JP2003050449A - Yellow coupler and silver halide color photographic sensitive material containing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a yellow coupler giving a dye having an excellent hue, a high molecular extinction coefficient and good storage stability, producible in a short process at a low cost and having high color developing property and to provide a silver halide color photographic sensitive material excellent in color reproducibility and sharpness and having good color image fastness. SOLUTION: The yellow coupler is represented by one of formulae (I)-(VII) and the silver halide color photographic sensitive material contains the coupler. In the formulae, R<1> is acyl which may have a substituent, carbamoyl, aryl, the residue of a heterocycle or the like; R<2> is alkyl which may have a substituent, aryl or the residue of a heterocycle; R<3> is aryl which may have a substituent or the residue of a heterocycle; R<4> , R<6> and R<9> are each a substituent; R<5> , R<7> and R<8> are each H or a substituent; (n) is an integer of 0-2; L is a divalent linking group; (k) is an integer of >=0; (m) is an integer of 0-4; and (j) is an integer of 0-3.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a dye-forming coupler which forms an azomethine dye by a coupling reaction with an oxidized product of a developing agent, and a silver halide photographic light-sensitive material containing the coupler.

[0002]

2. Description of the Related Art In a silver halide photographic light-sensitive material (hereinafter sometimes simply referred to as "light-sensitive material") by a subtractive color method, a color image is formed by dyes of three primary colors of yellow, magenta and cyan. In a color photographic method using a current p-phenylenediamine type color developing agent, an acylacetic anilide type compound is used as a yellow coupler. However, the hue of the yellow dye obtained from these couplers is reddish due to poor short-wavelength side absorption, and it is difficult to obtain a highly pure yellow hue, and the molecular absorption coefficient of the dye is also high. Has a problem that a large amount of couplers and silver halides are required to obtain a desired color density, and the sharpness of a color image obtained by increasing the film thickness of the light-sensitive material may decrease. It was Further, the above dyes are easily decomposed under high temperature and high humidity conditions or under light irradiation conditions, and there is a problem in image storability after development processing, and improvement is desired.

In order to solve these problems, the acyl group and the anilide group have been improved, and recently, as a coupler improved from the conventional acylacetic anilide system, a coupler described in JP-A-4-218042 was used. -Alkylcyclopropane carbonylacetic acid anilide compounds
Cyclic malondiamide type couplers described in Japanese Patent No. 11416, European Patent Publication Nos. 953870A1 and 9538.
71A1, No. 953872A1, No. 95387
No. 3A1, No. 953874A1, No. 953875
Pyrrole-2 or 3-yl or indol-2 or 3-ylcarbonylacetic acid anilide type couplers described in A1 etc. have been proposed. The dyes produced from these couplers have improved hue and molecular extinction coefficient over the conventional dyes. However, since these couplers had a low color-forming property, the coupler structure was very complicated in order to improve this. Therefore, it is difficult to synthesize, and the route becomes long, so that the coupler cost becomes high and there is a practical problem.

[0004]

Accordingly, it is an object of the present invention to provide a dye-forming coupler having a high color forming property which can be produced in a short process at a low cost, and further to a halogenated compound containing such a coupler. It is to provide a silver color photographic light-sensitive material.

[0005]

As a result of intensive studies, the present inventors have found that the above problems can be solved by the couplers represented by the following general formulas (I) to (VII). That is, the present invention provides the following yellow coupler and silver halide color photographic light-sensitive material. (1) Yellow couplers represented by the following general formulas (I) to (IV).

[0006]

[Chemical 5]

In the formula, R ¹ is an acyl group which may have a substituent, an aryl group, a heterocyclic residue, an alkoxycarbonyl group, an aryloxycarbonyl group, a carbamoyl group, a sulfamoyl group, an alkylsulfonyl group or an arylsulfonyl group. Or a cyano group or a nitro group.
R ² is an alkyl group, an aryl group or a heterocyclic residue, each of which may have a substituent. Each R ³ is an aryl group or a heterocyclic residue which may have a substituent. R ⁴ represents a substituent. n represents an integer of 0 or more and 2 or less. When n is 2, a plurality of R ⁴ may be the same or different. L represents a divalent linking group. k is an integer of 0 or more, and when k is 2 or more, L may be the same connecting group or different connecting groups.

(2) The yellow coupler as described in (1), wherein the coupler represented by the general formula (III) is represented by the following general formula (V).

[0009]

[Chemical 6]

In the formula, R ⁴ represents a substituent. n represents an integer of 0 or more and 2 or less. When n is 2, a plurality of R ⁴ may be the same or different. R ⁵ represents a hydrogen atom or a substituent. R ⁶ represents a substituent. m represents an integer of 0 or more and 4 or less, and when m is 2 or more, a plurality of R ⁶ may be the same or different and may form a ring with each other. L
Represents a divalent linking group. k is an integer of 0 or more, and k is 2
In the above case, L may be the same connecting group or different connecting groups.

(3) The yellow coupler as described in (1), wherein the coupler represented by the general formula (I) is represented by the following general formula (VI).

[0012]

[Chemical 7]

In the formula, R ⁴ represents a substituent. n represents an integer of 0 or more and 2 or less. When n is 2, a plurality of R ⁴ may be the same or different. R ⁶ represents a substituent. R ⁵ , R
⁷ represents a hydrogen atom or a substituent. m represents an integer of 0 or more and 4 or less, and when m is 2 or more, a plurality of R ⁶ may be the same or different and may form a ring with each other. L represents a divalent linking group. k is an integer of 0 or more, and when k is 2 or more, L may be the same connecting group or different connecting groups.

(4) The yellow coupler as described in (1), wherein the coupler represented by the general formula (III) is represented by the following general formula (VII).

[0015]

[Chemical 8]

Where R^FourRepresents a substituent. n is 0 or more and 2 or more
Represents the lower integer. When n is 2, multiple R4 are the same
But it can be different. R⁶, R⁹Represents a substituent. R
^Five, R ⁸Represents a hydrogen atom or a substituent. m is 0 or more and 4 or more
Represents the lower integer, and when m is 2 or more, multiple R⁶Is that
They may be the same or different, and may form a ring with each other.
good. L represents a divalent linking group. k is an integer of 0 or more
When k is 2 or more, L is the same but different.
It may be a linking group. j represents an integer of 0 or more and 3 or less, and j
When R is 2 or more, multiple R⁹Are the same or different
Or they may form a ring with each other.

(5) A silver halide color photographic light-sensitive material containing at least one of the yellow couplers represented by the general formulas (I) to (VII) described in (1) to (4) above. material.

[0018]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described in detail below. (Dye-forming coupler) Compounds represented by formulas (I) to (IV) of the present invention (also referred to as dye-forming coupler in the present application)
Will be described in detail.

[0019]

[Chemical 9]

In the formula, R ¹ is an acyl group which may have a substituent, an aryl group, a heterocyclic residue, an alkoxycarbonyl group, an aryloxycarbonyl group, a carbamoyl group, a sulfamoyl group, an alkylsulfonyl group, an arylsulfonyl group. Or a cyano group or a nitro group.
Examples of the substituent which R ¹ may have include, for example, a halogen atom, an alkyl group (including a cycloalkyl group and a bicycloalkyl group), an alkenyl group (including a cycloalkenyl group and a bicycloalkenyl group), an alkynyl group. , Aryl group, heterocyclic group, cyano group, hydroxyl group, nitro group, carboxyl group, alkoxy group, aryloxy group, silyloxy group, heterocyclic oxy group, acyloxy group, carbamoyloxy group, alkoxycarbonyloxy group, aryloxycarbonyl Oxy, amino group (including alkylamino group and anilino group), acylamino group, aminocarbonylamino group, alkoxycarbonylamino group, aryloxycarbonylamino group, sulfamoylamino group, alkyl and arylsulfonylamino group, mercapto , An alkylthio group, an arylthio group, a heterocyclic thio group, a sulfamoyl group, a sulfo group,
Alkyl and aryl sulfinyl groups, alkyl and aryl sulfonyl groups, acyl groups, aryloxycarbonyl groups, alkoxycarbonyl groups, carbamoyl groups, aryl and heterocyclic azo groups, imide groups, phosphino groups,
Examples thereof include a phosphinyl group, a phosphinyloxy group, a phosphinylamino group, and a silyl group.

The above-mentioned substituent may be further substituted with a substituent, and examples of the substituent include the above-mentioned groups. Further, the two substituents possessed by R ¹ can combine with each other to form a ring.

An example of R ¹ will be further described below. Acyl group (preferably formyl group, substituted or unsubstituted alkylcarbonyl group having 2 to 30 carbon atoms, substituted or unsubstituted arylcarbonyl group having 7 to 30 carbon atoms, and examples thereof include acetyl, pivaloyl, and 2-chloroacetyl. , Stearoyl, benzoyl, pn-octyloxyphenylcarbonyl), an aryl group (preferably having 6 to 3 carbon atoms).
0 substituted or unsubstituted aryl group such as phenyl, p-tolyl, naphthyl, m-chlorophenyl, o-
Hexadecanoylaminophenyl), a heterocyclic group (preferably a 5- to 7-membered substituted or unsubstituted, saturated or unsaturated, aromatic or non-aromatic, monocyclic or condensed heterocyclic group, and more preferably , A heterocyclic group having a ring-constituting atom selected from a carbon atom, a nitrogen atom and a sulfur atom and having at least one heteroatom selected from a nitrogen atom, an oxygen atom and a sulfur atom, and more preferably a carbon number of 3 to A 5- or 6-membered aromatic heterocyclic group of 30. For example, 2-furyl, 2-thienyl, 2-
Pyridyl, 4-pyridyl, 2-pyrimidinyl, 2-benzothiazolyl, quinazolinon-2-yl, 1,2,4-
Benzothiadiazin-1,1-dioxide-3-yl), alkoxycarbonyl group (preferably having 2 carbon atoms)
To 30 substituted or unsubstituted alkoxycarbonyl groups, for example, methoxycarbonyl, ethoxycarbonyl, t-butoxycarbonyl, n-octadecyloxycarbonyl), aryloxycarbonyl groups (preferably substituted or unsubstituted with 7 to 30 carbon atoms). An aryloxycarbonyl group of, for example, phenoxycarbonyl,
o-chlorophenoxycarbonyl, m-nitrophenoxycarbonyl, pt-butylphenoxycarbonyl), a carbamoyl group (preferably a substituted or unsubstituted carbamoyl having 1 to 30 carbon atoms, for example, carbamoyl, N-methylcarbamoyl, N). , N-dimethylcarbamoyl, N, N-di-n-octylcarbamoyl, N
-(Methylsulfonyl) carbamoyl), a sulfamoyl group (preferably a substituted or unsubstituted sulfamoyl group having 0 to 30 carbon atoms, for example, N-ethylsulfamoyl, N- (3-dodecyloxypropyl) sulfamoyl, N, N-dimethylsulfamoyl, N-acetylsulfamoyl, N-benzoylsulfamoyl, N-
(N′-phenylcarbamoyl) sulfamoyl), an alkyl and arylsulfonyl group (preferably a substituted or unsubstituted alkylsulfonyl group having 1 to 30 carbon atoms,
6-30 substituted or unsubstituted arylsulfonyl groups, such as methylsulfonyl, ethylsulfonyl,
Phenylsulfonyl, p-methylphenylsulfonyl), a cyano group, and a nitro group.

Hereinafter, examples of the substituent that R ¹ may have will be further described. As these substituents, a halogen atom (for example, a chlorine atom, a bromine atom, an iodine atom), an alkyl group (a linear or branched substituted or unsubstituted alkyl group, preferably an alkyl group having 1 to 30 carbon atoms) Yes,
For example, methyl, ethyl, n-propyl, isopropyl,
t-butyl, n-octyl, eicosyl, 2-chloroethyl, 2-cyanoethyl, 2-ethylhexyl, 3-
(2,4-di-t-amylphenoxy) propyl), a cycloalkyl group (preferably a substituted or unsubstituted cycloalkyl group having 3 to 30 carbon atoms, for example, cyclohexyl, cyclopentyl, 4-n-dodecylcyclohexyl). Examples thereof include polycycloalkyl groups such as bicycloalkyl groups (preferably substituted or unsubstituted bicycloalkyl groups having 5 to 30 carbon atoms, such as bicyclo [1,2,2] heptan-2-yl, bicyclo [2
2,2] octane-3-yl) and a group having a polycyclic structure such as a tricycloalkyl group. A monocyclic cycloalkyl group and a bicycloalkyl group are preferable, and a monocyclic cycloalkyl group is particularly preferable. ),

Alkenyl group [A linear or branched substituted or unsubstituted alkenyl group, preferably having 2 to 3 carbon atoms.
0 is an alkenyl group, for example, vinyl, allyl, prenyl, geranyl, oleyl), a cycloalkenyl group (preferably a substituted or unsubstituted cycloalkenyl group having 3 to 30 carbon atoms, for example, 2-cyclopentene-
1-yl, 2-cyclohexen-1-yl), a polycycloalkenyl group, for example, a bicycloalkenyl group (preferably a substituted or unsubstituted bicycloalkenyl group having 5 to 30 carbon atoms, for example, bicyclo [ Two
2,1] hept-2-en-1-yl, bicyclo [2,2]
2,2] oct-2-en-4-yl)], a tricycloalkenyl group or a bicycloalkenyl group, and a monocyclic cycloalkenyl group is particularly preferable. ), An alkynyl group (preferably a substituted or unsubstituted alkynyl group having 2 to 30 carbon atoms, for example, ethynyl, propargyl, trimethylsilylethynyl group),

An aryl group (preferably a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, for example, phenyl,
p-tolyl, naphthyl, m-chlorophenyl, o-hexadecanoylaminophenyl), a heterocyclic group (preferably 5 to 7 membered substituted or unsubstituted, saturated or unsaturated, aromatic or non-aromatic, monocyclic or A condensed ring heterocyclic group, more preferably a heterocycle having a ring-constituting atom selected from a carbon atom, a nitrogen atom and a sulfur atom, and having at least one heteroatom selected from a nitrogen atom, an oxygen atom and a sulfur atom. And more preferably a 5- or 6-membered aromatic heterocyclic group having 3 to 30 carbon atoms, for example, 2-furyl, 2-thienyl, 2-
Pyridyl, 4-pyridyl, 2-pyrimidinyl, 2-benzothiazolyl), cyano group, hydroxyl group, nitro group, carboxyl group,

Alkoxy group (preferably having 1 to 3 carbon atoms)
A substituted or unsubstituted alkoxy group of 0, for example, methoxy, ethoxy, isopropoxy, t-butoxy, n
-Octyloxy, 2-methoxyethoxy), an aryloxy group (preferably a substituted or unsubstituted aryloxy group having 6 to 30 carbon atoms, for example, phenoxy, 2
-Methylphenoxy, 2,4-di-t-amylphenoxy, 4-t-butylphenoxy, 3-nitrophenoxy, 2-tetradecanoylaminophenoxy), silyloxy group (preferably silyloxy group having 3 to 20 carbon atoms) And, for example, trimethylsilyloxy, t-butyldimethylsilyloxy), a heterocyclic oxy group (preferably a substituted or unsubstituted heterocyclic oxy group having 2 to 30 carbon atoms, and the heterocyclic moiety is the aforementioned heterocyclic group). The illustrated heterocycle is preferred, eg 1-phenyltetrazole-5-oxy, 2-tetrahydropyranyloxy),

