. 3,764,328 Issue No. 4,060,418
And JP-A-56-6235, JP-A-58-192031 and the like. However, since these aromatic primary amines and their precursors are unstable, they have the drawback that stains are generated during long-term storage or color development of unprocessed light-sensitive materials. Another effective means is, for example, European Patent Nos. 545,491A1 and 5
65,165A1 and the like, a method of incorporating the sulfone hydrazide type compound in the hydrophilic colloid layer can be mentioned. However, when a conventional phenol coupler is used, there is a problem that the color developability is low, and development of a technique for improving the color developability has been desired. On the other hand, when a conventional naphthol coupler is used, good color developability is exhibited, but there is a problem that the cyan dye produced has an absorption wavelength too short and a sufficient color reproducibility cannot be obtained. In order to solve this problem, it has been desired to develop a technique for increasing the absorption wavelength of the cyan dye.

[0004]

The object of the present invention is to enable processing with low replenishment and low discharge, exhibiting good color reproducibility,
Another object of the present invention is to provide a silver halide color light-sensitive material having good color developability.

[0005]

It has been found that the object of the present invention can be achieved by the following method. (1) In a silver halide color photographic light-sensitive material having a photographic constituent layer containing at least one silver halide emulsion layer on a support, at least one color represented by the following general formula (I) is formed in the photographic constituent layer. A silver halide color photographic light-sensitive material comprising a reducing agent for use and at least one dye-forming coupler represented by the following general formula (II). General formula (I)

[0006]

[Chemical 4]

In the general formula (I), R ¹¹ is an optionally substituted aryl group or heterocyclic group, and R ¹² is an optionally substituted alkyl group, alkenyl group, alkynyl group, aryl It is a group or a heterocyclic group. X is -SO
_2- , -CO-, -COCO-, -CO-O-, -CO
^{-N (R 13) -, -} COCO-O -, - COCO-N
(R ¹³⁾ - or -SO ₂ -N (R ¹³⁾ - is. Here, R ¹³ is a hydrogen atom or the group described for R ¹² . General formula (II)

[0008]

Embedded image

In the general formula (II), R ²¹ represents a substituted or unsubstituted aliphatic group, aromatic group, heterocyclic group, aromatic amino group or heterocyclic amino group, and R ²² represents a substituted or unsubstituted group. Represents a substituted acylamino group, X represents a hydrogen atom, a halogen atom, a substituted or unsubstituted aliphatic group, an aromatic group, or an acylamino group, and Z represents a hydrogen atom or a group capable of splitting off upon oxidative coupling with a color-forming reducing agent. Wherein R ²² and X are connected to each other by 5 to 7
A membered nitrogen-containing heterocycle may be formed, and R ²¹ , R ²² , X,
One group in Z may form a dimer or higher multimeric coupler. (2) A silver halide color photographic light-sensitive material having a photographic constituent layer containing at least one silver halide emulsion layer on a support, wherein the photographic constituent layer is at least one kind of color represented by the general formula (I). A silver halide color photographic light-sensitive material comprising a reducing agent and at least one dye-forming coupler represented by the following general formula (III). General formula (III)

[0010]

[Chemical 6]

In the general formula (III), R³¹Is -CONR³⁴
R³⁵-, -NHCOR³⁴-, -NHCOOR³⁶-, -N
HSO₂R³⁶-Or-NHCONR³⁴R³⁵-Show
Then R ³²Represents a group capable of substituting for a naphthol ring, and m is 0
Represents an integer of 3 to 3 and R³³Is an acyl group or oxyca
Represents a carbonyl group, Y is a hydrogen atom or a reducing agent for color development
Represents a group capable of splitting off upon oxidative coupling with. However
R³⁴And R³⁵Can be the same or different, independently
Represents a hydrogen atom, an aliphatic group, an aromatic group or a heterocyclic group,
R³⁶Represents an aliphatic group, an aromatic group or a heterocyclic group. m is
R when multiple³²Can be the same or different, and
They may combine with each other to form a ring. R³²And R³³,Also
Is R³³And X are bonded to each other to form a ring, respectively.
Good.

[0012]

BEST MODE FOR CARRYING OUT THE INVENTION When a phenol coupler is used for the color-forming reducing agent of the present invention, a magenta color image is obtained, and when a naphthol coupler is used, a cyan color image is obtained. However, the color image obtained from a conventional phenol coupler or naphthol coupler is not satisfactory in terms of color developability and color reproducibility. As a result of intensive studies, the inventors have found that among the phenol couplers, the phenol coupler represented by the general formula (II) and the naphthol coupler represented by the general formula (III) have good color development. It has been found that a magenta color image and a cyan color image exhibiting excellent color reproduction and color reproducibility are provided.
The reducing agent for color formation of the present invention is represented by the general formula (IV
The compound represented by formula (a) is preferable, and the compound represented by formula (V) is more preferable. In addition, the general formula (IV
The compound represented by -b) has a high color-forming property, a 2-equivalent coupler can be used as a corresponding coupler, and the increase in stain due to long-term storage of an unprocessed light-sensitive material is particularly low, which is preferable. Formula ^{(IV-b) R 11 -NHNHCO} (R 13) -R 12 formula (IV-a)

[0013]

[Chemical 7]

(In the general formula (IV-a), R ¹¹ is an aryl group or heterocyclic group which may have a substituent, and R ¹²
Is an alkyl group, alkenyl group, alkynyl group, aryl group or heterocyclic group which may have a substituent. ) General formula (V)

[0015]

Embedded image

(In the general formula (V), R ¹² represents an alkyl group or a heterocyclic group, and X ²¹ , X ²³ , and X ²⁵ represent a hydrogen atom, a nitro group, a cyano group, an alkylsulfonyl group, an arylsulfonyl group, an alkyl group. Represents a sulfinyl group, an arylsulfinyl group, a sulfamoyl group, a carbamoyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, an acyl group, or a trifluoromethyl group,
X ²² and X ²⁴ are hydrogen atom, nitro group, cyano group, alkylsulfonyl group, arylsulfonyl group, alkylsulfinyl group, arylsulfinyl group, sulfamoyl group, carbamoyl group, alkoxycarbonyl group, aryloxycarbonyl group, acyl group, tri group It represents a fluoromethyl group, a halogen atom, an acyloxy group, or an acylthio group. However, Hammett's σ _p value of X ²¹ , X ²³ , and X ²⁵ and X
The sum of Hammett's σ _m values of ²² and X ²⁴ must be 1.5 or more. According to the present invention, an open-chain methylene yellow coupler, a magenta coupler represented by the general formula (II) and a cyan coupler represented by the general formula (III) are combined to produce three colors of yellow, magenta and cyan. It is now possible to provide good color and good color development, and the present invention can be used to provide a full-color light-sensitive material.

The color-forming reducing agent used in the present invention is described in detail below. The color-forming reducing agent represented by the general formula (I) used in the present invention is a compound that oxidizes directly or indirectly with a developing agent oxidized by exposed silver halide in an alkaline solution and is a compound that is oxidized. Yes,
The oxidant is a compound characterized by further reacting with a dye-forming coupler to form a dye. In the general formula (I), R ¹¹ represents an aryl group or a heterocyclic group which may have a substituent. The aryl group of R ¹¹ preferably has 6 to 14 carbon atoms, and examples thereof include phenyl and naphthyl. The heterocyclic group for R ¹¹ is preferably a saturated or unsaturated 5-membered ring, 6-membered ring or 7 containing at least one of nitrogen, oxygen, sulfur and selenium.
It is a member's ring. A benzene ring or a hetero ring may be condensed with these. Examples of R ¹¹ heterocycles include:
Furanyl, thienyl, oxazolyl, thiazolyl, imidazolyl, triazolyl, pyrrolidinyl, benzoxazolyl, benzothiazolyl, pyridyl, pyridazyl, pyrimidinyl, pyrazinyl, triazinyl, quinolinyl,
Examples include isoquinolinyl, phthalazinyl, quinoxalinyl, quinazolinyl, purinyl, pteridinyl, azepinyl, benzoxepinyl and the like.

The substituent which R ¹¹ has is an alkyl group, an alkenyl group, an alkynyl group, an aryl group, a heterocyclic group, an alkoxy group, an aryloxy group, a heterocyclic oxy group, an alkylthio group, an arylthio group, a heterocyclic thio group. , Acyloxy group, acylthio group, alkoxycarbonyloxy group, aryloxycarbonyloxy group, carbamoyloxy group, alkylsulfonyloxy group, arylsulfonyloxy group, amino group, alkylamino group, arylamino group, amide group, alkoxycarbonylamino group , An aryloxycarbonylamino group, an ureido group, a sulfonamide group, a sulfamoylamino group,
Acyl group, alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl group, acylcarbamoyl group,
Carbamoylcarbamoyl group, sulfonylcarbamoyl group, sulfamoylcarbamoyl group, alkylsulfonyl group, arylsulfonyl group, alkylsulfinyl group, arylsulfinyl group, alkoxysulfonyl group, aryloxysulfonyl group, sulfamoyl group,
Examples thereof include an acylsulfamoyl group, a carbamoylsulfamoyl group, a halogen atom, a nitro group, a cyano group, a carboxyl group, a sulfo group, a phosphono group, a hydroxyl group, a mercapto group, an imide group and an azo group. R ¹² represents an optionally substituted alkyl group, alkenyl group, alkynyl group, aryl group or heterocyclic group.

The alkyl group of R ¹² is preferably a linear, branched or cyclic group having 1 to 16 carbon atoms, for example, methyl, ethyl, hexyl, dodecyl, 2-octyl, t-butyl, cyclopentyl, cyclooctyl. Etc. The alkenyl group for R ¹² is preferably a chain or cyclic group having 2 to 16 carbon atoms, and examples thereof include vinyl, 1-octenyl and cyclohexenyl.

The alkynyl group for R ¹² preferably has 2 to 16 carbon atoms, and examples thereof include 1-butynyl and phenylethynyl. Examples of the aryl group and heterocyclic group for R ¹² include those mentioned for R ¹¹ .
Examples of the substituent of R ¹² include those described for the substituent of R ¹¹ . Preferably as X include -SO ₂ -, - CO
-, -COCO-, or -CON (R < ¹³ >)-,
More preferably, -SO ₂ from the viewpoint of chromogenic - or -CON (R ¹³⁾ - is. Among them, X is -CON
In the case of (R ¹³ ) −, a 2-equivalent coupler can be used as the corresponding coupler, and further, the increase in stain that tends to occur when the unprocessed light-sensitive material is stored for a long period is low,
Particularly preferred.