An acyloxy group (preferably a formyloxy group, a substituted or unsubstituted alkylcarbonyloxy group having 2 to 30 carbon atoms, a substituted or unsubstituted arylcarbonyloxy group having 7 to 30 carbon atoms, for example, acetyloxy , Pivaloyloxy, stearoyloxy, benzoyloxy, p-methoxyphenylcarbonyloxy), a carbamoyloxy group (preferably a substituted or unsubstituted carbamoyloxy group having 1 to 30 carbon atoms, for example, N, N-dimethylcarbamoyloxy,
N, N-diethylcarbamoyloxy, morpholinocarbonyloxy, N, N-di-n-octylaminocarbonyloxy, Nn-octylcarbamoyloxy),
Alkoxycarbonyloxy group (preferably having 2 carbon atoms
~ 30 substituted or unsubstituted alkoxycarbonyloxy groups such as methoxycarbonyloxy, ethoxycarbonyloxy, t-butoxycarbonyloxy, n-
Octylcarbonyloxy), an aryloxycarbonyloxy group (preferably a substituted or unsubstituted aryloxycarbonyloxy group having 7 to 30 carbon atoms, such as phenoxycarbonyloxy, p-methoxyphenoxycarbonyloxy, pn-hexa). Decyloxyphenoxycarbonyloxy),

Amino group (preferably amino group, substituted or unsubstituted alkylamino group having 1 to 30 carbon atoms, substituted or unsubstituted arylamino group having 6 to 30 carbon atoms, heterocyclic ring having 0 to 30 carbon atoms) An amino group, for example, amino, methylamino, dimethylamino, anilino, N-methyl-anilino, diphenylamino, N-1,
3,5-triazin-2-ylamino), acylamino group (preferably formylamino group, substituted or unsubstituted alkylcarbonylamino group having 2 to 30 carbon atoms, substituted or unsubstituted arylcarbonyl group having 7 to 30 carbon atoms) An amino group, for example, acetylamino, pivaloylamino, lauroylamino, benzoylamino, 3,
4,5-tri-n-octyloxyphenylcarbonylamino), an aminocarbonylamino group (preferably a substituted or unsubstituted aminocarbonylamino group having 1 to 30 carbon atoms, for example, carbamoylamino, N, N-dimethylamino) Carbonylamino, N, N-diethylaminocarbonylamino, morpholinocarbonylamino), alkoxycarbonylamino group (preferably having 2 to 3 carbon atoms).
A substituted or unsubstituted alkoxycarbonylamino group of 0, for example, methoxycarbonylamino, ethoxycarbonylamino, t-butoxycarbonylamino, n-octadecyloxycarbonylamino, N-methyl-methoxycarbonylamino),

An aryloxycarbonylamino group (preferably a substituted or unsubstituted aryloxycarbonylamino group having 7 to 30 carbon atoms, for example, phenoxycarbonylamino, p-chlorophenoxycarbonylamino, m-n-octyloxyphenoxy). Carbonylamino), sulfamoylamino group (preferably having 0 carbon atoms
To 30 substituted or unsubstituted sulfamoylamino groups, for example, sulfamoylamino, N, N-dimethylaminosulfonylamino, Nn-octylaminosulfonylamino), alkyl and arylsulfonylamino groups (preferably A substituted or unsubstituted alkylsulfonylamino group having 1 to 30 carbon atoms, a substituted or unsubstituted arylsulfonylamino group having 6 to 30 carbon atoms,
For example, methylsulfonylamino, butylsulfonylamino, phenylsulfonylamino, 2,3,5-trichlorophenylsulfonylamino, p-methylphenylsulfonylamino), a mercapto group,

Alkylthio group (preferably having 1 to 1 carbon atoms)
A substituted or unsubstituted alkylthio group of 30 such as methylthio, ethylthio, n-hexadecylthio), an arylthio group (preferably a substituted or unsubstituted arylthio group having 6 to 30 carbon atoms such as phenylthio,
p-chlorophenylthio, m-methoxyphenylthio), a heterocyclic thio group (preferably a substituted or unsubstituted heterocyclic thio group having 2 to 30 carbon atoms, and the heterocyclic moiety is the heterocyclic group described above. The ring portion is preferable, for example, 2-benzothiazolylthio, 1-phenyltetrazol-5-ylthio), a sulfamoyl group (preferably a substituted or unsubstituted sulfamoyl group having 0 to 30 carbon atoms, for example, N-ethylsulfur). Famoyl, N- (3-
Dodecyloxypropyl) sulfamoyl, N, N-dimethylsulfamoyl, N-acetylsulfamoyl,
N-benzoylsulfamoyl, N- (N'-phenylcarbamoyl) sulfamoyl), sulfo group,

Alkyl and arylsulfinyl groups (preferably a substituted or unsubstituted alkylsulfinyl group having 1 to 30 carbon atoms, a substituted or unsubstituted arylsulfinyl group having 6 to 30 carbon atoms, for example, methylsulfinyl, ethylsulfinyl, Phenylsulfinyl, p-
Methylphenylsulfinyl), an alkyl and arylsulfonyl group (preferably a substituted or unsubstituted alkylsulfonyl group having 1 to 30 carbon atoms, a substituted or unsubstituted arylsulfonyl group having 6 to 30 carbon atoms, and examples thereof include methylsulfonyl and ethyl. Sulfonyl, phenylsulfonyl, p-methylphenylsulfonyl), an acyl group (preferably formyl group, a substituted or unsubstituted alkylcarbonyl group having 2 to 30 carbon atoms, a substituted or unsubstituted arylcarbonyl group having 7 to 30 carbon atoms) Yes, for example, acetyl, pivaloyl, 2-chloroacetyl, stearoyl, benzoyl, pn-octyloxyphenylcarbonyl), an aryloxycarbonyl group (preferably,
A substituted or unsubstituted aryloxycarbonyl group having 7 to 30 carbon atoms, for example, phenoxycarbonyl, o-
Chlorophenoxycarbonyl, m-nitrophenoxycarbonyl, pt-butylphenoxycarbonyl),

Alkoxycarbonyl group (preferably a substituted or unsubstituted alkoxycarbonyl group having 2 to 30 carbon atoms, for example, methoxycarbonyl, ethoxycarbonyl, t-butoxycarbonyl, n-octadecyloxycarbonyl), carbamoyl group (preferably A substituted or unsubstituted carbamoyl having 1 to 30 carbon atoms, for example, carbamoyl, N-methylcarbamoyl, N, N-
Dimethylcarbamoyl, N, N-di-n-octylcarbamoyl, N- (methylsulfonyl) carbamoyl),
Aryl and heterocyclic azo groups (preferably having 6 to 3 carbon atoms)
A substituted or unsubstituted arylazo group having 0 to 3 carbon atoms
30 substituted or unsubstituted heterocyclic azo groups (the heterocyclic part is preferably the heterocyclic part described in the above heterocyclic group), for example, phenylazo, p-chlorophenylazo, 5-ethylthio-1,3,4 -Thiadiazole-2
-Ylazo), an imide group (preferably having 2 to 30 carbon atoms)
A substituted or unsubstituted imide group, for example, N-succinimide, N-phthalimide), a phosphino group (preferably a substituted or unsubstituted phosphino group having 2 to 30 carbon atoms, for example, dimethylphosphino, diphenylphosphino, Methylphenoxyphosphino), a phosphinyl group (preferably a substituted or unsubstituted phosphinyl group having 0 to 30 carbon atoms, for example, phosphinyl, dioctyloxyphosphinyl, diethoxyphosphinyl),

Phosphinyloxy group (preferably a substituted or unsubstituted phosphinyloxy group having 2 to 30 carbon atoms, for example, diphenoxyphosphinyloxy, dioctyloxyphosphinyloxy), phosphinyl Amino group (preferably a substituted or unsubstituted phosphinylamino group having 2 to 30 carbon atoms, for example, dimethoxyphosphinylamino, dimethylaminophosphinylamino), a silyl group (preferably 0 to 0 carbon atoms) Thirty substituted or unsubstituted silyl groups, including, for example, trimethylsilyl, t-butyldimethylsilyl, phenyldimethylsilyl).

Among the above functional groups, those having a hydrogen atom may be removed by removing the hydrogen atom and further substituted with the above group. Examples of such functional groups include alkylcarbonylaminosulfonyl groups, arylcarbonylaminosulfonyl groups, alkylsulfonylaminocarbonyl groups,
Examples thereof include an arylsulfonylaminocarbonyl group, and specific examples thereof include a methylsulfonylaminocarbonyl group, a p-methylphenylsulfonylaminocarbonyl group, an acetylaminosulfonyl group, and a benzoylaminosulfonyl group.

R ¹ is preferably an acyl group which may have a substituent, a carbamoyl group, an aryl group or a heterocyclic residue, more preferably an acyl group which may have a substituent or carbamoyl. Group and a heterocyclic residue, more preferably an acyl group and a carbamoyl group, each of which may have a substituent, and most preferably a substituted carbamoyl group.

R in the general formulas (I) to (IV)²Is replaced
An alkyl group which may have a group, an aryl group or a hetero group
Ring residues, and examples of the substituents that these may have
Is R ¹Examples of the substituent that may have are given.

R ³ is an aryl group which may have a substituent or a heterocyclic residue, preferably a heterocyclic residue. Further, examples of the substituent which these may have are R
Examples of the substituent which ¹ may have are given.

R ⁴ is a substituent, and examples of these include the examples of the substituent which R ¹ may have. Also, n
When is 2, plural R ⁴ may be the same or different.

In order to immobilize the coupler in the light-sensitive material, at least one of R ¹ , R ² , R ^{3 and} R ⁴ preferably has a total carbon number including the substituents of 8 or more and 50 or less, More preferably, the total carbon number is 10 or more and 40 or less.

L represents a divalent linking group. Examples of L include, for example, methylene group, alkylene group such as ethylene group, arylene group such as phenylene group, heterocyclic group, oxygen atom, nitrogen atom, sulfur atom, carbonyl group, sulfonyl group, phosphorus atom, phosphonyl group, Examples thereof include boron atoms. An alkylene group is preferred, a methylene group and an ethylene group are more preferred, and a methylene group is most preferred.

Further, k is an integer of 0 or more, and when k is 2 or more, L may be the same connecting group or different connecting groups. Preferably, k is 0 or more and 5 or less, more preferably 0 or more and 2 or less, still more preferably 0 or 1, and most preferably 0.

In the present invention, among the general formulas (I) to (IV), a coupler represented by the general formula (I) is preferable, and in the general formula (I), R ¹ is an alkylcarbonyl group or aryl. Carbonyl group, heterocyclic carbonyl group, carbamoyl group, alkoxycarbonyl group,
It is a heterocyclic residue, more preferably R ¹ is an alkylcarbonyl group, a heterocyclic carbonyl group, or a carbamoyl group. More preferably, the following general formulas (V) to (VI
I) is preferable, and general formula (V) is particularly preferable.

Next, the compound represented by formula (V) of the present invention (also referred to as dye-forming coupler in the present application) will be described in detail.

[0044]

[Chemical 10]

In the general formula (V), R ⁴ , L, k and n are the same as those described in the general formulas (I) to (IV), and the preferred ranges are also the same.

R ⁵ represents a hydrogen atom or a substituent. Examples of this substituent include those mentioned above as examples of the substituent which R ¹ may have. R ⁵ is preferably a halogen atom, an alkyl group, an alkoxy group, an aryloxy group, an alkoxycarbonyl group, an aryloxycarbonyl group, a carbamoyl group, a sulfamoyl group, an acylamino group, an alkyl or arylsulfonylamino group, and more preferably a halogen atom. , An alkyl group, an alkoxy group, and an aryloxy group, more preferably a halogen atom and an alkoxy group, and most preferably an alkoxy group.

R ⁶ represents a substituent. Examples of this substituent include those mentioned above as examples of the substituent which R ¹ may have. Preferably, R ⁶ is a halogen atom, an alkyl group, an alkoxy group, an aryloxy group, an alkoxycarbonyl group, an aryloxycarbonyl group, a carbamoyl group, a sulfamoyl group, an acylamino group, an alkyl or arylsulfonylamino group. m represents an integer of 0 or more and 4 or less, and when m is 2 or more, a plurality of R ⁶ may be the same or different and may combine with each other to form a ring.

Next, the compound represented by formula (VI) of the present invention (also referred to as a dye-forming coupler in the present application) will be described in detail.

[0049]

[Chemical 11]

In the general formula (VI), R ⁴ , R ⁵ , R ⁶ ,
L, k and n represent the same as those described in the general formula (V), and the preferable ranges are also the same.

R⁷Represents a hydrogen atom or a substituent. this
Examples of the substituent include the aforementioned R¹Of the substituent that may have
Examples include the ones listed above. Preferably R⁷Is
Hydrogen atom, alkyl group, alkoxy group, aryloxy
It is a base. More preferably, R ⁷Is an alkyl group.

Next, the compound represented by formula (VII) of the present invention (also referred to as a dye-forming coupler in the present application) will be described in detail.

[0053]

[Chemical 12]

In the general formula (VII), R ⁴ , R ⁵ , R ⁶ ,
L, k and n represent the same as those described in the general formula (V), and the preferable ranges are also the same.

R ⁸ represents a hydrogen atom or a substituent. Examples of this substituent include those mentioned above as examples of the substituent which R ¹ may have. Preferably R ⁸ is an alkyl group or an aryl group. More preferably R ⁸ is an alkyl group.

R ⁹ represents a substituent. Examples of this substituent include those mentioned above as examples of the substituent which R ¹ may have. R ⁹ is preferably an alkyl group, an acyl group, a halogen atom, a carbonyl group, an alkoxy group, an albonamide group, a carbamoyl group, a heterocyclic group or an aryl group. More preferably, it is an aryl group. When R ⁹ is present as a substituent at the 2 or 5 position of the azo ring, it may form a ring with R ⁸ .

J represents an integer of 0 or more and 3 or less, and when j is 2 or more, a plurality of R ^9's may be the same or different and may combine with each other to form a ring.

Preferred examples of the couplers represented by formulas (I) to (VII) in the present invention are shown below, but the present invention is not limited thereto.

[0059]

[Chemical 13]

[0060]

[Chemical 14]

[0061]

[Chemical 15]

[0062]

[Chemical 16]

[0063]

[Chemical 17]

[0064]

[Chemical 18]

[0065]

[Chemical 19]

[0066]

[Chemical 20]

[0067]

[Chemical 21]

[0068]

[Chemical formula 22]

[0069]

[Chemical formula 23]

In the following description, when the exemplified compounds shown above (also referred to as dye-forming couplers) are cited, the number (x) in parentheses attached to each exemplified compound is used to indicate "coupler". (X) ”will be displayed.

Specific synthesis examples of the compounds represented by the above general formulas (I) to (VII) are shown below. Synthesis Example 1: Synthesis of coupler (1) Coupler (1) was synthesized by the route shown below.

[0072]

[Chemical formula 24]

Compound (A-0) (purity 95%) 83.4
1.0 liter of g methyl alcohol solution (hereinafter,
Also referred to as “L”. ) To 27.4 g of hydrazine hydrochloride
Was added, and the mixture was stirred at room temperature overnight. 400 ml of water
(Hereinafter also referred to as "mL"), ethyl ether 800
mL was added and stirred, and the insoluble material was filtered off. The filtrate was extracted with ethyl ether, the organic layer was dried over anhydrous magnesium sulfate, and the solvent was evaporated under reduced pressure. Crystallization from acetonitrile gave 40.0 g of compound (A-1).

4.5 mL of 1,8-diazabicyclo [5.4.0] -7-undecene was added to a solution of 3.4 g of the compound (A-1) in 50 mL of N, N-dimethylacetamide.
To this, 6 mL of N, N-dimethylacetamide containing 6.3 g of the compound (A) synthesized according to the method described in JP-A-5-11416 was added dropwise. After the completion of dropping, the mixture was stirred overnight at room temperature. Ethyl acetate and water were added and the layers were separated, and the organic layer was washed with diluted hydrochloric acid and saturated brine. After drying over anhydrous magnesium sulfate, the solvent was distilled off under reduced pressure and crystallization from a mixed solvent of ethyl acetate and hexane gave 6.1 g of compound (A-2).

To a mixed solution of 6.1 g of the compound (A-2) in 20 mL of tetrahydrofuran and 55 mL of methyl alcohol, 2
27 mL of N sodium hydroxide aqueous solution was added. 50 ° C
It was stirred for 3 hours. The mixture was neutralized with diluted hydrochloric acid and ethyl acetate was added to separate the layers. After drying over anhydrous magnesium sulfate, the solvent was distilled off under reduced pressure and crystallization from a mixed solvent of ethyl acetate and hexane gave 5.3 g of coupler (1).

Synthesis Example 2: Synthesis of coupler (2) The coupler (2) was synthesized by the route shown below.

[0077]

[Chemical 25]

24.0 g of sodium hydride (60%) was stirred in hexane to remove hexane. Add 400 mL of tetrahydrofuran and cool with ice, then acetylacetone 5
50 mL of 0.0 g tetrahydrofuran solution was added dropwise 1
Stir for hours. 50 mL of a tetrahydrofuran solution of 52.0 mL of ethyl α-bromoacetate was dropped, and after the dropping, the temperature was gradually raised to room temperature. After stirring for 4 hours, the mixture was poured into saturated saline and separated with ethyl acetate and water. The organic layer was dried over anhydrous magnesium sulfate, and the solvent was evaporated under reduced pressure to give the compound (B-
69.9 g of an oily substance of 1) was obtained.

A solution of 50 g of the compound (B-1) in 170 mL of ethyl alcohol was added with hydrazine monohydrate under ice cooling.
5g was added slowly. The temperature was raised to room temperature and the mixture was stirred overnight. Ethyl acetate and water were added for liquid separation, and the organic layer was washed with saturated brine. The organic layer was dried over anhydrous magnesium sulfate, and the solvent was evaporated under reduced pressure to give compound (B-2) oil 4
4.6 g was obtained.

To a solution of 7.6 g of compound (B-2) in 100 mL of N, N-dimethylacetamide, 6.7 mL of 1,8-diazabicyclo [5.4.0] -7-undecene was added. To this, 10 mL of N, N-dimethylacetamide containing 9.4 g of compound (A) was added dropwise. After the completion of dropping, the mixture was stirred overnight at room temperature. Ethyl acetate and water were added and the layers were separated, and the organic layer was washed with diluted hydrochloric acid and saturated brine. After drying over anhydrous magnesium sulfate, the solvent was evaporated under reduced pressure and crystallization from a mixed solvent of ethyl acetate and hexane gave 9.7 g of compound (B-3).

To a mixed solution of 7.2 g of the compound (B-3) in 30 mL of tetrahydrofuran and 80 mL of methyl alcohol, 2
30.0 mL of an aqueous solution of N-hydroxide atrium was added. 5
The mixture was stirred at 0 ° C for 3 hours. The mixture was neutralized with diluted hydrochloric acid and ethyl acetate was added to separate the layers. After drying over anhydrous magnesium sulfate, the solvent was distilled off under reduced pressure, and crystallization from a mixed solvent of ethyl acetate and hexane gave 6.0 g of coupler (2).

Synthesis Example 3: Synthesis of coupler (3) The coupler (3) was synthesized by the route shown below.

[0083]

[Chemical formula 26]

Acetone (8.5 mL) and dimethyl oxalate (13.7 g) were gradually added to a solution of sodium methoxide (9.41 g) in methyl alcohol (100 mL), and the mixture was heated under reflux for 3 times.
Stir for hours. After cooling to room temperature, it was concentrated under reduced pressure. Acidify the system with dilute hydrochloric acid and extract with ethyl acetate.
The organic layer was washed with saturated saline. The organic layer was dried over anhydrous magnesium sulfate, the solvent was evaporated under reduced pressure, and the residue was crystallized from a mixed solvent of ethyl alcohol and hexane to obtain 33.3 g of compound (C-1).

A solution of 33.3 g of compound (C-1) in 110 mL of ethyl alcohol was added to hydrazine monohydrate 1 under ice cooling.
0.5g was added slowly. The temperature was raised to room temperature and the mixture was stirred overnight. Ethyl acetate and water were added for liquid separation, and the organic layer was washed with saturated brine. The organic layer was dried over anhydrous magnesium sulfate, the solvent was distilled off under reduced pressure, and crystallized from a mixed solvent of ethyl acetate and hexane to obtain 30.0 g of compound (C-2).

To a solution of 6.9 g of the compound (C-2) in 100 mL of N, N-dimethylacetamide was added 6.7 mL of 1,8-diazabicyclo [5.4.0] -7-undecene. To this, 10 mL of N, N-dimethylacetamide containing 9.4 g of compound (A) was added dropwise. After the completion of dropping, the mixture was stirred overnight at room temperature. Ethyl acetate and water were added and the layers were separated, and the organic layer was washed with diluted hydrochloric acid and saturated brine. After drying over anhydrous magnesium sulfate, the solvent was distilled off under reduced pressure to obtain the compound (C-3).
8.9 g of oil was obtained.

2 g of a mixed solution of 7.0 g of compound (C-3) in 30 mL of tetrahydrofuran and 80 mL of methyl alcohol was added.
30.0 mL of an aqueous solution of N-hydroxide atrium was added. 5
The mixture was stirred at 0 ° C for 3 hours. The mixture was neutralized with diluted hydrochloric acid and ethyl acetate was added to separate the layers. After drying over anhydrous magnesium sulfate, the solvent was distilled off under reduced pressure, and crystallization was performed from a mixed solvent of ethyl acetate and hexane to obtain 5.7 g of coupler (3).

Synthesis Example 4: Synthesis of coupler (41) Coupler (41) was synthesized by the following route.

[0089]

[Chemical 27]

4.5 mL of 1,8-diazabicyclo [5.4.0] -7-undecene was added to a solution of 3.4 g of the compound (A-1) in 50 mL of N, N-dimethylacetamide.
To this product, 6 mL of N, N-dimethylacetamide of 8.9 g of compound (B) synthesized according to the method described in JP-A-4-218042 was added dropwise. After the completion of dropping, the mixture was stirred overnight at room temperature. Ethyl acetate and water were added and the layers were separated, and the organic layer was washed with diluted hydrochloric acid and saturated brine. After drying over anhydrous magnesium sulfate, the solvent was distilled off under reduced pressure, and crystallization was performed from a mixed solvent of ethyl acetate and hexane to obtain 7.6 g of compound (D-1).

To a mixed solution of 6.4 g of the compound (D-1) in 20 mL of tetrahydrofuran and 55 mL of methyl alcohol, 2
30 mL of N sodium hydroxide aqueous solution was added. 50 ° C
It was stirred for 3 hours. The mixture was neutralized with diluted hydrochloric acid and ethyl acetate was added to separate the layers. After drying over anhydrous magnesium sulfate, the solvent was distilled off under reduced pressure, and crystallization from a mixed solvent of ethyl acetate and hexane gave 4.5 g of coupler (41).

Synthesis Example 5: Synthesis of coupler- (51) Coupler- (51) was synthesized by the route shown below.

[0093]

[Chemical 28]

Compound (C) 12.1 g of dichloromethane 2 synthesized according to the method described in US 6,057,087
N-chlorosuccinimide (abbreviated as NCS) in a 00 ml solution
4.0 g was added and the mixture was stirred at room temperature for 2 hours. Ethyl acetate and water were added and the layers were separated, and the organic layer was washed with diluted hydrochloric acid and saturated brine. After drying over anhydrous magnesium sulfate, the solvent was distilled off under reduced pressure to obtain a compound (E-1) as a crude product.

9.0 mL of 1,8-diazabicyclo [5.4.0] -7-undecene was added to a solution of 7.6 g of the compound (A-1) in 100 mL of N, N-dimethylacetamide. To this, 20 mL of N, N-dimethylacetamide of compound (E-1) was added dropwise. After the dropping was completed, the temperature was raised to 70 ° C. and the mixture was stirred for 4 hours. Ethyl acetate and water were added and the layers were separated, and the organic layer was washed with diluted hydrochloric acid and saturated brine. After drying over anhydrous magnesium sulfate, the solvent was distilled off under reduced pressure, and the compound (E-2) 1 was crystallized from a mixed solvent of ethyl acetate and hexane.
0.2 g was obtained.

To a mixed solution of 7.9 g of compound (E-2) in 20 mL of tetrahydrofuran and 55 mL of methyl alcohol, 2
30 mL of N sodium hydroxide aqueous solution was added. 50 ° C
It was stirred for 3 hours. The mixture was neutralized with diluted hydrochloric acid and ethyl acetate was added to separate the layers. After drying over anhydrous magnesium sulfate, the solvent was distilled off under reduced pressure, and crystallization from a mixed solvent of ethyl acetate and hexane gave 5.0 g of coupler (51).

(Silver halide photographic light-sensitive material) The light-sensitive material of the present invention is a silver halide photographic light-sensitive material comprising a support and at least one light-sensitive layer formed on the support. It contains a dye-forming coupler which is a compound represented by the general formula (I) to (IV) or the general formula (V), and the coupler is contained in a hydrophilic colloid layer composed of a usual gelatin binder. It In a general light-sensitive material, at least one light-sensitive emulsion layer (light-sensitive layer) of a blue-sensitive silver halide emulsion layer, a green-sensitive silver halide emulsion layer and a red-sensitive silver halide emulsion layer is coated on a support. However, the order may be any order. Also, an infrared sensitive silver halide emulsion layer can be used in place of one of the above photosensitive emulsion layers. These photosensitive emulsion layers contain a silver halide emulsion having sensitivity in each wavelength range and a coupler that forms a dye having a complementary color relationship with the light to be exposed to perform color reproduction in the subtractive color method. You can However, the photosensitive emulsion layer and the hue of the coupler may not have the above correspondence.

The dye-forming couplers represented by the above formulas (I) to (IV) or the above formula (V) can be used in any photosensitive emulsion layer (preferably, a blue-sensitive silver halide emulsion layer or a green-sensitive halogen). It is a silver halide emulsion layer, and particularly preferably a blue-sensitive silver halide emulsion layer).

The dye-forming couplers represented by the general formulas (I) to (IV) or the general formula (V) are mainly yellow couplers when combined with a color developing agent of p-phenylenediamines. Alternatively, it is useful as a magenta coupler, particularly as a yellow coupler. Therefore, when the silver halide photographic light-sensitive material of the present invention uses p-phenylenediamines as a color developing agent, it can be expressed by the general formulas (I) to (IV) or the general formula (V).
The dye-forming coupler represented by the formula (1) is preferably contained in the yellow color-forming layer or the magenta color-forming layer, and particularly preferably in the yellow color-forming layer. Further, the dye-forming couplers represented by the above general formulas (I) to (IV) or the above general formula (V) give dyes of various hues even in a system using a color developing agent other than p-phenylenediamines. It is useful as a dye-forming coupler.

In the silver halide photographic light-sensitive material of the present invention
And the coupler is 1 × 1 per mol of silver halide.
0^-3~ 1 mol is preferably added, 2 x 10^-3~ 3x
10 ^-1More preferably, it is added in moles.

The coupler can be introduced into the light-sensitive material by various known dispersion methods, is dissolved in a high-boiling organic solvent (if necessary, a low-boiling organic solvent is also used), and is emulsified and dispersed in a gelatin aqueous solution to form a silver halide emulsion. The oil-in-water dispersion method of adding to is preferred. Examples of the high boiling point solvent used in the oil-in-water dispersion method are disclosed in JP-A-5-313327 and JP-A-5-323539.
No. 5,323,541, No. 6-258803, No. 8-262662, and US Pat. No. 2,322,027. Further, steps of latex dispersion method as one of polymer dispersion methods, effects, and specific examples of latex for impregnation are described in US Pat. No. 4,199,363 and West German Patent Application (OLS) 2,541,274. , The same 2,
No. 541,230, Japanese Patent Publication No. 53-41091, European Patent Publication No. 029104, and the like, and regarding dispersion with an organic solvent-soluble polymer, PCT International Publication No. WO88 / 00723 and JP-A-5-15042.
No. 0 etc. Methacrylate-based or acrylamide-based polymers are preferable, and acrylamide-based polymers are particularly preferable in terms of image fastness. Here, the high boiling point means a boiling point of 175 ° C. or higher under normal pressure.

Examples of the high boiling point solvent used in the present invention are described in US Pat. No. 2,322,027 and the like. Specific examples of the high-boiling point organic solvent having a boiling point of 175 ° C. or higher at atmospheric pressure include phthalic acid esters [eg, dibutyl phthalate, dicyclohexyl phthalate, di-2-ethylhexyl phthalate, decyl phthalate, bis (2,4-diethyl phthalate). -Tert-amylphenyl) phthalate, bis (2,4-di-tert-amylphenyl) isophthalate, bis (1,1-diethylpropyl) phthalate],
Esters of phosphoric acid or phosphonic acid (for example, triphenyl phosphate, tricresyl phosphate, 2-ethylhexyl diphenyl phosphate, tricyclohexyl phosphate, tri-2-ethylhexyl phosphate, tridodecyl phosphate, tributoxyethyl phosphate, trichloropropyl phosphate) , The-
2-ethylhexylphenylphosphonate), benzoic acid esters (eg, 2-ethylhexylbenzoate, dodecylbenzoate, 2-ethylhexyl-p-
Hydroxybenzoate), amides (eg, N, N
-Diethyldodecane amide, N, N-diethyllaurylamide, N-tetradecylpyrrolidone), sulfonamides (e.g., N-butylbenzenesulfonamide),
Alcohols or phenols (isostearyl alcohol, 2,4-di-tert-amylphenol), aliphatic carboxylic acid esters (eg, bis (2-ethylhexyl) sebacate, dioctyl azelate, glycerol tributyrate, isostearyl) Lactate, trioctyl citrate), aniline derivatives (N, N-dibutyl-2-butoxy-5-tert-octylaniline, etc.),
Hydrocarbons (eg paraffin, dodecylbenzene,
Diisopropylnaphthalene), chlorinated paraffins and the like. Particularly, phosphoric acid esters and JP-A-6-258
The hydrogen donating compounds described in No. 803 and No. 8-262662 are excellent in hue and can be preferably used.