R ¹¹ is preferably a nitrogen-containing heterocyclic group or a group represented by the general formula (VI), more preferably a 6-membered nitrogen-containing heterocyclic group or a general formula (VI). It is a base. When X is —SO _2, the group represented by formula (VI) is particularly preferable from the viewpoint of color developability. General formula (VI)

[0022]

[Chemical 9]

In the general formula (VI), X ²¹ , X ²³ , X ²⁵
Is a hydrogen atom, a nitro group, a cyano group, an alkylsulfonyl group, an arylsulfonyl group, an alkylsulfinyl group, an arylsulfinyl group, a sulfamoyl group, a carbamoyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, an acyl group or a trifluoromethyl group. represents, X ^22, X ²⁴ represents a hydrogen atom or a nitro group, a cyano group, an alkylsulfonyl group, an arylsulfonyl group, an alkylsulfinyl group, an arylsulfinyl group, a sulfamoyl group, a carbamoyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, an acyl Represents a group, a trifluoromethyl group, a halogen atom, an acyloxy group, an acylthio group. However, the sum of the Hammett σ _p values of X ²¹ , X ²³ , and X ^{25 and} the Hammett σ _m values of X ²² and X ²⁴ must be 1.5 or more. The color-forming reducing agent of the present invention is preferably non-diffusible in the emulsion layer. Hereinafter, specific compound examples of the general formula (I) will be shown.

[0024]

[Chemical 10]

[0025]

[Chemical 11]

[0026]

[Chemical 12]

[0027]

[Chemical 13]

[0028]

Embedded image

[0029]

[Chemical 15]

[0030]

Embedded image

[0031]

[Chemical 17]

[0032]

Embedded image

[0033]

[Chemical 19]

[0034]

Embedded image

[0035]

[Chemical 21]

[0036]

[Chemical formula 22]

[0037]

[Chemical formula 23]

[0038]

[Chemical formula 24]

[0039]

[Chemical 25]

[0040]

[Chemical formula 26]

[0041]

[Chemical 27]

[0042]

[Chemical 28]

[0043]

[Chemical 29]

[0044]

Embedded image

[0045]

[Chemical 31]

[0046]

Embedded image

Some of the compounds represented by the general formula (I) of the present invention are described in, for example, US Pat. Nos. 2,424,256, 4,481,268, European Patent 565,165,
It is described in JP-A No. 61-259249, and other compounds can be synthesized by the method described therein. The coupler represented by formula (II) is described in detail below. In the general formula (II), 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, etc.),
Alternatively, an aromatic or heterocyclic amino group (eg, anilino group, naphthylamino group, 2-benzothiazolyl group,
2-pyridylamino group), and these groups further include an alkyl group, an aryl group, a heterocyclic group, an alkoxy group (for example, a methoxy group and a 2-methoxyethoxy group), an aryloxy group (for example, 2,4). -Di-tert-
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 (eg 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, butylsulphone) Famoyl group, etc.), sulfamide group (eg, dipropylsulfamoylamino group, etc.),
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.

In the present specification, the "aliphatic group" may be linear, branched or cyclic and includes saturated and unsaturated groups such as alkyl, alkenyl and alkynyl groups (representative examples thereof). Methyl group, ethyl group, butyl group, dodecyl group, octadecyl group, eicosenyl group, iso-propyl group, tert-butyl group, tert-
Octyl group, tert-dodecyl group, cyclohexyl group, cyclopentyl group, allyl group, vinyl group, 2-hexadecenyl group, propargyl group, etc.). R ²² preferably represents an acylamino group having 1 to 36 carbon atoms (eg, acetylamino, butyrylamino, tetradecanoylamino, benzoylamino group, etc.), which is substituted with a substituent permissible in R ²¹ . Good. X is a hydrogen atom, a halogen atom (for example, a fluorine atom, a chlorine atom, a bromine atom, etc.), preferably an aliphatic group having 1 to 20 carbon atoms,
It represents an aromatic group having 6 to 20 carbon atoms or an acylamino group, and these groups may be substituted with a substituent allowed by R ²¹ .

R ²² and X may be linked to each other to form a 5- to 7-membered nitrogen-containing heterocycle, and such a ring is preferably a 5- to 6-membered nitrogen-containing heterocycle derived from an acylamino group. Z represents a hydrogen atom or a coupling-off group, and examples thereof include a halogen atom (eg, fluorine atom, chlorine atom, bromine atom, etc.), 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) , Toluene etc. sulfonylamino group), an alkoxycarbonyl group (e.g., ethoxycarbonyl group, benzyloxycarbonyl group), an aryloxycarbonyl group (e.g., a phenoxycarbonyl group),
An aliphatic or aromatic thio group (for example, an ethylthio group,
A phenylthio group, a tetrazolylthio group, etc.), an imide group (eg, a succinimide group, a hydantoinyl group, etc.), an aromatic azo group (eg, a phenylazo group, etc.) and the like. These leaving groups may include photographically useful groups. The general formula (II) is preferably a coupler represented by the following general formula (VII). General formula (VII)

[0050]

[Chemical 33]

In the above formula, R ²¹ is preferably a substituted alkyl group or a substituted or unsubstituted aryl group, and the substituent of the alkyl group is preferably an optionally substituted phenoxy group or a halogen atom. The group is particularly preferably a phenyl group substituted with at least one halogen atom, an alkyl group, a sulfonamide group or an acylamino group. Preferred R ²³ is a substituted alkyl group or a substituted aryl group, and an optionally substituted phenoxy group is particularly preferred as the substituent of the alkyl group. Preferred X is a hydrogen atom, an alkyl group, an alkenyl group, an aralkyl group or an acylamino group. It is preferable that X and R ²³ form a 5- to 7-membered ring, and it is particularly preferable to form a 5- and 6-membered ring. Preferred Z has the general formula (IV-a)
When using a color-forming reducing agent represented by, a hydrogen atom is preferable from the viewpoint of color forming property, while when using a color-forming reducing agent represented by the general formula (IV-b), a halogen atom or from the viewpoint of color forming property. Aryloxy groups are preferred. The coupler represented by formula (II) may be used alone or in combination of two or more, and may be used in combination with other known couplers (not limited to cyan). Specific examples of the cyan coupler represented by formula (II) are listed below.

[0052]

Embedded image

[0053]

Embedded image

[0054]

Embedded image

[0055]

Embedded image

The coupler represented by formula (III) is described in detail below. R ²¹ is -CONR ³⁴ R ³⁵ , -N
HCOR ³⁴ , -NHCOOR ³⁶ , -NHSO ₂ R ³⁶ ,-
Shows the NHCONR ³⁴ R ³⁵ or -NHSO ₂ NR ³⁴ R ^35. Examples of R ³⁴ , R ^35, and R ³⁶ include an aliphatic group having 1 to 30 carbon atoms, an aromatic group having 6 to 30 carbon atoms, and a heterocyclic group having 2 to 30 carbon atoms. R ²² represents a group capable of substituting on a naphthol ring (including atoms, the same applies hereinafter), and representative examples thereof include a halogen atom, a hydroxy group, an amino group, a carboxyl group, a sulfonic acid group, a cyano group, an aromatic group, and a heterocyclic group. , Carbonamide group, sulfonamide group, carbamoyl group,
Sulfamoyl group, ureido group, acyl group, acyloxy group, aliphatic oxy group, aromatic oxy group, aliphatic thio group, aromatic thio group, aliphatic sulfonyl group, aromatic sulfonyl group, sulfamoylamino group, nitro group , An imide group and the like, and the number of carbon atoms contained in R ³² is 0 to 30. An example of cyclic R ³² when m = 2 is a dioxymethylene group. R ³³ represents an acyl group or an oxycarbonyl group, preferably an aliphatic or aromatic acyl group or an oxycarbonyl group.
Substituents may be further bonded to these aliphatic groups and aromatic groups. As a specific example of the acyl group, a formyl group,
Acetyl group, trifluoroacetyl group, chloroacetyl group, benzoyl group, pentafluorobenzoyl group, p-
Examples thereof include a chlorobenzoyl group, and specific examples of the oxycarbonyl group include a methoxycarbonyl group, an ethoxycarbonyl group, a butoxycarbonyl group, a decyloxycarbonyl group, a methoxyethoxycarbonyl group, and a phenoxycarbonyl group.

Y represents a hydrogen atom or a coupling-off group (including a leaving atom; the same applies hereinafter). Typical examples of the coupling-off group are a halogen atom, -OR ⁴¹ and -S.
^{R 41, -O (C = O} ) R 41, -NHCOR 41, -NH
(C = O) SR ⁴¹ , -O (C = O) -OR ⁴¹ , -O (C
═O) NHR ⁴¹ , aromatic azo group having 6 to 30 carbon atoms, heterocyclic group having 1 to 30 carbon atoms and linked to the coupling active position of the coupler by a nitrogen atom (succinimide group, phthalimido group, hydantoinyl group) , A pyrazolyl group, a 2-benzotriazolyl group, etc.) and the like. Here, R ⁴¹ represents an aliphatic group having 1 to 30 carbon atoms, an aromatic group having 6 to 30 carbon atoms, or a heterocyclic group having 2 to 30 carbon atoms. In the present invention, the aliphatic group may be saturated / unsaturated, substituted / unsubstituted, linear / branched / cyclic, and typical examples include a methyl group, an ethyl group, a butyl group, Cyclohexyl group, allyl group, propargyl group, methoxyethyl group, n-decyl group, n-dodecyl group, n-hexadecyl group, trifluoromethyl group, heptafluoropropyl group, dodecyloxypropyl group, 2,4-di-tert. −
Examples include an amylphenoxypropyl group and a 2,4-di-tert-amylphenoxybutyl group. The aromatic group may be substituted or unsubstituted, and typical examples thereof include a phenyl group, a tolyl group, a 2-tetradecyloxyphenyl group, a pentafluorophenyl group and a 2-chloro-5 group.
-Dodecyloxycarbonylphenyl group, 4-chlorophenyl group, 4-cyanophenyl group, 4-hydroxyphenyl group and the like are included. The heterocyclic group may be substituted or unsubstituted, and typical examples thereof include a 2-pyridyl group, a 4-pyridyl group, a 2-furyl group, a 4-thienyl group, a quinolinyl group, and the like. . Preferred examples of the substituent in the present invention are described below. R ³¹ is preferably a substituted or unsubstituted carbamoyl group, and specific examples thereof include a carbamoyl group, an ethylcarbamoyl group, a morpholinocarbonyl group, a dodecylcarbamoyl group and a hexadecylcarbamoyl group.