Incidentally, in order to reduce the load on the environment,
Instead of phthalates, European Patent EP-9693
20A1 and EP-969321A1 are preferably used. In addition to these, tributyl citrate,
Examples thereof include pentaglycerin triester.

The dielectric constant of the high boiling point organic solvent varies depending on the purpose, but it is preferably 2.0 to 7.0, more preferably 3.0 to 6.0. The high boiling point organic solvent is a mass ratio of 0 to 10 times, preferably 0 to 4 times the amount of the coupler,
It is preferably used.

The auxiliary solvent may be an organic solvent having a boiling point of 30 ° C. or higher, preferably 50 ° C. or higher and about 160 ° C. or lower. Typical examples are ethyl acetate, butyl acetate, ethyl propionate and methyl ethyl ketone. ,
Cyclohexanone, 2-ethoxyethyl acetate, dimethylformamide are mentioned.

From the viewpoints of improving stability over time during storage in the state of emulsion dispersion, suppressing photographic performance change and improving stability over time in the final composition for coating mixed with an emulsion, the emulsion dispersion may be added as necessary. Then, all or part of the auxiliary solvent can be removed by a method such as vacuum distillation, noodle washing, or ultrafiltration.

The average particle size (diameter) of the lipophilic fine particle dispersion thus obtained is 0.001 to 1.0 μm.
Is more preferable, 0.05 to 0.30 μm is more preferable, and 0.08 to 0.20 μm is most preferable.
The average particle size can be measured using a Coulter submicron particle analyzer model N4 (Coulter Electronics Co., Ltd.) or the like. If the average particle size of the lipophilic fine particle dispersion is large, problems such as a decrease in coupler color development efficiency and deterioration of the glossiness of the surface of the light-sensitive material are likely to occur.If the size is too small, the dispersion viscosity increases. ， It becomes difficult to handle during manufacturing.

The amount of the lipophilic fine particle dispersion comprising the coupler of the present invention used with respect to the dispersion medium is preferably 2 to 0.1, and more preferably 1.
It is in the range of 0 to 0.2. Here, as the dispersion medium, for example, gelatin is representative, and hydrophilic polymers such as polyvinyl alcohol can be mentioned. The lipophilic fine particle dispersion may contain various compounds according to the purpose together with the coupler of the present invention.

The light-sensitive material used in the present invention can be provided with at least one layer of red-sensitive, green-sensitive and blue-sensitive layers on a support. As a typical example, a silver halide photographic light-sensitive material having on a support at least one light-sensitive layer composed of a plurality of silver halide emulsion layers having substantially the same color sensitivity but different sensitivities. Is. The photosensitive layer is a unit photosensitive layer having color sensitivity to any of blue light, green light, and red light, and in a multilayer silver halide color photographic light-sensitive material, the arrangement of the unit photosensitive layers is generally
The red color-sensitive layer, the green color-sensitive layer and the blue color-sensitive layer are arranged in this order from the support side. However, the order of installation may be reversed depending on the purpose, or the order of installation may be such that different photosensitive layers are sandwiched between the same color-sensitive layers. A non-photosensitive layer may be provided between the above-described silver halide photosensitive layers and as the uppermost layer and the lowermost layer. These may contain a coupler, a DIR compound, a color mixing inhibitor, etc. described later. The plurality of silver halide emulsion layers constituting each unit photosensitive layer is DE 1,
121, 470 or GB 923, 045, a high-sensitivity emulsion layer and a low-sensitivity emulsion layer.
It is preferable to arrange them so that the photosensitivity becomes lower toward the support. Further, JP-A-57-112751, 62.
-200350, 62-206541, 62-20
As described in 6543, a low-sensitivity emulsion layer may be provided on the side farther from the support, and a high-sensitivity emulsion layer may be provided on the side closer to the support.

As a specific example, from the side farthest from the support,
Low sensitivity blue sensitive layer (BL) / high sensitivity blue sensitive layer (BH) / high sensitivity green sensitive layer (GH) / low sensitivity green sensitive layer (GL) / high sensitivity red sensitive layer (RH) / low sensitivity red sensitive layer It can be installed in the order of (RL), in the order of BH / BL / GL / GH / RH / RL, or in the order of BH / BL / GH / GL / RL / RH. Further, as described in JP-B-55-34932, the layers can be arranged in the order of blue-sensitive layer / GH / RH / GL / RL from the side farthest from the support. Also, JP-A-56-25738 and JP-A-62-63936.
It is also possible to arrange in the order of blue-sensitive layer / GL / RL / GH / RH from the side farthest from the support, as described in 1.

Further, as described in JP-B-49-15495, the upper layer is a silver halide emulsion layer having the highest sensitivity, the middle layer is a silver halide emulsion layer having a lower sensitivity, and the lower layer is further than the middle layer. An arrangement may be mentioned in which a silver halide emulsion layer having a low photosensitivity is arranged and three layers having different sensitivities are sequentially lowered toward the support.

Even when it is composed of such three layers having different sensitivities, as described in JP-A-59-202464, a medium-sensitivity emulsion from the side remote from the support in the same color-sensitive layer. Layers / high-speed emulsion layers / low-speed emulsion layers may be arranged in this order. In addition, the layers may be arranged in the order of high-speed emulsion layer / low-speed emulsion layer / medium-speed emulsion layer, or low-speed emulsion layer / medium-speed emulsion layer / high-speed emulsion layer. Also, in the case of four or more layers, the arrangement may be changed as described above.

Further, it is preferable to utilize the interlayer suppression effect as a means for improving color reproducibility. The centroid sensitivity wavelength (λ _-R ) of the spectral sensitivity distribution of the multilayer effect that the above red-sensitive silver halide emulsion layer (when there are a plurality of layers, the plurality of layers as a whole) receives from other layers in the range of 500 nm to 600 nm. Is 500 nm <λ _-R ≤560 nm,
And the green-sensitive silver halide emulsion layer of the center of gravity sensitivity wavelength of the spectral sensitivity distribution of (plurality of cases as a whole their multiple layers) (lambda _G) is a 520nm <λ _G ≦ 580nm, and lambda _G It is preferable that −λ _−R ≧ 5 nm.

As the sensitizing dye and solid disperse dye used at this time, those described in JP-A No. 11-305396 can be used. The center-of-gravity sensitivity wavelength of the spectral sensitivity distribution of the multilayer effect that the red-sensitive silver halide emulsion layer receives from other layers can be determined by the method described in JP-A No. 11-305396.

The silver halide photographic light-sensitive material used in the present invention preferably contains at least one compound which reacts with the oxidation product of the developing agent obtained by development to release the development inhibitor or its precursor. For example, DIR (development inhibitor releasing type) coupler, DIR-hydroquinone, D
A coupler or the like that releases IR-hydroquinone or its precursor is used.

The silver halide grains used in the layer which gives a multi-layer effect to the red-sensitive layer are not particularly limited in size and shape, but so-called tabular grains having a high aspect ratio and monodisperse emulsions having a uniform grain size. Silver iodobromide grains having a layered structure of iodine are preferably used.
Further, in order to expand the exposure latitude, it is preferable to mix two or more kinds of emulsions having different grain sizes.

The donor layer which gives a multi-layer effect to the red-sensitive layer may be applied at any position on the support, but it is applied at a position closer to the support than the blue-sensitive layer and farther from the support than the red-sensitive layer. Preferably. Further, it is more preferably on the side closer to the support than the yellow filter layer.

The donor layer that gives the red-sensitive layer a layering effect is preferably closer to the support than the green-sensitive layer and farther from the support than the red-sensitive layer, and closer to the support of the green-sensitive layer. Most preferably, it is located adjacent to the side. In this case, "adjacent" means that no intermediate layer is interposed. The layer that gives the red-sensitive layer a multilayer effect may be composed of a plurality of layers. In that case, those positions may be adjacent to or apart from each other.

The emulsion used in the light-sensitive material used in the present invention may be a surface latent image type which forms a latent image mainly on the surface, an internal latent image type which is formed inside the grain, or a type which has a latent image both on the surface and inside. Either may be used, but it is necessary that the emulsion is a negative type. Among the internal latent image types, JP-A-63-26
The core / shell type internal latent image type emulsion described in 4740 may be used, and its preparation method is described in JP-A-59-133542. The thickness of the shell of this emulsion varies depending on the development process and the like, but is preferably 3 to 40 nm, particularly preferably 5 to 20 nm.

The silver halide emulsion is usually one which has been physically ripened, chemically sensitized and spectrally sensitized. The additive used in such a process is RD No. 1764
3, the same No. 18716 and the same No. No. 307105, and the relevant parts are summarized in the table below.

In the light-sensitive material used in the present invention, two or more kinds of emulsions having different characteristics of at least one of the grain size, grain size distribution, halogen composition, grain shape, and sensitivity of the light-sensitive silver halide emulsion are contained in the same layer. It can be used as a mixture.

US (US Patent) 4,082,553 grain surface-fogged silver halide grains, US
No. 4,626,498, and silver halide grains in which the inside of the grains is fogged, colloidal silver as a photosensitive silver halide emulsion layer and / or a substantially non-photosensitive hydrophilic colloid layer. Is preferably applied to.
The fogged silver halide grain inside or on the surface means a silver halide grain which enables uniform (non-imagewise) development regardless of the unexposed area and exposed area of the light-sensitive material. , Its preparation method is described in US Pat. No. 4,626,498 and JP-A-59-214852. The silver halide forming the inner core of a core / shell type silver halide grain having a fogged inside may have a different halogen composition. As the silver halide whose inside or surface is fogged, any of silver chloride, silver chlorobromide, silver iodobromide and silver chloroiodobromide can be used. The average grain size of these fogged silver halide grains is 0.01
˜0.75 μm, particularly preferably 0.05 to 0.6 μm. The grain shape may be regular grain or polydisperse emulsion, but monodispersity (at least 95% of the mass or number of silver halide grains has a grain size within ± 40% of the average grain size). It is preferable that

In the present invention, it is preferable to use a non-photosensitive fine grain silver halide. The non-photosensitive fine grain silver halide is a fine grain of silver halide which is not exposed to light during imagewise exposure for obtaining a dye image and is not substantially developed in the development process, and it is preferable that it is not fogged in advance. . The fine grain silver halide has a silver bromide content of 0 to 100 mol%, and may optionally contain silver chloride and / or silver iodide. Preferred is one containing 0.5 to 10 mol% of silver iodide. Fine grain silver halide has an average grain size (average diameter of circles equivalent to the projected area)
0.01 to 0.5 μm is preferable, and 0.02 to 0.2 μm is more preferable.

The fine grain silver halide can be prepared in the same manner as in the case of ordinary photosensitive silver halide. The surface of the silver halide grain does not need to be optically sensitized nor spectrally sensitized. However, prior to adding this to the coating liquid, triazole-based, azaindene-based,
It is preferable to add a known stabilizer such as a benzothiazolium-based or mercapto-based compound or a zinc compound. Colloidal silver can be contained in the fine silver halide grain-containing layer.

The above-mentioned various additives are used in the light-sensitive material of the present technology, but various additives other than the above can be used depending on the purpose. These additives are
For more details, Research Disclosure Item 176
43 (December 1978), Item 18716 (19)
1979 November) and the same Item 308119 (1989)
December, 2012), and the relevant parts are summarized in the table below. Additive type RD17643 RD18716 RD308119 1 Chemical sensitizer page 23 648 page right column 996 page 2 Sensitivity enhancer Same as above 3 Spectral sensitizer, pages 23 to 24 page 648 right column to 996 right to 998 right supersensitizer Page 649 right column 4 brightener page 24 998 right 5 antifoggant page 24 to 25 page 649 right column 998 right to 1000 right and stabilizer 6 light absorber, page 25 to 26 page 649 right column to 1003 left to 1003 Right Filter dye Page 650 Left column UV absorber 7 Anti-staining agent Page 25 Right column 650 Left to right column 1002 Right 8 Dye image stabilizer Page 25 1002 Right 9 Hardener 26 pages Page 651 Left column 1004 Right to 1005 Left 10 Binder page 26 Same as above 1003 Right to 1004 right 11 Plasticizer and lubricant page 27 650 Right column 1006 Left to 1006 right 12 Coating aid, page 26 to 27 Same as above 1005 Left to 1006 left Surfactant 13 Static page 27 Same as above 1006 Right to 1007 Left Preventive agent 14 Matting agent 1008 Left to 1009 Left

Various dye-forming couplers can be used in the light-sensitive material of the present invention in combination with the couplers represented by formulas (I) to (VII) according to the present invention.
The following couplers are particularly preferred. Yellow couplers: couplers represented by formulas (I) and (II) of EP 502,424A; couplers represented by formulas (1) and (2) of EP 513,496A (particularly Y-28 on page 18); EP 568,037A Claim 1
A coupler represented by formula (I) in US Pat. No. 5,066,576, column 1, lines 45 to 55; a coupler represented by formula (I) in paragraph 0008 of JP-A-4-274425; A coupler according to claim 1 of EP 498,381A1 on page 40 (particularly D-35 on page 18); a coupler of the formula (Y) on page 4 of EP 447,969A1 (in particular Y-1 (page 17), Y -54 (p. 41)); US
Couplers represented by formulas (II) to (IV) on lines 36 to 58 of column 4, 476, 219 (especially II-17, 19 (column 17), II-24 (column 19)).

Magenta coupler; JP-A-3-39737 (L-57 (1
Page 1 (bottom right), L-68 (page 12 bottom right), L-77 (page 13 bottom right); EP 456,
257 (A-4) -63 (page 134), (A-4) -73, -75 (page 139);
EP486,965 M-4, -6 (page 26), M-7 (page 27); EP 571,959A
M-45 (page 19); JP-A-5-204106 (M-1) (page 6); JP-A-4-
M-22 of paragraph 0237 of 362631.

Cyan coupler: CX-1, JP-A-4-204843
3,4,5,11,12,14,15 (pages 14 to 16); JP-A-4-43345, C-
7,10 (35 pages), 34, 35 (37 pages), (I-1), (I-17) (42 to 43 pages);
A coupler represented by formula (Ia) or (Ib) of claim 1 of JP-A-6-67385. Polymer coupler: P-1, P-5 of JP-A-2-44345 (page 11).

Examples of couplers in which the color forming dye has an appropriate diffusibility include US 4,366,237, GB 2,125,570, EP 96,873B,
Those described in DE 3,234,533 are preferred. The coupler for correcting the unwanted absorption of the color forming dye is a yellow-colored cyan coupler represented by the formulas (CI), (CII), (CIII) and (CIV) described on page 5 of EP 456,257A1 (especially on page 84). YC-86), the EP
Yellow colored magenta coupler ExM-7 (202
Page), EX-1 (page 249), EX-7 (page 251), US 4,833,069
Magenta colored cyan coupler CC-9 (column
8), CC-13 (column 10), US 4,837,136 (2) (column 8),
The colorless masking couplers represented by formula (A) in claim 1 of WO92 / 11575 (in particular, the exemplified compounds on pages 36 to 45) are preferred.

Examples of the compound (including coupler) which releases a photographically useful compound residue by reacting with an oxidized product of a developing agent include the following. Development inhibitor releasing compound:
Compounds represented by formulas (I), (II), (III) and (IV) described on page 11 of EP 378, 236A1 (particularly T-101 (page 30), T-104 (page 31), T-11
3 (page 36), T-131 (page 45), T-144 (page 51), T-158 (page 58)), EP43
Compounds represented by formula (I) on page 7 of 6,938A2 (especially D-49 (page 51)), compounds represented by formula (1) of EP 568,037A (especially (23) (page 11)), Compounds represented by formulas (I), (II) and (III) described on pages 5 to 6 of EP 440,195A2 (especially on page 29)
I- (1)); Bleach accelerator releasing compounds: compounds represented by formulas (I) and (I ') on page 5 of EP 310,125A2 (particularly (60) and (6 on page 1)
1)) and a compound represented by the formula (I) of claim 1 of JP-A-6-59411 (particularly (7) (page 7); Ligand releasing compound: US
Compound represented by LIG-X described in claim 1 of 4,555,478 (especially compound on lines 21 to 41 of column 12); Leuco dye releasing compound: Compound 1 of columns 3 to 8 of US 4,749,641
~ 6; Fluorescent dye-releasing compound: C in claim 1 of US 4,774,181
Compounds represented by OUP-DYE (particularly compounds 1 to 11 in columns 7 to 10); development accelerator or fogging agent releasing compound: US
4,656,123, column 3, compounds represented by formulas (1), (2), and (3) (particularly (I-22) in column 25) and EP 450,637A2
ExZK-2 on page 75, lines 36-38; compounds which release a dye group only upon leaving: Formula of claim 1 of US 4,857,447
Compounds represented by (I) (especially Y-1 to Y- of columns 25 to 36)
19).

As the additives other than the coupler, the following are preferable. Dispersion medium of oil-soluble organic compound: P-3,5 of JP-A-62-215272
16,19,25,30,42,49,54,55,66,81,85,86,93 (140〜144
Page); Latex for impregnation of oil-soluble organic compounds: US 4,199,
Latex described in 363; Oxidized developer scavenger: a compound represented by the formula (I) in column 2, lines 54 to 62 of US 4,978,606 (particularly I-, (1), (2), (6), (12 ) (Column 4-
5), US Pat. No. 4,923,787, column 2, lines 5-10 (especially compound 1 (column 3); stain inhibitor: EP 298321A, 4).
Formulas (I)-(III) on pages 30-33, especially I-47, 72, III-1, 27 (24
~ Page 48); Anti-fading agent: A-6,7,20,21,23,2 of EP 298321A
4,25,26,30,37,40,42,48,63,90,92,94,164 (69〜118
Pp.), US 5,122,444, columns 25-38, II-1 to III-23, especially
III-10, EP 471347A, pages 8-12, I-1 to III-4, especially II-
2, US 5,139,931 columns 32-40 A-1 to 48, especially A-39,
42; Materials that reduce the use of color-enhancing agents or color-mixing inhibitors: EP 411324A, I-1 to II-15, pages 5 to 24, especially I-4
6; Formalin scavenger: EP 477932A, pages 24 to 29, SCV-1 to 28, especially SCV-8; Hardener: JP-A 1-214845
Formulas in columns 13-23 of H-1,4,6,8,14, US 4,618,573 on page 17
Compounds (H-1 to 54) represented by (VII) to (XII), JP-A-2-
214852, page 8, lower right, compound represented by formula (6) (H-1 to 7
6), especially the compound described in claim 1 of H-14, US 3,325,287; Development inhibitor precursor: P-2 of JP-A-62-168139
4,37,39 (pages 6-7); compounds as claimed in claim 1 of US 5,019,492, in particular column 7, 28,29; preservatives, fungicides: US
4,923,790 columns 3 to 15 I-1 to III-43, especially II-1,
9,10,18, III-25; Stabilizers, antifoggants: US 4,923,79
I-1 to (14) in columns 6 to 16 of 3, especially I-1,60, (2), (13), U
S 4,952,483 columns 25-32 compounds 1-65, especially 36:
Chemical sensitizer: triphenylphosphine selenide, compound 50 of JP-A-5-40324; dye: 15-18 of JP-A-3-156450
A-1 to b-20, especially a-1,12,18,27,35,36, b-5,27 to 29
Pages V-1 to 23, especially V-1, EP 445627A pages 33 to 55 FI-
1 to F-II-43, especially FI-11, F-II-8, EP 457153A 17 to 28
Pages III-1 to 36, especially III-1,3, WO 88/04794 8-26
Microcrystalline dispersion of Dye-1 to 124, compounds 1 to 22 of EP 319999A, pages 6 to 11, especially compound 1, compounds D-1 to 87 (3) represented by formulas (1) to (3) of EP 519306A. ~ Page 28), US 4,26
Compounds 1-22 represented by formula (I) of 8,622 (columns 3-1
0), a compound (1) represented by the formula (I) of US 4,923,788 ~
(31) (Columns 2 to 9); UV absorber: Formula of JP-A-46-3335
Compounds (18b) to (18r), 101 to 427 (6 to
(Page 9), compounds (3) to (6 represented by formula (I) of EP 520938A.
6) (pages 10 to 44) and the compound HBT-1 represented by the formula (III).
~ 10 (page 14), compounds represented by formula (1) of EP 521823A
(1) to (31) (columns 2 to 9).

The present invention can be applied to various color light-sensitive materials such as color negative films for general use or movies, color reversal films for slides or televisions, color papers, color positive films and color reversal papers. In addition, Japanese Examined Fairness 2-32615, Actual Fairness 3
Suitable for the film unit with a lens described in -39784. Suitable supports that can be used in the present invention include
For example, page 28 of the above-mentioned RD. No. 17643, 64 of the same RD.
From page 7, right column to page 648, left column, and No. 307105, page 879.

In the light-sensitive material of the present invention, the thickness from the light-sensitive silver halide layer closest to the support to the surface of the photographic light-sensitive material is preferably 24 μm or less, more preferably 22 μm or less. The film swelling speed T _1/2 is preferably 30 seconds or less, more preferably 20 seconds or less. T _1/2 is the time until the film thickness reaches 1/2 when 90% of the maximum swollen film thickness reached when the film is processed with a color developer at 30 ° C. for 3 minutes and 15 seconds is a saturated film thickness. It is defined as The film thickness is 25 ° C and 55% relative humidity
Means the film thickness measured in tone humidity (2 days), T _1/2 is, er Green (A.Green) et al., Photographic Science and Engineering (Photogr.Sci.En
It can be measured by using a swellometer (swelling meter) of the type described in g.), page 19, pages 2,124 to 129. T
_1/2 can be adjusted by adding a hardening agent to gelatin as a binder or changing the aging condition after coating. The swelling rate is preferably 150 to 400%. The swelling ratio can be calculated from the maximum swollen film thickness under the conditions described above by the formula: (maximum swollen film thickness-film thickness) / film thickness.

The light-sensitive material of the present invention is preferably provided with a hydrophilic colloid layer (referred to as a back layer) having a total dry film thickness of 2 μm to 20 μm on the side opposite to the side having the emulsion layer. This back layer contains the above-mentioned light absorber, filter dye, ultraviolet absorber, antistatic agent, hardener, binder,
It is preferable to add a plasticizer, a lubricant, a coating aid, and a surface active agent. The swelling ratio of this back layer is preferably 150 to 500%.

The light-sensitive material of the present invention has the above-mentioned RD. No. 1764.
Pp. 28-29, No. 18716, 651, left column to right column, and N.
It can be developed by a usual method described on pages 880 to 881 of O.307105.

Next, the processing liquid for the color negative film used in the present invention will be described. The color developing solution used in the present invention is described on page 9, upper right column, line 1 of JP-A-4-121739.
The compounds described on page 11, lower left column, line 4 can be used. As a color developing agent for particularly rapid processing, 2-methyl-4- [N-ethyl-N- (2-hydroxyethyl) amino] aniline, 2-methyl-4- [N
-Ethyl-N- (3-hydroxypropyl) amino] aniline and 2-methyl-4- [N-ethyl-N- (4-hydroxybutyl) amino] aniline are preferred.

These color developing agents are preferably used in the range of 0.01 to 0.08 mol per liter of color developing solution,
Particularly, it is preferably used in the range of 0.015 to 0.06 mol, more preferably 0.02 to 0.05 mol. The replenisher for the color developing solution preferably contains 1.1 to 3 times the concentration of the color developing agent, and particularly preferably 1.3 to 2.5 times the concentration.

Hydroxylamine can be widely used as a preservative in the color developing solution, but when higher preservability is required, substitution of an alkyl group, a hydroxyalkyl group, a sulfoalkyl group, a carboxyalkyl group or the like is required. A hydroxylamine derivative having a group is preferable, and specifically, N, N-di (sulfoethyl) hydroxylamine, monomethylhydroxylamine, dimethylhydroxylamine, monoethylhydroxylamine, diethylhydroxylamine, N, N-di (carboxyethyl). Hydroxylamine is preferred. Among the above, N, N-di (sulfoethyl) hydroxylamine is particularly preferable. These may be used in combination with hydroxylamine, but it is preferable to use one type or two or more types in place of hydroxylamine.

The preservative is preferably used in the range of 0.02 to 0.2 mol, particularly 0.03 to 0.15 mol, and further preferably 0.04 to 0.1 mol, per liter. The replenisher preferably contains a preservative at a concentration 1.1 to 3 times that of the mother liquor (processing tank liquid), as in the case of the color developing agent.

In the color developing solution, a sulfite is used as an anti-tarring agent for the oxide of the color developing agent. The sulfite is preferably used in the range of 0.01 to 0.05 mol per liter, particularly preferably in the range of 0.02 to 0.04 mol. It is preferable to use the replenisher at a concentration of 1.1 to 3 times these concentrations.

The pH of the color developer is preferably in the range of 9.8 to 11.0, particularly preferably 10.0 to 10.5, and the replenisher is set to a high value in the range of 0.1 to 1.0 from these values. It is preferable to set. Known buffers such as carbonates, phosphates, sulfosalicylates and borates are used to maintain such a pH stable. The replenishing amount of the color developing solution is preferably 80 to 1300 mL per 1 m ² of the light-sensitive material, but is preferably smaller from the viewpoint of reducing environmental pollution load, specifically 80 to 600 mL, further 80 to 400 mL.
mL is preferred.

The bromide ion concentration in the color developing solution is usually 0.01 to 0.06 mol per liter, but fog is suppressed while maintaining sensitivity, improving discrimination, and improving graininess. From the purpose, per 1L
It is preferably set to 0.015 to 0.03 mol. When the bromide ion concentration is set in such a range, the replenisher may contain the bromide ion calculated by the following formula. However, when C becomes negative, it is preferable that the replenisher do not contain bromide ions. C = A-W / V C: Bromide ion concentration (mol / L) in color developing replenisher A: Target bromide ion concentration (mol / L) in color developing solution W: 1 m ² of light-sensitive material is colored Amount of bromide ions eluted from the light-sensitive material to the color-developing solution when developed (mol) V: Replenishment amount (L) of color-developing replenisher for the light-sensitive material of 1 m ²

When the replenishment amount is reduced or when the bromide ion concentration is set to a high level, 1-phenyl-3-pyrazolidone or 1-phenyl-
Pyrazolidones represented by 2-methyl-2-hydroxymethyl-3-pyrazolidone and 3,6-dithia-1,8
It is also preferable to use a development accelerator such as a thioether compound represented by octanediol.

The compounds and processing conditions described in JP-A-4-125558, page 4, lower left column, line 16 to page 7, lower left column, line 6 can be applied to the processing solution having a bleaching ability in the present invention. . The bleaching agent preferably has an oxidation-reduction potential of 150 mV or higher, and specific examples thereof include JP-A-5-72694 and JP-A-5-17331.
The compounds described in 2 are preferred, and 1,3-diaminopropanetetraacetic acid, and the ferric complex salt of the compound of Specific Example 1 on page 7 of JP-A No. 5-173312 are particularly preferred.

Further, in order to improve the biodegradability of the bleaching agent, JP-A-4-218845, 4-268552, EP588,289, 591,
It is preferable to use the compound ferric iron complex salt described in 934 and JP-A-6-208213 as a bleaching agent. The concentration of these bleaching agents is preferably 0.05 to 0.3 mol per 1 L of the bleaching solution, and particularly 0.1% for the purpose of reducing the amount discharged to the environment.
It is preferable to design in the range of 0.15 to 0.15 mol. When the bleaching solution has a bleaching ability, it is 0.2 mol / L or less.
It is preferred to include 1 mole of bromide, especially 0.3
It is preferable to contain ~ 0.8 mol.

The replenisher for the solution having the bleaching ability basically contains the concentrations of the respective components calculated by the following formula. Thereby, the concentration in the mother liquor can be maintained constant. CR = CT × (V1 + V2) / V1 + CP CR: Concentration of component in replenishing solution CT: Concentration of component in mother liquor (processing tank solution) CP: Concentration of component consumed during processing V1: 1 m ² for light-sensitive material Replenishing amount of replenisher having bleaching capacity (mL) V2: 1m ² of light-sensitive material brought in from the previous bath (m
L)

In addition, it is preferable to add a pH buffer to the bleaching solution, and it is particularly preferable to add a dicarboxylic acid having a low odor, such as succinic acid, maleic acid, malonic acid, glutaric acid and adipic acid. In addition, JP-A-53-9
It is also preferred to use the known bleaching accelerators described in 5630, RD No. 17129, US 3,893,858. The bleaching solution is preferably supplemented with 50 to 1000 mL of the bleach replenishing solution per 1 m ² of the light-sensitive material, particularly 80 to 500 mL, and further 100 to 300 m.
It is preferable to supplement L. Further, the bleaching solution is preferably aerated.

For the processing liquid having fixing ability, see Japanese Patent Application Laid-Open No.
The compounds and treatment conditions described in 4-125558, page 7, lower left column, line 10 to page 8, lower right column, line 19 can be applied. In particular, in order to improve the fixing speed and the homeostasis, the compounds represented by the general formulas (I) and (II) of JP-A-6-301169 are contained alone or in combination in a processing solution having fixing ability. It is preferable. In addition to the p-toluenesulfinic acid salt, the sulfinic acid described in JP-A 1-224762 can also be used.
It is preferable from the viewpoint of improving the homeostasis.

It is preferable to use ammonium as a cation in a liquid having a bleaching ability and a liquid having a fixing ability from the viewpoint of improving desilvering property, but for the purpose of reducing environmental pollution, the amount of ammonium is reduced or reduced to zero. Is preferred.

In the bleaching, bleach-fixing and fixing steps, jet stirring described in JP-A-1-309059 is particularly preferable. The replenishing amount of the replenishing solution in the bleach-fixing or fixing step is 100 to 1000 mL, preferably 150 to 700 mL, and particularly preferably 200 to 600 mL per 1 m ² of the light-sensitive material.

In the bleach-fixing and fixing steps, it is preferable to install various kinds of silver recovery devices in-line or off-line to recover silver. By installing in-line, it is possible to reduce the silver concentration in the solution and process it, and as a result, the replenishment amount can be reduced. It is also preferable to recover silver off-line and reuse the residual liquid as a replenisher.