R ³² and m are most preferably m = 0, that is, unsubstituted, and then R ³² is a halogen atom.
Aliphatic groups, carbonamide groups, sulfonamide groups and the like are acceptable substituents. Y is preferably a hydrogen atom, a chlorine atom, an aliphatic oxy group [for example, 2-hydroxyethoxy group, 2-chloroethoxy group, carboxymethyloxy group, 1-carboxyethoxy group, 2-methanesulfonylethoxy group, 3-carboxypropyl group]. Oxy group, 2-methoxyethoxycarbamoylmethyloxy group, 1-carboxytridecyl group, 2- (1-carboxytridecylthio) ethyloxy group, 2-carboxymethylthioethyloxy group, 2-methanesulfonamidoethyloxy group, etc.] An aromatic oxy group [eg, 4-acetamidophenoxy group, 2-acetamidophenoxy group, 4- (3-carboxypropanamide) phenoxy group, etc.] and a carbamoyloxy group (eg, ethylcarbamoyloxy group,
A phenylcarbamoyloxy group). General formula (IV-
When using the color-forming reducing agent represented by a), a hydrogen atom is most preferable from the viewpoint of color-forming property, and when using the color-forming reducing agent represented by the general formula (IV-b), halogen is used from the viewpoint of color-forming property. Most preferred are atoms or aromatic oxy groups. General formula (II
The coupler represented by I) may form a dimer or a multimer of the substituents R ³¹ , R ³² , R ³³ or X, which are bonded to each other through a divalent or divalent or higher valent group. . In this case, the carbon number range shown in each of the above substituents may be out of the range. Below is the general formula (III)
Specific examples of the coupler represented by are shown below, but the coupler used in the present invention is not limited thereto.

[0059]

[Chemical 38]

[0060]

[Chemical Formula 39]

[0061]

[Chemical 40]

[0062]

Embedded image

The color-forming reducing agent of the present invention contains 0.01 mmol / m ² to 10 mmol / m ² per color-forming layer in order to obtain a sufficient color-forming density.
It is preferred to use mmol / m ² . A more preferred amount used is 0.05 mmol / m ² to ⁵ mmol / m ² , and a particularly preferred amount used is 0.1 mmol / m ^{2 to 1} mmol / m ² . The preferred amount of the coupler in the color forming layer in which the color forming reducing agent of the present invention is used is 0.05 in terms of mol based on the color forming reducing agent.
It is 20 to 20 times, more preferably 0.1 to 10 times, and particularly preferably 0.2 to 5 times.

The color light-sensitive material of the present invention basically comprises a support having thereon a photographic constituent layer containing a light-sensitive silver halide, a dye-forming coupler, a color-forming reducing agent and a binder. . The dye-forming coupler and the color-forming reducing agent used in the present invention are most typically added to the same layer, but they can be added separately to separate layers if they are in a reactive state. . These components are preferably added to the silver halide emulsion layer in the light-sensitive material or a layer adjacent thereto, and particularly preferably added to the silver halide emulsion layer.

The color-forming reducing agent and coupler of the present invention can be introduced into a light-sensitive material by various known dispersion methods, dissolved in a high-boiling organic solvent (a low-boiling organic solvent is optionally used together), and emulsified in a gelatin aqueous solution. An oil-in-water dispersion method of dispersing and adding to a silver halide emulsion is preferred. The high boiling organic solvent used in the present invention has a melting point of 100 ° C. or lower and a boiling point of 140 ° C.
The above-mentioned water-immiscible compound can be used as long as it is a color-forming reducing agent and a good solvent for the coupler. The melting point of the high boiling point organic solvent is preferably 80 ° C. or lower. The boiling point of the high boiling point organic solvent is preferably 160 ° C. or higher, more preferably 170 ° C. or higher. Details of these high boiling point organic solvents are described in JP-A No. 62-215272, page 137, lower right column to page 144, upper right column.
In the present invention, the amount of the high-boiling organic solvent used may be any amount, but preferably with respect to the color-forming reducing agent,
The weight ratio of the high-boiling organic solvent / reducing agent for color development is preferably 20 or less, more preferably 0.02 to 5. A known polymer dispersion method may be used in the present invention. The process of latex dispersion method as one of polymer dispersion methods, effects, and specific examples of latex for impregnation are described in US Pat. No. 4,199,3.
63, West German Patent Application (OLS) 2,541,274
No. 2, 542, 230, Japanese Patent Publication No. 53-4109
No. 1 and European Patent Publication No. 029104, and the dispersion method using an organic solvent-soluble polymer is described in PCT International Publication No. WO88 / 00723.

The average particle size of the new oily fine particles containing the reducing agent for color development of the present invention is not particularly limited, but it is preferably 0.05 to 0.3 μ from the viewpoint of color developability, and 0.0
5μ to 0.2μ 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 support used in the present invention includes glass,
Any support such as paper or plastic film can be used as long as it is a transmission type or reflection type support capable of coating a photographic emulsion layer. The plastic film used in the present invention,
Polyester films such as polyethylene terephthalate, polyethylene naphthalate, cellulose triacetate or cellulose nitrate, polyamide films, polycarbonate films, polystyrene films and the like can be used. The "reflective support" that can be used in the present invention,
It is one that enhances the reflectivity and makes the dye image formed on the silver halide emulsion layer clear, and such a reflection type support includes titanium oxide, zinc oxide, calcium carbonate, calcium sulfate, etc. on the support. And those coated with a hydrophobic resin containing the light-reflecting substance dispersed therein, and those using the hydrophobic resin itself containing the light-reflecting substance dispersed therein as a support. For example, polyethylene coated paper, polyester coated paper,
Polypropylene-based synthetic paper, support provided with a reflective layer or used in combination with a reflective material, for example, glass plate, polyethylene terephthalate, polyester film such as cellulose triacetate or cellulose nitrate, polyamide film, polycarbonate film, polystyrene film, chloride Vinyl resin etc. are available. As the polyester-coated paper, the polyester-coated paper containing polyethylene terephthalate as a main component described in European Patent EP 0,507,489 is preferably used.

The reflective support used in the present invention is preferably a paper support whose both surfaces are coated with a water resistant resin layer and at least one of the water resistant resins contains white pigment fine particles. The white pigment particles are preferably contained in a density of 12% by weight or more, more preferably 14% by weight or more. As the light-reflecting white pigment, it is preferable to sufficiently knead the white pigment in the presence of a surfactant, and pigment particles whose surface is treated with a divalent to tetravalent alcohol are preferable. In the present invention, a support having a surface of diffuse reflection of the second kind is preferably used. The second-class diffuse reflectivity is the diffusion obtained by giving unevenness to the surface having a mirror surface and dividing it into fine mirror surfaces facing different directions, and dispersing the divided fine surface (mirror surface) directions. It is reflective. The unevenness of the surface of the diffuse reflection property of the second type has a three-dimensional average roughness of 0.1 to 2 μm, preferably 0.1 to 1.2 μm with respect to the center plane. Details of such a support are described in JP-A-2-239244.

In order to obtain a wide range of colors on the chromaticity diagram by using the three primary colors of yellow, magenta and cyan, a combination of at least three layers of silver halide emulsion layers having photosensitivity in different spectral regions is used. To be For example, three layers of a blue-sensitive layer, a green-sensitive layer and a red-sensitive layer and a three-layer of a green-sensitive layer, a red-sensitive layer and an infrared-sensitive layer are combined and coated on the above support. Each of the light-sensitive layers can take various arrangement orders known in ordinary color light-sensitive materials. Further, each of these photosensitive layers may be divided into two or more layers if necessary. The light-sensitive material includes the above-mentioned light-sensitive layer and protective layer, an undercoat layer, an intermediate layer,
A photographic constituent layer comprising various auxiliary layers such as an antihalation layer and a back layer can be provided. Further, various filter dyes can be added to the photographic layers to improve color separation.

The silver halide grains used in the present invention are silver bromide, silver chloride, silver iodide, silver chlorobromide, silver chloroiodide, silver iodobromide,
It is silver chloroiodobromide. Other silver salts, such as Rhodan silver,
Silver sulfide, silver selenide, silver carbonate, silver phosphate, and organic acid silver may be contained as separate grains or as a part of silver halide grains. When rapid development / desilvering (bleaching, fixing and bleach-fixing) steps are desired, silver chlorobromide grains or silver chloride grains having a high silver chloride content (preferably 95 mol% or more) are desirable. Further, in the case of suppressing development appropriately, it is preferable to contain silver iodide. The preferred silver iodide content varies depending on the intended light-sensitive material. For example X-
The preferred range is 0.1 to 15 mol% for the ray sensitive material and 0.1 to 5 mol% for the graphic arts and the micro sensitive material. In the case of a photographic light-sensitive material represented by a color negative, silver halide containing 1 to 30 mol% of silver iodide is preferable, 5 to 20 mol% is more preferable, and 8 to 15 mol% is particularly preferable. . It is preferable that the silver iodobromide grains contain silver chloride in order to reduce lattice strain. For a reflective type photographic material that requires rapid processing, the silver iodide content is preferably zero or 1 mol% or less.

Even if the silver halide grains used in the present invention are normal crystals that do not contain twin planes, they are described in Japan Photographic Society, Fundamentals of the Photographic Industry, Silver Salt Photographs (Corona Publishing Co.), P.163. For example, a single twin containing one twin plane, a parallel multiple twin containing two or more parallel twin planes, a non-parallel multiple twin containing two or more non-parallel twin planes, etc. It can be selected and used accordingly. An example of mixing particles having different shapes is disclosed in US Pat. No. 4,865,964, but this method can be selected as necessary. In the case of normal crystal, a cube consisting of (100) plane, (111)
An octahedron having a plane, a dodecahedral grain having a (110) plane disclosed in JP-B-55-42737 and JP-A-60-222842 can be used. In addition, Jo
urnal of Imaging Science 30, 247, 1986.
(211) as reported in the year (h)
11) face particles, (331) representative (hh1) face particles, (210) face representative (hk0) face particles and (32)
(Hk1) plane particles typified by the 1) plane also require devising in the preparation method, but can be selected and used according to the purpose. (1
A tetrahedral grain in which (00) plane and (111) plane coexist in one grain, a grain in which (100) plane and (110) plane coexist,
Alternatively, particles having two planes or a large number of planes, such as particles having (111) planes and (110) planes, can be selected and used according to the purpose.