The bleach-fixing step and the fixing step can be composed of a plurality of processing tanks, and it is preferable that each tank is of a multistage countercurrent system by cascade piping. In consideration of the balance with the size of the developing machine, the two-tank cascade configuration is generally efficient, and the processing time ratio between the front tank and the rear tank is preferably in the range of 0.5: 1 to 1: 0.5. Particularly, the range of 0.8: 1 to 1: 0.8 is preferable.

From the viewpoint of improving the preservability, it is preferable to allow a free chelating agent which is not a metal complex to be present in the bleach-fixing solution or the fixing solution. As these chelating agents, the bleaching solution is described. It is preferred to use biodegradable chelating agents.

With respect to the washing and stabilizing steps, the contents described in JP-A-4-125558, page 12, lower right column, line 6 to page 13, lower right column, line 16 can be preferably applied. In particular,
Instead of formaldehyde for stabilizers, use EP 504,609,
Azolylmethylamines described in 519,190 and JP-A-4-36
It is preferable to use the N-methylolazoles described in 2943, or to dimerize the magenta coupler into a surfactant solution containing no image stabilizer such as formaldehyde, from the viewpoint of maintaining the working environment. . Further, in order to reduce the adhesion of dust to the magnetic recording layer coated on the light-sensitive material, the stabilizing solution described in JP-A-6-289559 can be preferably used.

The amount of washing and replenishment of the stabilizing solution depends on the amount of the light-sensitive material 1.
80-1000 mL is preferred per m ² , especially 100-500 m
L, and further, 150 to 300 mL is a preferable range from the viewpoint of both ensuring the washing or stabilizing function and reducing the waste liquid for environmental protection. In the process performed with such a supplement amount,
In order to prevent the reproduction of bacteria and mold, known antifungal agents such as thiabendazole, 1,2-benzisothiazolin-3-one and 5-chloro-2-methylisothiazolin-3-one, and antibiotics such as gentamicin, It is preferable to use water deionized with an ion exchange resin or the like. It is more effective to use deionized water in combination with antibacterial agents and antibiotics.

The liquid in the tank for washing or stabilizing liquid is
JP-A-3-46652, JP-A-3-53246, JP-A-355542, JP-A-3-121448,
It is also preferable to perform the reverse osmosis membrane treatment described in JP-A 3-126030 to reduce the replenishment amount. In this case, the reverse osmosis membrane is preferably a low pressure reverse osmosis membrane.

In the processing of the present invention, it is particularly preferable to carry out the evaporation correction of the processing liquid disclosed in the Technical Report of the Institute of Invention, Technical Report 94-4992. In particular, a method of making a correction using the temperature and humidity information of the environment where the developing machine is installed is preferable based on (Equation-1) on page 2. The water used for evaporation correction is preferably collected from the replenishment tank for washing,
In that case, it is preferable to use deionized water as the replenishing water for washing.

As the treating agent used in the present invention, those described on page 3, right column, line 15 to page 4, left column, line 32 of the above-mentioned Kokai Giho are preferable. Also, as a developing machine used for this,
The film processors described in lines 22 to 28 in the right column of page 3 are preferred.

Specific examples of preferred processing agents, automatic processors, and evaporation correction methods for carrying out the present invention are described on page 5, right column, line 11 to page 7, right column, last line of the above-mentioned published technical report. Has been done.

The supply form of the treating agent used in the present invention is as follows:
It may be in any form such as a concentrated or concentrated liquid preparation, a granule, a powder, a tablet, a paste or an emulsion. As an example of such a treating agent, JP-A-63-1
7453 is a liquid agent stored in a container with low oxygen permeability,
19655, 4-230748, vacuum packed powder or granules, 4-221951 granules containing a water-soluble polymer,
JP-A-51-61837 and JP-A-6-102628 have tablets and special tables
00485 discloses a paste-like treatment agent, and any of them can be preferably used, but from the viewpoint of convenience in use,
It is preferable to use a liquid which has been prepared in advance in a concentration at the state of use.

Polyethylene, polypropylene, polyvinyl chloride, polyethylene terephthalate, nylon and the like are used alone or as a composite material in the container for accommodating these treating agents. These are selected according to the level of oxygen permeability required. For a liquid such as a color developing solution which is easily oxidized, a material having low oxygen permeability is preferable, and specifically, polyethylene terephthalate or a composite material of polyethylene and nylon is preferable. These materials have a thickness of 500 to 1500 μm, are used for a container, and preferably have an oxygen permeability of 20 mL / m ² · 24 hrs · atm or less.

Next, the processing liquid for color reversal film used in the present invention will be explained. Regarding processing for color reversal film, known technology No. 6 (April 1, 1991), page 1, line 5 to page 10, line 5, and page 15, line 8 to page 24, 2 of Aztec Co., Ltd. It is described in detail in the line, and any of its contents can be preferably applied.

In the processing of the color reversal film, the image stabilizer is contained in the conditioning bath or the final bath. Examples of such an image stabilizer include formaldehyde sodium bisulfite and N-methylolazoles in addition to formalin, and sodium formaldehyde bisulfite or N-methylolazoles are preferable from the viewpoint of working environment, and N-methylol is preferable. As the azole, N-methyloltriazole is particularly preferable. The contents relating to the color developing solution, the bleaching solution, the fixing solution, the washing water, etc. described in the processing of the color negative film can be preferably applied to the processing of the color reversal film. As a preferred color reversal film processing agent containing the above contents, Eastman Kodak E-6 processing agent and Fuji Photo Film Co., Ltd.
The CR-56 treating agent can be used.

Next, the magnetic recording layer preferably used in the present invention will be described. The magnetic recording layer preferably used in the present invention is a layer in which an aqueous or organic solvent-based coating liquid in which magnetic particles are dispersed in a binder is coated on a support.

The magnetic particles used in the present invention are γFe ₂ O.
Ferromagnetic iron oxide such as _3, Co deposited γFe ₂ O _3, Co coated magnetite, Co containing magnetite, ferromagnetic chromium dioxide, ferromagnetic metal, ferromagnetic alloy, hexagonal system Ba ferrite, Sr ferrite, Pb ferrite , Ca ferrite, etc. can be used. Co-deposited ferromagnetic iron oxides such as Co-deposited γFe ₂ O ₃ are preferred. The shape may be needle-like, rice grain-like, spherical, cubic, plate-like or the like. Preferably at least 20 m ² / g in S _BET is the specific surface area, and particularly preferably equal to or greater than 30 m ² / g.

The saturation magnetization (σs) of the ferromagnetic material is preferably 3.0 × 10 ^{4 to} 3.0 × 10 ⁵ A / m, particularly preferably 4.0 ×.
10 ^{4 to} 2.5 × 10 ⁵ A / m. The ferromagnetic particles may be surface-treated with silica and / or alumina or an organic material. Further, the magnetic particles may be treated with a silane coupling agent or a titanium coupling agent on the surface thereof as described in JP-A-6-101632. In addition, JP-A-4-25
Inorganic on the surface described in No. 9911 and No. 5-81652,
Magnetic particles coated with an organic substance can also be used.

The binder used for the magnetic particles is a thermoplastic resin, a thermosetting resin, a radiation curable resin, a reactive resin, an acid, an alkali or a biodegradable polymer, a natural product described in JP-A-4-219569. Polymers (cellulose derivatives, sugar derivatives, etc.) and mixtures thereof can be used. The Tg of the above resin is -40 ° C to 300 ° C, and the mass average molecular weight is 20,000 to 1,000,000. Examples thereof include vinyl copolymers, cellulose diacetate, cellulose triacetate, cellulose acetate propionate, cellulose acetate butyrate, cellulose tripropionate and other cellulose derivatives, acrylic resins, polyvinyl acetal resins, and gelatin is also preferable. Cellulose di (tri) acetate is particularly preferable.
The binder can be hardened by adding an epoxy-based, aziridine-based, or isocyanate-based crosslinking agent.
Examples of the isocyanate-based cross-linking agent include isocyanates such as tolylene diisocyanate, 4,4′-diphenylmethane diisocyanate, hexamethylene diisocyanate, and xylylene diisocyanate, and reaction products of these isocyanates and polyalcohols (for example, tolylene diisocyanate). Examples thereof include a reaction product of 3 mol of isocyanate and 1 mol of trimethylolpropane, and polyisocyanate produced by condensation of these isocyanates, which are described in, for example, JP-A-6-59357.

As a method for dispersing the above-mentioned magnetic material in the above binder, a kneader, a pin type mill, an annular type mill or the like is preferable and a combination thereof is also preferable, as in the method described in JP-A-6-35092. JP-A-5-08828
The dispersant described in No. 3 and other known dispersants can be used. The thickness of the magnetic recording layer is 0.1 μm to 10 μm, preferably 0.2 μm to 5 μm, more preferably 0.3 μm to 3 μm. The mass ratio of the magnetic particles and the binder is preferably 0.5:
It is composed of 100 to 60: 100, and more preferably 1: 100 to 30: 100. The coating amount of the magnetic particles is 0.005 to 3 g / m ² , preferably
It is 0.01 to ² g / m ² , and more preferably 0.02 to 0.5 g / m ² .
The transmission yellow density of the magnetic recording layer is preferably 0.01 to 0.50, more preferably 0.03 to 0.20, and particularly preferably 0.04 to 0.15.

The magnetic recording layer can be provided on the entire back surface of the photographic support by coating or printing, or in the form of a stripe. As a method of applying the magnetic recording layer, an air doctor, a blade, an air knife, a squeeze, an impregnation, a reverse roll, a transfer roll, a gravure, a kiss,
Cast, spray, dip, bar, extrusion and the like can be used, and the coating liquids described in JP-A-5-341436 and the like are preferable.

In the magnetic recording layer, improvement of lubricity, curl adjustment,
It may have functions such as antistatic, adhesion prevention, and head polishing, or may be provided with another functional layer to impart these functions, and at least one kind of particles has a Mohs hardness of 5 or more. The above-mentioned non-spherical inorganic particle abrasives are preferable. The composition of the non-spherical inorganic particles is preferably oxides such as aluminum oxide, chromium oxide, silicon dioxide and titanium dioxide, carbides such as silicon carbide, silicon carbide and titanium carbide, and fine powder such as diamond. The surface of these abrasives may be treated with a silane coupling agent or a titanium coupling agent. These particles may be added to the magnetic recording layer, or may be overcoated (for example, a protective layer, a lubricant layer, etc.) on the magnetic recording layer. As the binder used at this time, the above-mentioned binders can be used, and preferably the same binder as that of the magnetic recording layer is used. US Pat. No. 5,336,589, US Pat. No. 5,250,404, US Pat.
5,229,259, 5,215,874 and EP 466,130.

Next, the polyester support preferably used in the present invention will be described. For details, including the light-sensitive material, processing, cartridges and examples described later, open technical report, official technique number 94-6023 (Invention Society; 1994.3.15.). The polyester used in the present invention is formed by using a diol and an aromatic dicarboxylic acid as essential components. As the aromatic dicarboxylic acid, 2,6-, 1,5-, 1,4-, and 2,7-naphthalenedicarboxylic acid, terephthalic acid are used. Examples of the acid, isophthalic acid, phthalic acid and diol include diethylene glycol, triethylene glycol, cyclohexanedimethanol, bisphenol A and bisphenol. Examples of the polymerized polymer include homopolymers such as polyethylene terephthalate, polyethylene naphthalate, and polycyclohexanedimethanol terephthalate. Particularly preferred is a polyester containing 50 to 100 mol% of 2,6-naphthalenedicarboxylic acid. Among them, particularly preferred is polyethylene-2,
It is 6-naphthalate. Average molecular weight range is about 5,000
To 200,000. The polyester of the present invention has a Tg of 50.
C. or higher, more preferably 90.degree. C. or higher.

Next, the polyester support has a curl habit.
In order to make it difficult to heat, the heat treatment temperature should be 40 ° C or higher and lower than Tg.
More preferably, the heat treatment is carried out at Tg-20 ° C or higher and lower than Tg.
The heat treatment may be carried out at a constant temperature within this temperature range,
You may heat-process, cooling. This heat treatment time is 0.
1 hour or more and 1500 hours or less, more preferably 0.5 hours or more
It is less than 200 hours. The heat treatment of the support is roll-like and practical.
It may be applied, or it may be carried out in web form.
Good. Unevenness is added to the surface (eg SnO₂And Sb₂O _FiveGuidance of etc.
Electrolytic inorganic fine particles may be applied), and the surface condition may be improved.
Yes. In addition, knurling is added to the ends so that only the ends are slightly raised.
By doing so, we will take measures such as preventing the cut end of the core from appearing.
Is desirable. These heat treatments are performed on the surface after the support is formed into a film.
After processing, after applying the back layer (antistatic agent, slip agent, etc.), below
It may be carried out at any stage after coating. Preferred
Is after application of the antistatic agent.

An ultraviolet absorber may be kneaded into this polyester. In order to prevent light piping, it is possible to achieve the object by kneading commercially available dyes or pigments for polyester such as Diaresin manufactured by Mitsubishi Kasei and Kayaset manufactured by Nippon Kayaku.

Next, in the present invention, it is preferable to carry out a surface treatment in order to bond the support and the light-sensitive material constituting layer. Chemical treatment, mechanical treatment, corona discharge treatment, flame treatment, ultraviolet treatment, high frequency treatment, glow discharge treatment, active plasma treatment,
Surface activation treatments such as laser treatment, mixed acid treatment and ozone oxidation treatment can be mentioned. Among the surface treatments, ultraviolet irradiation treatment, flame treatment, corona treatment and glow treatment are preferable.

The undercoating method may be a single layer or two or more layers. As the binder for the undercoat layer,
Starting with copolymers starting from monomers selected from vinyl chloride, vinylidene chloride, butadiene, methacrylic acid, acrylic acid, itaconic acid, maleic anhydride, etc., polyethyleneimine, epoxy resin, grafting Examples thereof include gelatin, nitrocellulose, and gelatin.
Compounds that swell the support include resorcin and p-chlorophenol. In the undercoat layer, as a gelatin hardening agent, chromium salts (chrome alum, etc.), aldehydes (formaldehyde, glutaraldehyde, etc.), isocyanates, active halogen compounds (2,4-dichloro-6) are used.
-Hydroxy-S-triazine, etc.), epichlorohydrin resin, active vinyl sulfone compound and the like. SiO ₂ , TiO ₂ , inorganic fine particles or polymethylmethacrylate copolymer fine particles (0.01 to 10 μm) may be contained as a matting agent.

Further, in the present invention, an antistatic agent is preferably used. As those antistatic agents, carboxylic acids and carboxylates, polymers containing sulfonates,
Examples thereof include cationic polymers and ionic surfactant compounds.

The most preferable antistatic agent is Zn.
O, TiO₂, SnO₂, Al₂O₃, In₂O₃, SiO ₂, MgO, BaO, Mo
O₃, V₂O_FiveAt least one volume resistivity selected from
Ten⁷Ω · cm or less, more preferably 10^FiveGrains that are Ω · cm or less
Child size 0.001-1.0μm Crystalline metal oxide or
Fine particles of these complex oxides (Sb, P, B, In, S, Si, C, etc.),
Furthermore, sol-like metal oxides or their composite oxides
It is a fine particle.

The content in the light-sensitive material is 5 to 500 mg / m²But
Particularly preferably 10 to 350 mg / m ²Is. Conductive
Ratio of crystalline oxide or its composite oxide to binder
Is preferably 1/300 to 100/1, more preferably 1/100 to 100
/ 5.

The light-sensitive material used in the present invention preferably has a slip property. The slip agent-containing layer is preferably used on both the photosensitive layer surface and the back surface. A preferable sliding property is a dynamic friction coefficient of 0.25 or less and 0.01 or more. The measurement at this time is 5 mm in diameter
The value when transported at 60 cm / min with respect to the stainless steel ball of (25 ° C, 60% RH). In this evaluation, even if the surface of the photosensitive layer is replaced as the mating material, the values are almost the same.

The slip agents that can be used in the present invention include polyorganosiloxane, higher fatty acid amides, higher fatty acid metal salts, esters of higher fatty acids and higher alcohols, and the like, and polyorganosiloxanes include polydimethylsiloxane and polydiethylsiloxane. Siloxane, polystyrylmethylsiloxane, polymethylphenylsiloxane, or the like can be used. The addition layer is preferably the outermost layer of the emulsion layer or the back layer. Particularly, polydimethylsiloxane and ester having a long chain alkyl group are preferable.

The sensitive material used in the present invention preferably contains a matting agent. The matting agent may be either on the emulsion side or the back side, but it is particularly preferable to add it to the outermost layer on the emulsion side. The matting agent may be soluble in the treatment liquid or insoluble in the treatment liquid, and preferably both are used in combination. For example, polymethylmethacrylate, poly (methylmethacrylate /
Methacrylic acid = 9/1 or 5/5 (molar ratio)), polystyrene particles and the like are preferable. The particle size is preferably 0.8 to 10 μm, and the particle size distribution is preferably narrow, and the average particle size is 0.
It is preferable that 90% or more of the total number of particles be contained within the range of 9 to 1.1 times. In addition, it is also preferable to add fine particles of 0.8 μm or less at the same time in order to enhance the matting property, for example, polymethylmethacrylate (0.2 μm), poly (methylmethacrylate / methacrylic acid = 9/1 (molar ratio), 0.3 μm)),
Polystyrene particles (0.25 μm), colloidal silica (0.
03 μm).

Next, the film cartridge used in the present invention will be described. The main material of the cartridge used in the present invention may be metal or synthetic plastic. Preferred plastic materials are polystyrene, polyethylene, polypropylene, polyphenyl ether and the like. Further, the cartridge used in the present invention may contain various antistatic agents, and carbon black, metal oxide particles, nonions, anions, cations, betaine-based surfactants or polymers can be preferably used. These antistatic patrones are disclosed in JP-A 1-312537,
No. 1-312538. 25 ° C, 25
The resistance at% RH is preferably 10 ¹² Ω or less. Usually, a plastic patrone is manufactured by using a plastic in which carbon black, a pigment and the like are kneaded in order to impart a light shielding property. The size of the patrone may be the same size as the current 135 size, or the size of the current 135 size is 25m for the miniaturization of the camera.
It is also effective to set the diameter of the m cartridge to 22 mm or less. The volume of the case of the cartridge is 30 cm ³ or less, preferably 25 cm ³ or less. The weight of the plastic used for the cartridge and cartridge case is 5g.
~ 15g is preferred.

Further, a cartridge which rotates the spool to feed the film may be used. Further, the film tip may be housed in the cartridge body, and the film tip may be sent to the outside from the port section of the cartridge by rotating the spool shaft in the film feeding direction. These are US
4,834,306 and 5,226,613. The photographic film used in the present invention may be a so-called raw film before development or a developed photographic film.
Further, the raw film and the developed photographic film may be housed in the same new cartridge, or may be different cartridges.

The color photographic light-sensitive material used in the present invention is also suitable as a negative film for advanced photo system (hereinafter referred to as AP system), and can be manufactured by Fuji Photo Film Co., Ltd. (hereinafter referred to as Fuji film) NEXIA A. , N
Examples include EXIA F and NEXIA H (ISO 200/100/400 in order), which are processed into AP system format and stored in a special cartridge. These AP
The system cartridge film is used by being loaded into an AP system camera such as the Fuji Film Epion series (Epion 300Z etc.). Further, the color photographic light-sensitive material used in the present invention is also suitable for a film with a lens such as Fuji Color Fujirun Super Slim manufactured by Fuji Film.

The film photographed by these is printed through the following steps in the minilab system. (1) Receiving (keeping the exposed cartridge film from the customer) (2) Detaching process (transferring the film from the cartridge to the intermediate cartridge for the developing process) (3) Film developing (4) Rear-attaching process (developing negative film) (Return the film to the original cartridge) (5) Print (C / H / P3 type print and index print are continuously and automatically printed on color paper [preferably Fujifilm SUPER FA8]) (6) Verification / shipment ( (Cartridge and index print are collated by ID number and shipped together with print)

As these systems, Fuji Film Minilab Champion Super FA-298 / FA-278 / FA-258 / F
A-238 and Fujifilm Digital Lab System Frontier are preferred. FP922AL / FP562B / FP562B, AL / FP362B / FP as a minilab champion film processor
362B, AL are listed, and recommended treatment chemicals are Fujicolor Justit CN-16L and CN-16Q. As a printer processor, PP3008AR / PP3008A / PP1828AR / PP1828A /
PP1258AR / PP1258A / PP728AR / PP728A are listed, and recommended treatment chemicals are Fuji Color Justit CP-47L and CP-4.
It is 0FAII. In Frontier System, Scanner & Image Processor SP-1000 and Laser Printer & Paper Processor LP-1000P or Laser Printer LP-1000W are used. The detacher used in the detaching process and the rear attacher used in the rear attach process are FUJIFILM's DT200 / DT100 and AT200 / AT1 respectively.
00 is preferable.

The AP system can also be enjoyed by a photo joy system centering on the Fuji Film digital image workstation Aladdin 1000. For example, you can directly load the developed AP system cartridge film on the Aladdin 1000, or use the 35mm film scanner FE to display the image information of negative film, positive film, and print.
The digital image data obtained by inputting using the -550 or PE-550 flat head scanner can be easily processed and edited. The data are digital color printer NC-550AL by photo-fixing type thermal color printing system and Pictrography 3000 by laser exposure thermal development transfer system.
Or as a print by existing lab equipment through a film recorder. The Aladdin 1000 can also output digital information directly to a floppy (registered trademark) disk or Zip disk, or to a CD-R via a CD writer.

On the other hand, at home, the developed AP system cartridge film is used as a photo player AP made by FUJIFILM.
-You can enjoy photos on TV just by loading it in -1,
By loading it on the Fujifilm Photo Scanner AS-1, it is possible to transfer image information to a PC continuously at high speed. In addition, to input film, prints or three-dimensional objects to a personal computer, you can use FUJIFILM Photo Vision FV-10 / FV.
-5 available. Furthermore, the image information recorded on a floppy disk, Zip disk, CD-R or hard disk can be processed and enjoyed on a personal computer using Fuji Photo application software Photo Factory. To output high-quality prints from a personal computer, Fuji Film's digital color printer NC-2 / NC-2D, which is a light-fixing thermal color printing system, is suitable. To store the developed AP system cartridge film, Fuji Color Pocket Album AP-5 Pop L, A
P-1 Pop L, AP-1 Pop KG or Cartridge File 16
Is preferred.

[0189]

EXAMPLES The present invention will now be specifically described with reference to examples, but the invention is not limited thereto. (Comparative Example-1) Preparation of sample 101 Preparation of triacetyl cellulose film Dissolve triacetyl cellulose in dichloromethane / methanol = 92/8 (mass ratio) by a normal solution casting method (13% by mass). ), A plasticizer triphenyl phosphate and biphenyl diphenyl phosphate were added at a mass ratio of 2: 1 so that the total amount was 14% with respect to triacetyl cellulose, and the mixture was prepared by the band method. The thickness of the support after drying was 97 μm.

Content of Undercoat Layer The following undercoat was applied to both sides of the above triacetyl cellulose film. The numbers represent the weight contained per 1.0 L of the undercoat liquid. Before applying the undercoat, corona discharge treatment was applied to both surfaces. Gelatin 10.0 g Salicylic acid 0.5 g Glycerin 4.0 g Acetone 700 mL Methanol 200 mL Dichloromethane 80 mL Formaldehyde 0.1 mg Water was added to 1.0 L

Coating of Back Layer The back layer shown below was coated on one surface of the undercoated support. 1st layer Binder: Acid-treated gelatin (isoelectric point 9.0) 1.00 g Polymer latex: P-2 (average particle size 0.1 μm) 0.13 g Polymer latex: P-3 (average particle size 0.2 μm) 0.23 g UV absorption Agent U-1 0.030 g Ultraviolet absorber U-3 0.010 g Ultraviolet absorber U-4 0.020 g High boiling organic solvent Oil-2 0.030 g Surfactant W-3 0.010 g Surfactant W-6 3.0 mg

[0192]   Second layer Binder: Acid-treated gelatin (isoelectric point 9.0) 3.10 g           Polymer latex: P-3 (average particle size 0.2 μm) 0.11 g           UV absorber U-1 0.030g           UV absorber U-3 0.010g           UV absorber U-4 0.020 g           High boiling organic solvent Oil-2 0.030g           Surfactant W-3 0.010g           Surfactant W-6 3.0mg           Dye D-2 0.10g           Dye D-10 0.12g           Potassium sulfate 0.25g           Calcium chloride 0.5mg           Sodium hydroxide 0.03g

[0193]   3rd layer Binder: Acid-treated gelatin (isoelectric point 9.0) 3.30 g           Surfactant W-3 0.020g           Potassium sulfate 0.30g           Sodium hydroxide 0.03g

[0194]   4th layer Binder: Lime-treated gelatin (isoelectric point 5.4) 1.15g           1: 9 copolymer of methacrylic acid and methyl methacrylate               (Average particle size 2.0 μm) 0.040 g           6: 4 copolymer of methacrylic acid and methyl methacrylate               (Average particle size 2.0 μm) 0.030 g           Surfactant W-3 0.060g           Surfactant W-2 7.0mg           Hardener H-1 0.23g

Coating of Photosensitive Emulsion Layer A sample 101 was prepared by coating the following photosensitive emulsion layer on the side opposite to the side coated with the back layer. The numbers represent the amount added per m ² . The effect of the added compound is not limited to the described use.

First layer: antihalation layer Black colloidal silver 0.25g 2.40 g gelatin UV absorber U-1 0.15g UV absorber U-3 0.15g UV absorber U-4 0.10g UV absorber U-5 0.10g High boiling organic solvent Oil-1 0.10 g High boiling organic solvent Oil-2 0.10 g High boiling organic solvent Oil-5 0.010 g Dye D-4 1.0mg Dye D-8 2.5mg Microcrystalline solid dispersion of Dye E-1 0.05g

Second layer: intermediate layer Gelatin 0.50g Compound Cpd-A 0.2 mg Compound Cpd-K 3.0 mg Compound Cpd-M 0.030 g UV absorber U-6 6.0mg High boiling organic solvent Oil-3 0.010g High boiling organic solvent Oil-4 0.010 g High boiling organic solvent Oil-7 2.0 mg Dye D-7 4.0mg

[0198]   Third layer: Middle layer       Yellow colloidal silver 0.020g       Silver iodobromide emulsion whose surface and inside have been previously covered       (Cube, average silver iodide content 1 mol%, average sphere-equivalent particle size 0.06 μm)                                     Silver amount 0.010g       Gelatin 0.60 g       Compound Cpd-D 0.020 g       High boiling organic solvent Oil-3 0.010g       High boiling organic solvent Oil-8 0.010 g

Fourth layer: low-sensitivity red-sensitive emulsion layer Emulsion A Silver amount 0.10g Emulsion B Silver amount 0.15g Emulsion C Silver amount 0.15g Gelatin 0.80g Coupler C-1 0.15g Coupler C-2 7.0mg Coupler C-10 3.0mg Coupler C-11 2.0mg UV absorber U-3 0.010g Compound Cpd-I 0.020 g Compound Cpd-D 3.0 mg Compound Cpd-J 2.0 mg High boiling organic solvent Oil-10 0.030 g Additive P-1 5.0 mg

Fifth layer: Medium sensitivity red-sensitive emulsion layer Emulsion C Silver amount 0.15g Emulsion D Silver amount 0.15g Gelatin 0.70 g Coupler C-1 0.15g Coupler C-2 7.0mg Coupler C-10 3.0mg Compound Cpd-D 3.0 mg UV absorber U-3 0.010g High boiling organic solvent Oil-10 0.030 g Additive P-1 7.0 mg

Sixth layer: High-sensitivity red-sensitive emulsion layer Emulsion E Silver amount 0.15g Emulsion F Silver amount 0.20g 1.50 g gelatin Coupler C-1 0.60g Coupler C-2 0.015g Coupler C-3 0.030g Coupler C-10 5.0 mg UV absorber U-1 0.010g UV absorber U-2 0.010g High boiling organic solvent Oil-6 0.030g High boiling organic solvent Oil-9 0.020 g High boiling organic solvent Oil-10 0.050 g Compound Cpd-D 5.0 mg Compound Cpd-K 1.0 mg Compound Cpd-F 0.030 g Compound Cpd-L 1.0 mg Additive P-1 0.010g Additive P-4 0.030g

Seventh layer: intermediate layer Gelatin 0.70 g Addition P-2 0.10g Dye D-5 0.020 g Dye D-9 6.0mg Compound Cpd-I 0.010 g Compound Cpd-M 0.040 g Compound Cpd-O 3.0 mg Compound Cpd-P 5.0 mg High boiling organic solvent Oil-6 0.050g

Eighth layer: intermediate layer Yellow colloidal silver Silver amount 0.020g Gelatin 1.00g Additive P-2 0.05g UV absorber U-1 0.010g UV absorber U-3 0.010g Compound Cpd-A 0.050 g Compound Cpd-D 0.030 g Compound Cpd-M 0.050 g High boiling organic solvent Oil-3 0.010g High boiling organic solvent Oil-6 0.050g

Ninth layer: low-sensitivity green-sensitive emulsion layer Emulsion G Silver amount 0.25g Emulsion H Silver amount 0.30g Emulsion I Silver amount 0.25g 1.30 g gelatin Coupler C-4 0.20g Coupler C-5 0.050g Coupler C-6 0.020g Compound Cpd-A 5.0 mg Compound Cpd-B 0.030 g Compound Cpd-D 5.0 mg Compound Cpd-G 2.5mg Compound Cpd-F 0.010 g Compound Cpd-K 2.0 mg UV absorber U-6 5.0 mg High boiling organic solvent Oil-2 0.25g Additive P-1 5.0 mg

[0205]   10th layer: Medium sensitivity green sensitive emulsion layer       Emulsion I Silver amount 0.30g       Emulsion J Silver amount 0.30g       Silver bromide emulsion covered inside (cube, sphere-equivalent average particle diameter 0.11 μm)                                   Silver amount 3.0mg       Gelatin 0.70 g       Coupler C-4 0.25g       Coupler C-5 0.050g       Coupler C-6 0.020g       Compound Cpd-A 5.0 mg       Compound Cpd-B 0.030 g       Compound Cpd-F 0.010 g       Compound Cpd-G 2.0 mg       High boiling organic solvent Oil-2 0.20g       High boiling organic solvent Oil-9 0.050g