The value obtained by dividing the circle-equivalent diameter of the projected area by the grain thickness is called the aspect ratio, and defines the shape of tabular grains. Tabular grains having an aspect ratio of greater than 1 can be used in the present invention. Tabular grains are described in Cleve, Photography Theory and Practice.
(1930)), p. 131; Gatov, Photographic Science and Engineering (Gutoff, Photogr
aphic Science and Engineering), Volume 14, 248-257
Page (1970); U.S. Pat. Nos. 4,434,226, 4,414,310, 4,433,048, 4,439,520 and British Patent 2,112,1.
It can be prepared by the method described in No. 57, etc.
When the tabular grains are used, there are advantages such as an increase in covering power and an increase in color sensitization efficiency by the sensitizing dye, which are described in detail in US Pat. No. 4,434,226 cited above. . The average aspect ratio of 80% or more of the total projected area of the grains is preferably 1 or more and less than 100. It is more preferably 2 or more and less than 20, and particularly preferably 3 or more and less than 10. The shape of tabular grains can be selected from triangles, hexagons, circles, and the like. U.S. Pat. No. 4,79
A regular hexagon with six sides of approximately equal length as described in 7,354 is a preferred form.

Although the equivalent circle diameter of the projected area is often used as the grain size of tabular grains, US Pat.
The average diameter as described in No. 8,106 is 0.6
Particles of micron or smaller are preferable for improving image quality. An emulsion having a narrow grain size distribution as described in U.S. Pat. No. 4,775,617 is also preferable. It is preferable to increase the sharpness by limiting the grain thickness of the tabular grains to 0.5 μm or less, more preferably 0.3 μm or less. Further, an emulsion having a highly uniform thickness having a variation coefficient of grain thickness of 30% or less is also preferable. Further, grains described in JP-A-63-163451, in which the grain thickness and the interplanar distance between twin planes are defined, are also preferable.

In the case of tabular grains, dislocation lines can be observed with a transmission electron microscope. It is preferable to select particles containing no dislocation lines, particles containing several dislocations or particles containing many dislocations according to the purpose. It is also possible to select dislocations or curved dislocations introduced linearly with respect to a specific direction of the crystal orientation of the particles, or to introduce the dislocations throughout the particles or only in specific parts of the particles, for example, The dislocation can be introduced only in the fringe portion of the grain. The introduction of dislocation lines is preferable not only in the case of tabular grains but also in the case of regular grains or amorphous grains typified by potato grains. In this case as well, it is a preferable form to limit the particles to specific portions such as vertices and edges.

The silver halide emulsion used in the present invention is a treatment for rounding grains as disclosed in European Patent Nos. 96,727B1 and 64412B1, or West German Patent No. 2,306,447C2. , JP Sho 60
The surface may be modified as disclosed in US Pat. A structure having a flat particle surface is generally used, but intentionally forming irregularities is sometimes preferable. JP-A-58-106532, JP-A-60-221
Examples are the part of the crystals described in U.S. Pat. No. 320, for example the method of drilling holes in the centers of vertices or planes, or the ruffled particles described in U.S. Pat. No. 4,643,966.

The grain size of the emulsion used in the present invention depends on the circle equivalent diameter of the projected area using an electron microscope, the sphere equivalent diameter of the grain volume calculated from the projected area and the grain thickness, or the sphere equivalent diameter of the volume by the Coulter counter method. Can be evaluated. It can be used by selecting from ultrafine particles having a sphere-equivalent diameter of 0.05 micron or less, and coarse particles having a sphere-equivalent diameter of more than 10 microns. Preferably, grains having a size of 0.1 micron or more and 3 microns or less are used as the photosensitive silver halide grains.

The emulsion used in the present invention may be a so-called polydisperse emulsion having a wide grain size distribution or a monodisperse emulsion having a narrow size distribution, and can be selected and used according to the purpose. As a scale representing the size distribution, the variation coefficient of the projected area circle diameter of particles or the sphere equivalent diameter of volume may be used. When using a monodisperse emulsion, the coefficient of variation is 25% or less,
It is preferable to use an emulsion having a size distribution of 20% or less, and more preferably 15% or less.

In order to satisfy the target gradation of the light-sensitive material, two or more kinds of monodisperse silver halide emulsions having different grain sizes are mixed in the same layer in the emulsion layers having substantially the same color sensitivity. Alternatively, it can be applied in multiple layers as separate layers. Further, two or more kinds of polydisperse silver halide emulsions or a combination of a monodisperse emulsion and a polydisperse emulsion can be used as a mixture or as a mixture.

The photographic emulsion used in the present invention is described in "Physics and Chemistry of Photography" by Graphide, published by Paul Montel (P.Gl.
afkides, Chimie et Physique Photographique Paul Mo
ntel, 1967), "Photoemulsion Chemistry" by Duffin, published by Focal Press (GFDuffin, Photographic Emulsion Chem
istry (Focal Press, 1966), "Manufacturing and coating of photographic emulsions" by Zelikmann et al., published by Focal Press (VLZelikm
an et al, Making andCoating Photographic Emulsion,
Focal Press, 1964) and the like. That is, any of an acidic method, a neutral method, an ammonia method and the like may be used, and a method of reacting a soluble silver salt and a soluble halogen salt may be a one-sided mixing method, a simultaneous mixing method, a combination thereof or the like. Good. A method of forming grains in the presence of excess silver ions (so-called reverse mixing method) can also be used. 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 substantially uniform grain size can be obtained.

During preparation of the emulsion of the present invention, for example, during grain formation,
In the desalting step, during chemical sensitization, it is preferable to allow a salt of a metal ion to exist before coating, depending on the purpose. When the grains are doped, they are preferably added at the time of grain formation, when the grains are modified, or when used as a chemical sensitizer, after grain formation and before the end of chemical sensitization. A method of doping the entire grain, a method of doping only the core portion of the grain, only the shell portion, only the epitaxial portion, or only the base grain can be selected. Ag, Ca, Sr, Ba, Al, S
c, Y, La, Cr, Mn, Fe, Co, Ni, Cu,
Zn, Ga, Ru, Rh, Pd, Re, Os, Ir, P
t, Au, Cd, Hg, Tl, In, Sn, Pb, Bi
Etc. can be used. These metals can be added in the form of salts such as ammonium salts, acetates, nitrates, sulfates, phosphates, hydroxides or hexacoordinated complex salts and tetracoordinated complex salts which can be dissolved at the time of grain formation. For example CdB
_{r 2, CdCl 2, Cd (} NO 3) 2, Pb (NO 3) 2,
Pb (CH ₃ COO) ₂ , K ₃ [Fe (CN) ₆ ], (N
H _{4) 4} [Fe (CN) _{6], K 3 IrCl 6, (NH} 4) 3
RhCl ₆ , K ₄ Ru (CN) _{6 and the} like can be mentioned. Halogen, H ₂ O, cyano group, as ligand of coordination compound,
It can be selected from a cyanate group, a thiocyanate group, a nitrosyl group, a thionitrosyl group, an oxo group and a carbonyl group. These metal compounds may be used alone or in combination of two or more. The method of adding a chalcogen compound as described in U.S. Pat. No. 3,772,031 during emulsion preparation may be useful. In addition to S, Se and Te, cyanide salt,
A thiocyan salt, selenocyanic acid, carbonate, phosphate or acetate may be present.

The silver halide grains of the present invention have at least one of sulfur sensitization, selenium sensitization, tellurium sensitization (these three types are collectively called chalcogen sensitization), noble metal sensitization, or reduction sensitization. It can be applied at any step of the process for producing a silver halide emulsion. It is preferable to combine two or more sensitizing methods. Various types of emulsions can be prepared depending on which step is chemically sensitized. There are a type in which chemically sensitized nuclei are embedded inside a grain, a type in which a chemical sensitized nucleus is embedded at a shallow position from the grain surface, and a type in which a chemically sensitized nucleus is formed on the surface. In the emulsion of the present invention, the location of the chemically sensitized nucleus can be selected according to the purpose, but it is generally preferable that at least one type of chemically sensitized nucleus is formed near the surface.

The chemical sensitization that can be preferably carried out in the present invention is a chalcogen sensitization and a noble metal sensitization alone or in combination thereof, and is written by TH James in The Photographic Process, 4th edition, published by Macmillan. , 1977,
(TH James, The Theory of the Photographic Proces
s, 4th ed, Macmillan, 1977) using active gelatin as described on pages 67-76, and Research Disclosure Item 12008 (April 1974).
Month); Item 13452 (June 1975); Item 307105 (1
(November 989), U.S. Patent Nos. 2,642,361, 3,297,446, 3,772,031, 3,857,711, 3,901,714, 4 , 266,018, and 3,904,415.
And pAg 5-10, pH 5-8 and temperature 30-as described in GB 1,315,755.
It can be carried out at 80 ° C. with sulfur, selenium, tellurium, gold, platinum, palladium, iridium or combinations of these sensitizers.

The photographic emulsion used in the present invention may contain various compounds for the purpose of preventing fog during the manufacturing process of the light-sensitive material, storage or photographic processing, or stabilizing photographic performance. . That is, thiazoles, such as benzothiazolium salts, nitroimidazoles, nitrobenzimidazoles, chlorobenzimidazoles, bromobenzimidazoles, mercaptothiazoles, mercaptobenzothiazoles, mercaptobenzimidazoles, mercaptothiadiazoles, aminotriazoles. , Benzotriazoles, nitrobenzotriazoles, mercaptotetrazoles (especially 1-phenyl-5-mercaptotetrazole)
Etc .; mercaptopyrimidines; mercaptotriazines; thioketo compounds such as oxadrinethione; azaindenes, such as triazaindenes, tetraazaindenes (especially 4-hydroxy-6-methyl (1,3,3a, 7) Tetraazaindene), many compounds known as antifoggants or stabilizers such as pentaazaindenes and the like can be added.
For example, US Pat. Nos. 3,954,474 and 3,98
Nos. 2,947 and 52-28660 can be used. One of the preferred compounds is the compound described in Japanese Patent Application No. 62-47225. Antifoggants and stabilizers are used at various times before particle formation, during particle formation, after particle formation, during the water washing step, during dispersion after water washing, before chemical sensitization, during chemical sensitization, after chemical sensitization, and before coating. It can be added depending on the purpose. In addition to adding the original antifoggant and stabilizing effects during emulsion preparation,
It can be used for various purposes such as controlling the crystal habit of grains, reducing the grain size, reducing the solubility of grains, controlling chemical sensitization, and controlling the arrangement of dyes.

The photographic emulsion used in the present invention is preferably spectrally sensitized with a methine dye or the like in order to exert the effects of the present invention. The dyes used include cyanine dyes, merocyanine dyes, complex cyanine dyes, complex merocyanine dyes, holopolar cyanine dyes, hemicyanine dyes, styryl dyes and hemioxonol dyes. Particularly useful dyes are those belonging to the cyanine dyes, merocyanine dyes, and complex merocyanine dyes. Any of the nuclei normally used for cyanine dyes as a basic heterocyclic nucleus can be applied to these dyes. That is, a pyrroline nucleus, an oxazoline nucleus, a thiozoline nucleus, a pyrrole nucleus, an oxazole nucleus, a thiazole nucleus, a selenazole nucleus, an imidazole nucleus, a tetrazole nucleus, a pyridine nucleus and the like; a nucleus in which an alicyclic hydrocarbon ring is fused to these nuclei; and these A nucleus in which an aromatic hydrocarbon ring is fused to the nucleus of
That is, indolenine nucleus, benzindolenine nucleus, indole nucleus, benzoxadol nucleus, naphthoxazole nucleus, benzothiazole nucleus, naphthothiazole nucleus, benzoselenazole nucleus, benzimidazole nucleus, quinoline nucleus and the like can be applied. These nuclei may be substituted on carbon atoms.

In the merocyanine dye or the complex merocyanine dye, as a nucleus having a ketomethylene structure, a pyrazolin-5-one nucleus, a thiohydantoin nucleus, a 2-thiooxazolidine-2,4-dione nucleus, a thiazolidine-2,4-
A 5-6 membered heterocyclic nucleus such as a dione nucleus, a rhodanine nucleus or a thiobarbituric acid nucleus can be applied. Further, as the red-sensitive spectral sensitizing dye for silver halide emulsion grains having a particularly high silver chloride content, the spectral sensitizing dye described in JP-A-3-123340 is stable, has strong adsorption, and has an exposure temperature. It is very preferable from the viewpoint of dependency. In the case of efficiently spectrally sensitizing the infrared region in the light-sensitive material of the present invention, it is disclosed in
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, EP
No. 0,420,011, page 4, line 21 to page 6, line 54, EP
No. 0,420,012, page 4, line 12 to page 10, line 33, E
P-0,443,466, US-4,975,362.
The sensitizing dyes described in No. 1 are preferably used.

The timing at which the sensitizing dye is added to the emulsion may be at any stage in the emulsion preparation which has heretofore been known to be useful. Most commonly, it is carried out after the completion of chemical sensitization and before coating, but it is described in US Pat. No. 3,62.
It is also possible to add spectral sensitization simultaneously with chemical sensitization by adding it at the same time as the chemical sensitizer as described in JP-A-8-969 and 4,225,666.
It can be carried out prior to chemical sensitization as described in US Pat. No. 3,928, or it can be added before the completion of silver halide grain precipitation to initiate spectral sensitization. It is also possible to add these said compounds separately, as taught in U.S. Pat. No. 4,225,666, i.e. to add some of these compounds prior to chemical sensitization and the rest to chemical sensitization. It can be added after the sensation, and can be added at any time during the formation of silver halide grains, including the method disclosed in US Pat. No. 4,183,756.

In the present invention, a colored layer that can be decolorized by treatment is used in combination with a water-soluble dye. The coloring layer that can be decolorized by the treatment used may be in direct contact with the emulsion layer,
You may arrange | position so that it may contact via the intermediate | middle layer containing a processing color mixture 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 also possible to install all the colored layers corresponding to each primary color individually.
It is also possible to arbitrarily select and 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 the wavelength with the highest optical density in the wavelength range used for exposure (visible light range from 400 nm to 700 nm in normal printer exposure, wavelength of scanning exposure light source used in scanning exposure). 2. The optical density value is 0.2 or more.
It is preferably 0 or less. More preferably 0.5
It is preferably 2.5 or more and 2.5 or less, particularly 0.8 or more and 2.0 or less.

In order to form the colored layer, conventionally known methods may be used in combination. For example, JP-A-2-2822
A hydrophilic colloid layer in the form of a solid fine particle dispersion such as the dyes described in No. 44, page 3, upper right column to page 8 and the dyes described in JP-A-3-7931, page 3, upper right column to page 11, lower left column. , A method of mordanting an anionic dye with a cationic polymer, a method of adsorbing the dye to fine particles such as silver halide and fixing it in the layer, JP-A-1-23954.
No. 4, using colloidal silver, 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. 2-3
08244, pp. 4-13. Also,
For example, as a method of mordanting an anionic dye onto a cationic polymer, there are disclosed Nos. 18 to 26 of JP-A-2-84637.
Page. A method for preparing colloidal silver as a light absorber is shown in US Pat. Nos. 2,688,601 and 3,459,563. 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 pp
It is preferable to use low calcium gelatin of m 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 exposing the light-sensitive material of the present invention to a printer, US Pat. No. 4,880,726
It is preferable to use the band stop filter described in No. As a result, light color mixture is removed, and color reproducibility is significantly improved.

Although the above-mentioned various additives are used in the light-sensitive material of the present technology, various additives other than the above can be used according to the purpose. For more information on these additives, see Research Disclosure Item 17643.
(December 1978), Item 18716 (November 1979) and
It is described in Item 307105 (November 1989), and the relevant parts are summarized in the table below.

[0091]

[Table 1]

The total coating amount of silver in the light-sensitive material of the present invention is 0.003 to 1 g per m ^{2 in} terms of silver, but the desilvering step can be omitted for faster processing, and the waste liquid load can be further reduced. Is preferred. The coated silver amount of each layer is preferably 0.001 to 0.4 g per photosensitive layer. Particularly when the light-sensitive material of the present invention is subjected to intensification processing, 0.003 to 0.
3 g is preferable, more preferably 0.01 to 0.1 g,
Particularly preferably, it is 0.015 to 0.05 g. In this case, it is preferably 0.001 to 0.1 g, and more preferably 0.003 to 0.03 g per photosensitive layer. In the present invention, if the coating amount of silver in each light-sensitive material layer is less than 0.001 g per 1 m ² , the dissolution of the silver salt will proceed and a sufficient color development density will not be obtained. If it exceeds, Dmin increases and bubbles are generated, which makes it difficult to endure viewing.

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. In order to make the system compact and 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 such a scanning exposure light source is used,
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 light source obtained by combining a semiconductor laser with a nonlinear optical crystal can halve the oscillation wavelength of the laser, 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, it becomes less necessary for at least two layers to have a spectral sensitivity maximum at 670 nm or more.

In such scanning exposure, the time for which the silver halide in the photosensitive 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 practically 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.

Processing materials and processing methods used in the present invention will be described. In the present invention, the light-sensitive material is subjected to development (silver development / cross oxidation of built-in reducing agent), (desilvering) and washing or stabilization treatment. In addition, after washing or stabilizing treatment, treatment for enhancing color development such as application of alkali may be performed. When developing the light-sensitive material in the present invention,
A compound having a function of functioning as a developing agent for silver halide and / or a function of cross-oxidizing a reducing agent for color formation contained in a light-sensitive material by an oxidized product of a developing agent generated in silver development is used for a developing solution. Preferably pyrazolidones,
Dihydroxybenzenes, reductones and aminophenols are used, particularly preferably pyrazolidones.

Pyrazolidones include 1-phenyl-3
-Pyrazolidones are preferable, 1-phenyl-3-pyrazolidone, 1-phenyl-4,4-dimethyl-3-pyrazolidone, 1-phenyl-4-methyl-4-hydroxymethyl-3-pyrazolidone, 1-phenyl-4. , 4-dihydroxymethyl-3-pyrazolidone, 1-phenyl-
5-methyl-3-pyrazolidone, 1-phenyl-5-phenyl-3-pyrazolidone, 1-p-tolyl-4-methyl-4-hydroxymethyl-3-pyrazolidone, 1-p
-Chlorophenyl-4-methyl-4-hydroxymethyl-3-pyrazolidone, 1-phenyl-2-hydroxymethyl-4,4-dimethyl-3-pyrazolidone, 1-phenyl-2-acetyl-3-pyrazolidone, 1-phenyl 2-hydroxymethyl-5-phenyl-3-pyrazolidone and the like. Examples of dihydroxybenzenes include hydroquinone, chlorohydroquinone, bromhydroquinone, isopropylhydroquinone, methylhydroquinone, 2,3-dichlorohydroquinone, 2,5-dichlorohydroquinone, 2,5-dimethylhydroquinone and potassium hydroquinone monosulfonate.

As the reductones, ascorbic acid or its derivatives are preferable, and the compounds described on pages 3 to 10 of JP-A-6-148822 are used. Particularly, sodium L-ascorbate and sodium erythorbate are preferable. As p-aminophenols, N-methyl-p-aminophenol, N- (β-hydroxyethyl) -p-aminophenol, N- (4-hydroxyphenyl) glycine, 2-methyl-p-aminophenol, and so on. These compounds are usually used alone,
It is also preferable to use two or more kinds in combination in order to enhance the developing and cross-oxidizing activities. The amount of these compounds used in the developer is 2.5 × 10 ⁻⁴ mol / liter to 0.2 mol / liter, preferably 0.0025 mol / liter to 0.1 mol / liter, and more preferably 0. It is 0.001 mol / liter to 0.05 mol / liter. The pH of the developer used in the present invention is preferably 8 to 13, and more preferably 9 to 12. In order to maintain the above pH, it is preferable to use various buffer solutions. Further, conventionally known organic preservatives, development accelerators, anti-settling agents, optical brighteners and the like can be added to the developer.

The processing temperature of the developing solution applied to the present invention is 2
The temperature is 0 to 50 ° C, preferably 30 to 45 ° C. The treatment temperature is 5 seconds to 2 minutes, preferably 10 seconds to 1 minute. It is preferable that the replenishing amount is small, but 15 to ⁶ per 1 m ^{2 of} light-sensitive material
00 ml, preferably 25 to 200 ml, more preferably 3
5 to 100 ml. After the development, desilvering is generally performed. The desilvering process may be a fixing process or a bleaching and fixing process. When the bleaching and fixing treatments are carried out, the bleaching treatment and the fixing treatment may be carried out individually or simultaneously (bleach-fixing treatment). Further, treatment with two continuous bleach-fixing baths, fixing treatment before the bleach-fixing treatment, or bleaching treatment after the bleach-fixing treatment can be optionally carried out. As the bleaching bath and fixing bath, those conventionally known can be used. Further, it is also preferable to carry out a stabilization treatment without performing desilvering treatment after development to stabilize a silver salt or a color image.

After development, West German Patent (OLS) 1,
813, 920, 2,044,993, 2,7
35,262, JP-A-48-9728, and JP-A-49-8.
No. 4240, No. 49-102314, No. 51-538.
No. 26, No. 52-13336, No. 52-73731 and the like, it is possible to perform an image reinforcing treatment (intensification) using a peroxide, a halous acid, an iodoso compound and a cobalt (III) complex compound. . Further, in order to strengthen the image reinforcement, it is also possible to add the above-mentioned oxidizing agent for image reinforcement to the developing solution and simultaneously perform development and image intensification in one bath.
Hydrogen peroxide is particularly preferred because of its high amplification factor. These image intensification methods can significantly reduce the amount of silver in the light-sensitive material, so bleaching is unnecessary and it is possible to eliminate silver (and silver salt) emissions during stabilization processing, etc. This is a preferable treatment method. The processing temperature of the desilvering process is 20 to 50 ° C,
It is preferably 30 to 45 ° C. Processing time is 5 seconds to 2
Minutes, preferably 10 seconds to 1 minute. The replenishment amount is preferably small, but 15 to 600 ml, preferably 25 to 200 ml, and more preferably 35 to 100 ml per 1 m ^{2 of} the light-sensitive material.
ml. It is also preferable to carry out the treatment without supplementing the amount of the evaporated component with water. The light-sensitive material of the present invention generally undergoes a washing step after desilvering. When the stabilization treatment is performed, the water washing step may be omitted. The pH of the washing or stabilizing solution is 4-9, preferably 5-8. The treatment temperature is 15 to 45 ° C, preferably 25 ° C to 40 ° C. Treatment time is 5 seconds to 2 minutes, preferably 10 seconds to 40
Seconds. The overflow solution accompanying the above washing with water and / or supplementation of the stabilizing solution can be reused in other steps such as the desilvering step.

The amount of washing water and / or the stabilizing solution can be set within a wide range depending on various conditions, but the replenishing amount is preferably 15 to 360 ml per 1 m ² of the light-sensitive material, and 25 to 120 ml.
Is more preferable. The processing time of each processing step in the present invention means the time required from the start of the processing of the photosensitive material in one step to the start of the processing in the next step.
The actual processing time in an automatic processor is usually determined by the linear velocity and the capacity of the processing bath, but in the present invention, the standard linear velocity is 500 to 4000 mm / min. Particularly in the case of a small developing machine, 500 to 2500 mm / min is preferable. All processing steps, that is, the processing time from the development step to the drying step,
It is preferably 360 seconds or less, more preferably 120 seconds or less, and particularly preferably 90 to 30 seconds. Here, the processing time is the time from the immersion of the photosensitive material in the developing solution to the exit from the drying section of the processor.

[0102]

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 After corona discharge treatment was applied to the surface of a paper support laminated on both sides with polyethylene, a gelatin subbing layer containing sodium dodecylbenzene sulfonate was provided, and two kinds of photographic constituent layers were further coated, A photographic printing paper (100) having a two-layer structure shown in 1 was prepared. The coating liquid was prepared as follows. 1st layer coating liquid 18.5 g of coupler (ExM-1), reducing agent for color development (I
-9) 20 g and the solvent (Solv-2) 80 g are dissolved in 100 ml of ethyl acetate, and this solution is emulsified by dispersing in 270 g of 16% gelatin aqueous solution containing 16 ml of 10% sodium dodecylbenzenesulfonate and 0.4 g of citric acid. Dispersion B was prepared. On the other hand, silver chlorobromide emulsion B (cubic, large size emulsion having an average grain size of 0.55 μm and 0.
1: 3 mixture with 39 μm small size emulsion (silver molar ratio). Coefficients of variation of particle size distribution are 0.10 and 0.08, respectively. For each size emulsion, 0.8 mol% of silver bromide was locally contained in a part of the surface of the grain based on silver chloride). This emulsion contains the green sensitizing dye D shown below,
For large emulsions where E and F are per mole of silver,
3.0 × 10 ^-4 mol, 4.0 × 10 ^-5 mol, respectively
2.0 × 10 ^-4 mol, and for small-sized emulsions, 3.6 × 10 ^-4 mol, 7.0 × 10 ^-5 mol, and 2.
8 × 10 ⁻⁴ mol is added. The chemical ripening of this emulsion was carried out by adding a sulfur sensitizer and a gold sensitizer. The above emulsified dispersion B and this silver chlorobromide emulsion B were mixed and dissolved to prepare a coating solution for the first layer having the composition shown below. The emulsion coating amount is the silver equivalent coating amount.

The coating solution for the second layer was prepared in the same manner as the coating solution for the first layer. As the gelatin hardener for each layer, 1-oxy-3,5-dichloro-s-triazine sodium salt was used. In addition, Cpd-2, Cpd-3, Cpd
-4 and Cpd-5 in total amount of 15.0 mg /
m ² , 60.0 mg / m ² , 50.0 mg / m ² and 10.0 mg
/ M ² was added. The following spectral sensitizing dyes were used in the first layer of silver chlorobromide emulsion.

[0105]

Embedded image

(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 [the first layer of polyethylene contains a white pigment (TiO ₂ ) and a bluish dye (ultraviolet)] First layer Silver chlorobromide emulsion B 0.20 Gelatin 1.50 Magenta coupler ( ExM-1) 0.185 Color developing agent (I-9) 0.20 Solvent (Solv-2) 0.80

Second Layer (Protective Layer) Gelatin 1.01 Polyvinyl alcohol acrylic modified copolymer (modification degree 17%) 0.04 Liquid paraffin 0.02 Surfactant (Cpd-1) 0.01 First layer Sample (101) was prepared in the same manner as Sample (100), except that the magenta coupler and the color-forming reducing agent in the coating liquid of Example 1 were replaced with the magenta coupler and the color-forming reducing agent shown in Table a in equimolar amounts. (133) were produced.

[0108]

[Chemical 43]

[0109]

[Chemical 44]

[0110]

Embedded image

Samples (100) to (133) prepared as described above using an FWH type sensitometer manufactured by FUJIFILM Corporation (color temperature of light source: 3200 ° K) were ground with a green filter for sensitometry. Toned exposure was given. The exposed sample was processed in the following processing steps using the following processing solutions. Processing process Temperature Time Image 40 ° C 15 seconds Bleaching / fixing 40 ° C 45 seconds Linth room temperature 45 seconds Alkaline treatment room temperature 30 seconds

Developer Water 800 ml Potassium phosphate 40 g Disodium-N, N-bis (sulfonate ethyl) hydroxylamine 10 g KCl 5 g Hydroxyethylidene-1,1-diphosphonic acid (30%) 4 ml 1-phenyl-4-methyl -4-Hydroxymethyl-3-pyrazolidone 1 g Water was added to 1000 ml pH (25 ° C / potassium hydroxide) 12

Bleach-fixing solution Water 600 ml Ammonium thiosulfate (700 g / l) 93 ml Ammonium sulfite 40 ml Ethylenediaminetetraacetic acid iron (III) ammonium 55 g Ethylenediaminetetraacetic acid 2 g Nitric acid (67%) 30 g Water was added 1000 ml pH (25 ° C / acetic acid and acetic acid and Ammonia water) 5.8

Rinsing solution Sodium chlorinated isocyanurate 0.02 g Deionized water (conductivity 5 μs / cm or less) 1000 ml pH 6.5 Alkaline treatment water 800 ml Potassium carbonate 30 g Water is added to 1000 ml pH (25 ° C./in sulfuric acid 10.0) The maximum color density portion of the sample after the treatment was measured with green light. The results are shown in Tables a-1 and a-2.

[0115]

[Table 2]

[0116]

[Table 3]

As is clear from Tables a-1 and a-2, the sample using the phenol coupler of the present invention shows higher color density than the sample using the comparative phenol coupler. Further, when the color-forming reducing agent (I-9) represented by the general formula (IV) is used, it is found that the color-forming property is high among the present invention. Further, in the case of using the color-forming reducing agent (I-56) represented by the general formula (V),
It can be seen that the color developability is high.

Example 2 The silver chlorobromide emulsion B in the coating solution for the first layer of the sample (100) of Example 1 was replaced with the silver chlorobromide emulsion C shown below in an equal amount of silver to prepare a coupler and a color developing agent. Samples (200) to (200) were prepared in exactly the same manner as sample (100) except that the reducing agent was replaced with the cyan coupler shown in Table b and the reducing agent for color formation in equimolar amounts.
(226) was produced. (However, the solvent is Solv-
Solv-1 was used instead of 2. ) Silver chlorobromide emulsion C: cubic, 1: 4 mixture of large size emulsion C having an average grain size of 0.5 μm and small size emulsion of 0.41 μm (Ag molar ratio). Coefficients of variation of grain size distribution are 0.09 and 0.11, AgBr for each size emulsion
0.8 mol% was locally contained in a part of the surface of the grain based on silver chloride.

The silver chlorobromide emulsion C contains the following spectral sensitizing dye G
And H were used respectively.

[0120]

Embedded image

(5.0 × 10 ^-5 mol was added to the large-sized emulsion and 8.0 × 10 ^-5 mol to the small-sized emulsion, respectively, per mol of silver halide.)

[0122]

[Chemical 47]

With respect to the samples (200) to (226) prepared as described above using the FWH type sensitometer manufactured by FUJIFILM Corporation (color temperature of light source: 3200 ° K), the color density was 0.5. And exposed with green light.

The same treatment as in Example 1 was performed on all the exposed samples.

The reflection spectra of all the samples after the treatment were measured, and the maximum absorption wavelength (λmax) was read from the spectra. The results are shown in Table b.

[0126]

[Table 4]

As is apparent from Table b, the maximum absorption wavelength of the color forming dye in the sample using the naphthol coupler of the present invention is longer than that in the sample using the comparative naphthol coupler. This means that the color reproducibility of natural colors has been greatly improved. Further, color-forming reducing agents (I-5), (I-11), (I-2
0), (I-54) and (I-55) were also found to have similar effects by using the coupler of the present invention.

Example 3 The coupler and the color-forming reducing agent in the coating solution for the first layer of the sample (200) of Example 2 were replaced by equimolar amounts of the cyan coupler and the color-forming reducing agent shown in Table c, respectively. Is the sample (1
(300) to (333) in exactly the same manner as in (00).
Was produced.

Samples (300) to (333) prepared as described above using a FWH type sensitometer manufactured by Fuji Film Co., Ltd. (color temperature of light source: 3200 ° K) were ground with a red filter for sensitometry. Toned exposure was given.

The same treatment as in Example 1 was performed on all the exposed samples.

The maximum color density portion of the processed sample was measured with red light. The results are shown in Table c.

[0132]

[Table 5]

As is clear from Table c, even when the naphthol coupler of the present invention is used, when the color-forming reducing agent (I-9) represented by the general formula (IV-a) is used, It can be seen that among the inventions, the coloring property is high. Furthermore, the general formula (V)
It can be seen that when the reducing agent for color formation (I-56) represented by is used, the color developability is higher.

Example 4 Various photographic constituent layers were coated on a polyethylene laminated paper support surface-treated and undercoated in the same manner as in Example 1 to prepare a multilayer color photographic paper (40
0) was prepared. First layer coating liquid 17 g of coupler (ExY-1), reducing agent for color development (I-
9) 20 g and 80 g of the solvent (Solv-1) are dissolved in 100 ml of ethyl acetate, and this solution is emulsified and dispersed in 270 g of a 16% gelatin aqueous solution containing 16 ml of 10% sodium dodecylbenzenesulfonate and 0.4 g of citric acid. Material A was prepared. On the other hand, silver chlorobromide emulsion A (cubic, large size emulsion having an average grain size of 0.88 μm and 0.
3: 7 mixture (silver mole ratio) with 70 μm small size emulsion. The coefficient of variation of the grain size distribution was 0.08 and 0.10, respectively. In each size emulsion, 0.3 mol% of silver bromide was locally contained in a part of the grain surface based on silver chloride. did. This emulsion contains blue-sensitive sensitizing dye A shown below,
B and C were added in an amount of 1.4 × 10 ⁻⁴ mol per mol of silver to the large size emulsion and 1.7 × 10 ⁻⁴ mol to each of the small size emulsion. The chemical ripening of this emulsion was carried out 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 is the silver equivalent coating amount.

[0135]

Embedded image

The third layer coating solution was the same as that in Example 1, and the fifth layer coating solution was the same as that in Example 2. Other coating solutions for the second to seventh layers were prepared in the same manner as the first layer coating solution. As the gelatin hardener for each layer, 1-oxy-3,5-dichloro-s-triazine sodium salt was used. Further, the same four kinds of preservatives used in Example 1 were added to each layer in the same amount as in Example 1. The following compounds were further added to the fifth layer (red-sensitive layer) in an amount of 2.6 × 10 ^-2 mol per mol of silver halide.

[0137]

[Chemical 49]

For the blue-sensitive emulsion layer, the green-sensitive emulsion layer and the red-sensitive emulsion layer, 1- (5-methylureidophenyl)-
5-Mercaptotetrazole to silver halide 1
3.5 × 10 ⁻⁴ mol, 3.0 × 10 ⁻³ mol per mol,
2.5 × 10 ^-4 mol was added. Further, 4-hydroxy-6-methyl-1,
3,3a, 7-Tetrazaindene was added at 1 × 10 ⁻⁴ mol and 2 × 10 ⁻⁴ mol per mol of silver halide, respectively. To prevent irradiation, the following dyes (the amount in parentheses represents the coating amount) were added to the emulsion layer.

[0139]

Embedded image

(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 [Polyethylene on the first layer side contains a white pigment (TiO ₂ ) and a bluish dye (ultraviolet)]

First Layer (Blue Sensitive Emulsion Layer) The Silver Chlorobromide Emulsion A 0.20 Gelatin 1.50 Yellow Coupler (ExY-1) 0.17 Coloring Reducing Agent (I-9) 0.20 Solvent (Solv-1) 0.80

Second Layer (Color Mixing Prevention Layer) Gelatin 1.09 Color Mixing Preventer (Cpd-6) 0.11 Solvent (Solv-1) 0.19 Solvent (Solv-3) 0.07 Solvent (Solv-4) 0.25 solvent (Solv-5) 0.09

Third Layer (Green Sensitive Emulsion Layer) Silver Chlorobromide Emulsion B 0.20 Gelatin 1.50 Magenta Coupler (ExM-1) 0.24 Coloring Reducing Agent (I-9) 0. 20 Solvent (Solv-2) 0.80

Fourth Layer (Color Mixing Prevention Layer) Gelatin 0.77 Color mixing inhibitor (Cpd-6) 0.08 Solvent (Solv-1) 0.14 Solvent (Solv-3) 0.05 Solvent (Solv-4) 0.14 Solvent (Solv-5) 0.06

Fifth layer (red-sensitive emulsion layer) Silver chlorobromide emulsion C 0.20 of Example 2 Gelatin 1.50 Cyan coupler (ExC-1) 0.20 Coloring reducing agent (I-9) 0.20 Solvent (Solv-1) 0.18

Sixth Layer (UV Absorbing Layer) Gelatin 0.64 UV Absorbing Agent (UV-1) 0.39 Color Image Stabilizer (Cpd-7) 0.05 Solvent (Solv-6) 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-1) 0.01

[0149]

[Chemical 51]

[0150]

Embedded image

[0151]

Embedded image

[0152]

[Chemical 54]

With respect to the sample (400), a reducing agent for color development,
Sample (4) was prepared in exactly the same manner as Sample (400) except that the magenta coupler and cyan coupler were replaced with the color-forming reducing agent, magenta coupler and cyan coupler shown in Table d.
01) to (405) were produced.

An FWH type sensitometer manufactured by Fuji Film Co., Ltd. (color temperature of light source: 3200 ° K) was used to perform gradation exposure of a three-color separation filter for sensitometry.

The exposed sample was processed in the following processing steps using the following processing solutions. Processing process Temperature Time Image 40 ° C 15 seconds Bleaching / fixing 40 ° C 45 seconds Linth room temperature 45 seconds Alkaline treatment room temperature 30 seconds

Developer water 800 ml Potassium phosphate 40 g Disodium-N, N-bis (sulfonatoethyl) hydroxylamine 10 g KCl 5 g Hydroxyethylidene-1,1-diphosphonic acid (30%) 4 ml 1-phenyl-4-methyl -4-Hydroxymethyl-3-pyrazolidone 1 g Water was added to 1000 ml pH (25 ° C / potassium hydroxide) 12

Bleach-fixing solution Water 600 ml Ammonium thiosulfate (700 g / l) 93 ml Ammonium sulfite 40 ml Ethylenediaminetetraacetic acid iron (III) ammonium 55 g Ethylenediaminetetraacetic acid 2 g Nitric acid (67%) 30 g Water was added to 1000 ml pH (25 ° C / acetic acid and acetic acid and Ammonia water) 5.8

Rinsing solution Sodium chlorinated isocyanurate 0.02 g Deionized water (conductivity 5 μs / cm or less) 1000 ml pH 6.5

Alkaline-treated solution Water 800 ml Potassium carbonate 30 g Water was added to 1000 ml pH (at 25 ° C./sulfuric acid) 10.0

The magenta coloring portion and the maximum coloring portion of the cyan coloring portion of the processed sample were measured with green light and red light, respectively. The results are shown in Table d.

[0161]

[Table 6]

For samples (400) to (405), a FWH type sensitometer manufactured by FUJIFILM Corporation (color temperature of light source: 3200 ° K) was used to obtain red light with a cyan density of 0.5. Exposed.

The same processing as described above was performed on all exposed samples.

The reflection spectra of all the samples after the treatment were measured, and from the spectra, the maximum absorption wavelength (λmax) for cyan color development was obtained.
Read. The results are shown in Table d.

As is apparent from Table d, in the case of the multi-layered light-sensitive materials, the same results as those of the single-layered light-sensitive materials shown in Examples 1 to 3 were obtained.

Example 5 A surface of a paper support laminated on both sides with polyethylene was subjected to a corona discharge treatment and then provided with a gelatin subbing layer containing sodium dodecylbenzenesulfonate, and various photographic constituent layers were further coated thereon. A multilayer color photographic paper (500) having the layer structure shown was produced. The coating liquid was prepared as follows. Third layer coating liquid Coupler (EXM-2) 19.7 g, color reducing agent (I
-78) 21.1 g and a solvent (Solv-1) 80 g were dissolved in ethyl acetate, and this solution was emulsified and dispersed in 400 g of a 16% gelatin solution containing 10% sodium dodecylbenzenesulfonate and citric acid to obtain an emulsified dispersion E. Was prepared. On the other hand, a silver chlorobromide emulsion E (a cubic mixture, a 1: 3 mixture of a large size emulsion E having an average grain size of 0.10 μm and a small size emulsion E of 0.08 μm (Ag molar ratio). Coefficient of variation of grain size distribution. Was prepared by locally adding 0.10 and 0.08, respectively, and 0.8 mol% of AgBr in each size emulsion to a portion of the surface of the grain based on silver chloride.
In this emulsion, the above-mentioned sensitizing dye D per mol of silver halide was 1.5 × 10 ⁻³ mol for large size emulsion, 1.8 × 10 ⁻³ mol for small size emulsion, and The sensitizing dye E is 2.0 × 10 ^-4 mol for a large-sized emulsion, 3.5 × 10 ^-4 mol for a small-sized emulsion, and the sensitizing dye E per mol of silver halide. F is 1.0 × 10 per mol of silver halide for large-sized emulsions.
^-3 mol, and 1.4 × 10 ^-3 mol was added to the small size emulsion. The chemical ripening of this emulsion was carried out by adding a sulfur sensitizer and a gold sensitizer. The emulsified dispersion E
And this silver chlorobromide emulsion E were mixed and dissolved to prepare a coating solution for the third layer having the composition shown below. The emulsion coating amount is the silver equivalent coating amount.

The coating solutions for the first layer, the second layer, and the fourth to seventh layers were prepared in the same manner as the coating solution for the third layer. As a gelatin hardener for each layer, 1-oxy-3,5-dichloro-
The s-triazine sodium salt was used. Cp for each layer
d-2, Cpd-3, Cpd-4 and Cpd-5 to the total amount of each ^{15.0mg / m 2, 60.0mg / m} 2, 50.0mg
/ M ² and 10.0 mg / m ² were added. The blue-sensitive sensitizing dyes A, B and C and the red-sensitive sensitizing dyes G and H were used in the following amounts in the blue-sensitive emulsion layer and the red-sensitive emulsion layer, respectively. Blue-sensitive emulsion layer (Blue-sensitive sensitizing dyes A, B and C are 7.0 × 10 ⁻⁴ mol for each of the following large-sized emulsions D per mol of silver, and each of the following small-sized emulsions D). Each is 8.5 × 10 ^-4 mol) Red-sensitive emulsion layer (red-sensitive sensitizing dyes G and H per 1 mol of silver halide,
2.5 × 10 ⁻⁴ mol each for the following large size emulsion F, and 4.0 × 10 ^{4 for} the following small size emulsion F.
^-4 mol)

In the fifth layer (red-sensitive layer), the same compound as used in Example 4 was further added at 2.6 × per mol of silver halide.
10 ^-2 mol was added. Further, 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 3.5 × 10 ^-4 mol / mol of silver halide and 3 0.0 x 1
0 ⁻³ mol and 2.5 × 10 ⁻⁴ mol were added. Further, 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene was added to the blue-sensitive emulsion layer and the green-sensitive emulsion layer in an amount of 1 × 10 ⁻⁴ mol and 2 mol, respectively, per mol of silver halide. × 10
^-4 mol was added. The same trimethine oxonol dye and pentamethine oxonol dye used in Example 4 were added in the same amounts as in Example 4. 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 15 wt.
%) And a bluish dye (ultraviolet)] First layer (blue-sensitive emulsion layer) Silver chlorobromide emulsion D 0.01 (cubic, large emulsion D with average grain size 0.10 μm and small emulsion 0.08 μm) 3: 7 mixture (silver mole ratio) with size emulsion D. Coefficients of variation of grain size distribution are 0.08 and 0.10, respectively, 0.3 mol% of silver bromide and silver chloride are added to each size emulsion. It was locally contained on a part of the surface of the base grain.Chemical ripening of this emulsion was performed by adding a sulfur sensitizer and a gold sensitizer.) Gelatin 1.50 Yellow coupler (ExY-2 ) 0.183 Coloring reducing agent (I-76) 0.211 Solvent (Solv-1) 0.80

Second Layer (Color Mixing Prevention Layer) Gelatin 1.09 Color mixing inhibitor (Cpd-7) 0.11 Solvent (Solv-1) 0.19 Solvent (Solv-3) 0.07 Solvent (Solv-4) 0.25 Solvent (Solv-5) 0.09 1,5-Diphenyl-3-pyrazolidone 0.03 (fine particle solid dispersion state) Third layer (green sensitive emulsion layer) Silver chlorobromide emulsion E 0.01 Gelatin 1.50 Magenta coupler (ExM-2) 0.197 Coloring reducing agent (I-78) 0.211 Solvent (Solv-1) 0.80 Fourth layer (color mixing prevention layer) Gelatin 0.77 Color mixing inhibitor (CpD-7) 0.08 solvent (Solv-1) 0.14 solvent (Solv-3) 0.05 solvent (Solv-4) 0.14 solvent (Solv-5) 0.06 1,5-diphenyl- 3-pyrazoli Down 0.02 (particle solid dispersion state)

Fifth Layer (Red Sensitive Emulsion Layer) Silver chlorobromide emulsion F 0.01 (cubic, large size emulsion F having an average grain size of 0.10 μm and small size emulsion F having a size of 0.08 μm, 1: 4). Mixture (Ag molar ratio) Coefficients of variation of grain size distribution are 0.09 and 0.11, and 0.8 mol% of AgBr was locally contained in a part of grain surface based on silver chloride in each size emulsion. Chemical ripening of this emulsion was performed by adding a sulfur sensitizer and a gold sensitizer.) Gelatin 0.15 Cyan coupler (ExC-2) 0.223 Coloring reducing agent (I-78) 0. 211 Solvent (Solv-1) 0.80 Sixth layer (UV absorbing layer) Gelatin 0.64 UV absorber (UV-1) 0.39 Color image stabilizer (Cpd-8) 0.05 Solvent (Solv-6) ) 0.05 seventh layer (protective layer) gelatin 1.0 Acrylic-modified copolymer of polyvinyl alcohol (modification degree 17%) 0.04 Liquid paraffin 0.02 Surfactant (Cpd-1) 0.01

[0171]

[Chemical 55]

Sample (500) was prepared in the same manner as in sample (500) except that the coupler and the color-forming reducing agent were replaced with the coupler and color-forming reducing agent shown in Table e in equimolar amounts. 500) to (505) were produced. All the samples prepared as described above were subjected to gradation exposure of a three-color separation filter for sensitometry using an FWH type sensitometer manufactured by Fuji Film Co., Ltd. (color temperature of light source: 3200 ° K). The exposed sample was processed in the following processing steps using the following processing solutions. Treatment process I Treatment process Temperature Time Development 40 ℃ 40 seconds Rinse room temperature 45 seconds Alkaline treatment Room temperature 30 seconds

Developer Water 600 ml Potassium phosphate 40 g KCl 5 g Hydroxyethylidene-1,1-diphosphonic acid (30%) 4 ml H ₂ O ₂ 10 ml Water was added to 1000 ml pH (at 25 ° C./potassium hydroxide) 11. 5 The same rinse solution and alkaline treatment solution as those used in Example 1 were used. The maximum color densities of the magenta color development part and the cyan color development part of the processed sample are respectively set to green light,
It was measured with red light. The results are shown in Table e. Sample (5
00) to (505) for F manufactured by FUJIFILM Corporation
Exposure was performed with red light using a WH type sensitometer (color temperature of light source: 3200 ° K) so that the cyan density was 0.5.
All the exposed samples were processed in the same manner as the above. The reflection spectra of all the samples after the treatment were measured, and the maximum absorption wavelength (λmax) for cyan color development was read from the spectra. The results are shown in Table e.

[0174]

[Table 7]

As can be seen from Table e, by using the phenol coupler of the present invention even in the case of using the multilayer photosensitive material having a low coating amount of silver, compared with the case of using the naphthol coupler for comparison, a higher magenta Indicates the color density,
It can be seen that by using the naphthol coupler of the present invention, the maximum absorption wavelength becomes a long wave and a high cyan color density is exhibited, as compared with the case of using the comparative naphthol coupler.

According to the present invention, the yellow coupler, the magenta coupler and the cyan coupler shown in the examples are combined so that the three colors of yellow, magenta and cyan can be colored with good color reproducibility and color developability. As a result, it becomes possible to provide a full-color light-sensitive material using the system of the present invention.

[0177]

According to the present invention, a silver halide color light-sensitive material capable of low replenishment and low discharge processing and exhibiting good color reproducibility and good color forming property can be obtained. Further, the desilvering process can be omitted by using a light-sensitive material having a low coating silver amount as in the present invention.

Claims (2)

[Claims] 1. A silver halide color photographic light-sensitive material having a photographic constituent layer containing at least one silver halide emulsion layer on a support, wherein the photographic constituent layer is represented by at least one of the following general formulas (I). A silver halide color photographic light-sensitive material containing a color-forming reducing agent and a dye-forming coupler represented by the following general formula (II). General formula (I) In the general formula (I), R ¹¹ is an optionally substituted aryl group or heterocyclic group, and R ¹² is optionally substituted alkyl group, alkenyl group, alkynyl group, aryl group or hetero group. It is a cyclic group. X is -SO ₂ -, - CO
-, - COCO -, - CO -O -, - CO-N (R 13)
-, - COCO-O -, - COCO-N (R 13) - or -SO ₂ -N (R ¹³⁾ - it is. Here, R ¹³ is a hydrogen atom or the group described for R ¹² . General formula (II) In the general formula (II), R ²¹ represents a substituted or unsubstituted aliphatic group, aromatic group, heterocyclic group, aromatic amino group, or heterocyclic amino group, and R ²² represents a substituted or unsubstituted acylamino group. Represents a group, X represents a hydrogen atom, a halogen atom, a substituted or unsubstituted aliphatic group, an aromatic group or an acylamino group, and Z represents a hydrogen atom or a group capable of splitting off upon oxidative coupling with a reducing agent for color formation. Represents
Here, R ²² and X may be linked to each other to form a 5- to 7-membered nitrogen-containing heterocycle, and one of R ²¹ , R ²² , X and Z is
One group may form a dimer or higher multimeric coupler. 2. A silver halide color photographic light-sensitive material having a photographic constituent layer containing at least one silver halide emulsion layer on a support, wherein the photographic constituent layer is represented by at least one general formula (I). A silver halide color photographic light-sensitive material comprising a color-forming reducing agent and at least one dye-forming coupler represented by the following general formula (III). General formula (III): In the general formula (III), R ³¹ is —CONR ³⁴ R ³⁵ —, —N
HCOR ³⁴ −, −NHCOOR ³⁶ −, −NHSO ₂ R ³⁶
-, - NHCONR ³⁴ R ³⁵ - represents, R ³² represents a group substitutable on the naphthol ring, m is 0 to an integer of 3, R ³³ represents an acyl group or an oxycarbonyl group,
Y represents a hydrogen atom or a group capable of splitting off upon oxidative coupling with a reducing agent for color formation. However, R ³⁴ and R ³⁵ may be the same or different and each independently represent a hydrogen atom, an aliphatic group, an aromatic group or a heterocyclic group, and R ³⁶ is an aliphatic group,
Represents an aromatic group or a heterocyclic group. R ³² when m is plural
May be the same or different, and may combine with each other to form a condensed ring. R ³² and R ³³ , or R ³³ and Y may be bonded to each other to form a ring.