Eleventh layer: High-sensitivity green-sensitive emulsion layer Emulsion K Silver amount 0.40g Gelatin 0.80g Coupler C-4 0.30g Coupler C-5 0.080g Coupler C-7 0.050g Compound Cpd-A 5.0 mg Compound Cpd-B 0.030 g Compound Cpd-F 0.010 g High boiling organic solvent Oil-2 0.20g High boiling organic solvent Oil-9 0.050g

Twelfth layer: yellow filter layer Yellow colloidal silver Silver amount 0.010g Gelatin 1.0g Compound Cpd-C 0.010 g Compound Cpd-M 0.10 g High boiling organic solvent Oil-1 0.020 g High boiling organic solvent Oil-6 0.10 g Microcrystalline solid dispersion of Dye E-2 0.20 g

Thirteenth layer: Intermediate layer Gelatin 0.40g Compound Cpd-Q 0.20 g Dye D-6 3.0mg

Fourteenth layer: Low-sensitivity blue-sensitive emulsion layer Emulsion L Silver amount 0.15g Emulsion M Silver amount 0.20g Emulsion N Silver amount 0.10g Gelatin 0.80g Coupler Cp-1 0.22g Compound Cpd-B 0.10 g Compound Cpd-I 8.0 mg Compound Cpd-K 1.0 mg Compound Cpd-M 0.010 g UV absorber U-6 0.010 g High boiling organic solvent Oil-2 0.010 g

[0210]   Fifteenth layer: Medium sensitivity blue-sensitive emulsion layer       Emulsion N Silver amount 0.20g       Emulsion O Silver amount 0.20g       Silver bromide emulsion covered inside (cube, sphere-equivalent average particle diameter 0.11 μm)                                   Silver amount 3.0mg       Gelatin 0.80g       Coupler Cp-1 0.20g       Compound Cpd-B 0.10 g       Compound Cpd-E 0.030 g       Compound Cpd-N 2.0 mg       High boiling organic solvent Oil-2 0.010 g

Sixteenth layer: High-sensitivity blue-sensitive emulsion layer Emulsion P Silver amount 0.20g Emulsion Q Silver amount 0.25g Gelatin 2.00g Coupler C-3 5.0 mg Coupler Cp-1 0.77g High boiling organic solvent Oil-2 0.10 g High boiling organic solvent Oil-3 0.020g UV absorber U-6 0.10g Compound Cpd-B 0.20 g Compound Cpd-N 5.0 mg

Seventeenth layer: First protective layer Gelatin 1.00 g UV absorber U-1 0.15g UV absorber U-2 0.050g UV absorber U-5 0.20g Compound Cpd-O 5.0 mg Compound Cpd-A 0.030 g Compound Cpd-H 0.20 g Dye D-1 8.0mg Dye D-2 0.010g Dye D-3 0.010g High boiling organic solvent Oil-3 0.10 g

[0213]   18th layer: 2nd protective layer       Colloidal silver Silver amount 2.5 mg       Fine grain silver iodobromide emulsion (average grain size 0.06 μm, AgI content 1 mol%)                                   Silver amount 0.10g       Gelatin 0.80g       UV absorber U-1 0.030g       UV absorber U-6 0.030g       High boiling organic solvent Oil-3 0.010g

[0214]   19th layer: 3rd protective layer       Gelatin 1.00g       Polymethylmethacrylate (average particle size 1.5 μm)                                           0.10 g       6: 4 copolymer of methyl methacrylate and methacrylic acid         (Average particle size 1.5 μm) 0.15 g       Silicone oil SO-1 0.20g       Surfactant W-1 3.0mg       Surfactant W-2 8.0 mg       Surfactant W-3 0.040g       Surfactant W-7 0.015g

In addition to the above composition, additives F-1 to F-9 were added to all emulsion layers. In addition to the above composition, gelatin hardener H-1 and coating and emulsifying surfactants W-3, W-4, W-5 and W-6 were added to each layer. Furthermore, phenol, 1,2-benzisothiazolin-3-one, 2-phenoxyethanol, phenethyl alcohol, and p-benzoic acid butyl ester were added as antiseptic and antifungal agents.

[0216]

[Table 1-1]

[0217]

[Table 1-2]

[0218]

[Table 2-1]

[0219]

[Table 2-2]

[0220]

[Table 2-3]

[0221]

[Chemical 29]

[0222]

[Chemical 30]

[0223]

[Chemical 31]

[0224]

[Chemical 32]

[0225]

[Chemical 33]

[0226]

[Chemical 34]

[0227]

[Chemical 35]

[0228]

[Chemical 36]

[0229]

[Chemical 37]

[0230]

[Chemical 38]

[0231]

[Chemical Formula 39]

[0232]

[Chemical 40]

[0233]

[Chemical 41]

[0234]

[Chemical 42]

[0235]

[Chemical 43]

[0236]

[Chemical 44]

[0237]

[Chemical formula 45]

[0238]

[Chemical formula 46]

Preparation of Dispersion of Organic Solid Disperse Dye (Preparation of Dispersion of Dye E-1) A wet cake of Dye E-1 (270 g as a net amount of E-1) was mixed with P manufactured by BASF.
100 g of luronic F88 (ethylene oxide-propylene oxide block copolymer) and water were added and stirred to make 4000 g. Next, 1700 mL of zirconia beads having an average particle size of 0.5 mm was filled in Ultra Visco Mill (UVM-2) manufactured by IMEX Co., Ltd., and the slurry was passed through the slurry at a peripheral speed of about 10 m / sec and a discharge rate of 0.5 L / min for 2 hours. Crushed. The beads are filtered off and water is added to give a dye concentration of 3%
After dilution, it was heated at 90 ° C. for 10 hours for stabilization. The average particle size of the obtained dye fine particles was 0.30 μm, and the breadth of the particle size distribution (particle size standard deviation × 100 / average particle size) was 20%.

(Preparation of Solid Dispersion of Dye E-2)
270 g of water and W-4 were added to 1400 g of a wet cake of E-2 containing 0% by mass and stirred to obtain a slurry having an E-2 concentration of 40% by mass. Next, crusher, IMEX Co., Ltd.
Ultra Visco Mill (UVM-2) manufactured by Japan has an average particle size of 0.5
1700mL of mm zirconia beads are filled, the peripheral speed is about 10m / sec and the discharge rate is 0.5L / mi through the slurry.
The mixture was ground for 8 hours to obtain a solid fine particle dispersion of E-2.
This was diluted to 20% by mass with ion-exchanged water to obtain a solid fine particle dispersion. Each of the yellow coupler-containing lipophilic fine particle dispersions prepared here had an average particle size of 0.1.
It was in the range of 0 to 0.20 μm.

<Comparative Examples-2 to 7> Preparation of Samples 102 to 107 Instead of the comparative coupler (Cp-1) of Comparative Example-1, a comparative coupler (Cp-2) (compound (A -2)), comparative coupler (Cp-3) (compound (B-3) in Synthesis Example 2 of this patent) and comparative coupler (Cp-4) (compound (C- in Synthesis Example 3 of this patent))
3)), comparative coupler (Cp-5), comparative coupler (Cp-5)
-6) and the comparative coupler (Cp-7) were replaced by the same molar amounts, respectively, and Sample 1 was prepared in the same manner as Comparative Example-1.
02 (using the comparative coupler (Cp-2)), Sample 103 (using the comparative coupler (Cp-3)) and Sample 104 (using the comparative coupler (Cp-4)), Sample 105 ( Comparative coupler (Cp-5) was used), Sample 106 (Comparative coupler (Cp-6) was used) and Sample 107 (Comparative coupler (Cp-7)).
Was used). The average particle size of the yellow coupler-containing lipophilic fine particle dispersions prepared here was in the range of 0.10 to 0.20 μm.

[0242]

[Chemical 47]

[0243]

[Chemical 48]

<Examples 1 to 5> Preparation of Samples 108 to 112 In Comparative Example 1, instead of the comparative coupler (Cp-1), the exemplified coupler (1), the coupler (2), and the coupler ( 3), coupler (41), and coupler (59), respectively, were replaced by the same molar amounts as in Comparative Example 1, except that Sample 108 (using coupler (1)) as a light-sensitive material of the present invention, Sample 109
Samples (using coupler (2)), sample 110 (coupler (3), sample 111 (using coupler (41)), and sample 112 (using coupler (59)) were prepared. The average particle size of the yellow coupler-containing lipophilic fine particle dispersions prepared here was in the range of 0.10 to 0.20 μm.

<Color development test> Samples 101 to 112 obtained in Comparative Examples 1 to 7 and Examples 1 to 5 above were exposed under ordinary sensitometric conditions, and then subjected to the following development processing steps ( Development processing A) was performed. In addition, in processing, each sample was subjected to a running process at a ratio of 1: 1 of unexposed sample and completely exposed sample until the replenishment amount was 4 times the tank capacity, and then the evaluation process. It was

Treatment process time Temperature Tank capacity Replenishment amount First development 6 minutes 38 ° C 37L 2200mL / m ² First water washing 2 minutes 38 ° C 16L 4000mL / m ² Inversion 2 minutes 38 ° C 17L 1100mL / m ² Color development 6 minutes 38 ℃ 30L 2200mL / m ² before bleaching 2 min 38 ℃ 19L 1100mL / m ² bleaching 6 min 38 ℃ 30L 220mL / m ² Fixing 4 min 38 ℃ 29L 1100mL / m ² second water washing 4 minutes 38 ° C. 35L 4000 mL / m ² Final rinse 1 min 25 ℃ 19L 1100mL / m ²

The composition of each processing liquid was as follows.   [First developer] [Tank liquid] [Replenisher] ]   Nitrilo-N, N, N-trimethylenephosphonic acid     ・ 5 sodium salt 1.5 g 1.5 g   Diethylenetriamine pentaacetic acid / 5 sodium salt 2.0 g 2.0 g   Sodium sulfite 30 g 30 g   Hydroquinone / potassium monosulfonate 20 g 20 g   Potassium carbonate 15 g 20 g   Potassium bicarbonate 12 g 15 g   1-phenyl-4-methyl-4-hydroxymethyl     -3-Pyrazolidone 2.5 g 3.0 g   Potassium bromide 2.5 g 1.4 g   Potassium thiocyanate 1.2 g 1.2 g   Potassium iodide 2.0 mg −   Diethylene glycol 13 g 15 g   Add water to add 1000mL 1000mL     pH 9.60 9.60     The pH was adjusted with sulfuric acid or potassium hydroxide.

[0248]   [Reversal liquid] [Tank liquid] [Replenisher]   Nitrilo-N, N, N-trimethylenephosphonic acid tank liquid     ・ Same as 3.0 g of 5 sodium salt   Stannous chloride / dihydrate 1.0 g   p-aminophenol 0.1 g   Sodium hydroxide 8 g   Glacial acetic acid 15mL   1000 mL with water added     pH 6.00     The pH was adjusted with acetic acid or sodium hydroxide.

[0249]   [Color developer] [Tank liquid] [Replenisher] ]   Nitrilo-N, N, N-trimethylenephosphonic acid   ・ 5 sodium salt 2.0 g 2.0 g   Sodium sulfite 7.0 g 7.0 g   Trisodium phosphate dodecahydrate 36 g 36 g   Potassium bromide 1.0 g −   Potassium iodide 90 mg −   Sodium hydroxide 12.0 g 12.0 g   Citrazine acid 0.5 g 0.5 g   N-ethyl-N- (β-methanesulfonamidoethyl)     -3-Methyl-4-aminoaniline ・ 3/2 sulfuric acid ・     1 water salt 10 g 10 g   3,6-dithiaoctane-1,8-diol 1.0 g 1.0 g   Add water to add 1000mL 1000mL     pH 11.80 12.00     The pH was adjusted with sulfuric acid or potassium hydroxide.

[0250]   [Pre-bleaching] [Tank liquid] [Replenisher] ]   Ethylenediaminetetraacetic acid ・ disodium salt ・ dihydrate 8.0 g 8.0 g   Sodium sulfite 6.0 g 8.0 g   1-thioglycerol 0.4 g 0.4 g   Formaldehyde sodium bisulfite adduct 30 g 35 g   Add water to add 1000mL 1000mL     pH 6.30 6.10     The pH was adjusted with acetic acid or sodium hydroxide.

[0251]   [Bleach] [Tank] [Replenisher] ]   Ethylenediaminetetraacetic acid ・ disodium salt ・ dihydrate 2.0 g 4.0 g   Ethylenediaminetetraacetic acid-Fe (III) -Ammonium     ・ Dihydrate 120 g 240 g   Potassium bromide 100 g 200 g   Ammonium nitrate 10 g 20 g   Add water to add 1000mL 1000mL     pH 5.70 5.50     The pH was adjusted with nitric acid or sodium hydroxide.

[0252]   [Fixer] [Tank] [Replenisher]   Ammonium thiosulfate 80 g Same as tank liquid   Sodium sulfite 5.0 g 〃   Sodium bisulfite 5.0 g 〃   Add water to 1000mL     pH 6.60     The pH was adjusted with acetic acid or aqueous ammonia.

[0253]   [Stabilizer] [Tank liquid] [Replenisher] ]   1,2-benzisothiazolin-3-one 0.02g 0.03g   Polyoxyethylene-p-monononylphenyl ether     (Average degree of polymerization 10) 0.3 g 0.3 g   Polymaleic acid (average molecular weight 2,000) 0.1 g 0.15 g   Add water to add 1000mL 1000mL     pH 7.0 7.0.

In the development processing step, each bath continuously circulates and stirs the liquid, and further, on the lower surface of each tank, a foam tube having small holes of 0.3 mm in diameter at 1 cm intervals is arranged. Nitrogen gas was continuously bubbled and stirred. The treated samples each develop yellow color, and as can be seen from Table 3,
Samples 108 to 112 of the photosensitive material of the present invention had higher Dmax than Samples 101 to 107 of the comparative photosensitive material.
Further, the hue was sharp.

[0255]

[Table 3]

Example 6 ExY-2 and E of the 13th and 14th layers of Sample 101 of JP-A-11-305396.
A light-sensitive material was prepared, except that xY-3 was changed to the dye-forming coupler (1) of the present invention in an equimolar amount, and exposed and developed by the method described in Example 1 of JP-A No. 11-305396. As a result of evaluation by the method described in Example of the present application, the same result as that of Example 1 of the present application was obtained.

Example 7 In Example 1 of JP-A-11-84601, couplers C-5, C-6 and C-10 of the 13th and 14th layers of Sample 107 and C- of the 15th layer were used.
A light-sensitive material was prepared in which 6 and C-10 were changed to the dye-forming coupler (1) of the present invention in an equimolar ratio, and exposed and developed by the method described in Example 1 of JP-A No. 11-84601. As a result of treatment and evaluation by the method described in Example of the present application, the same result as that of Example 1 of the present application was obtained.

[0258]

According to the present invention, it is possible to provide a dye-forming coupler having a high hue, a large molecular extinction coefficient and a high storage stability, which gives a dye having good storage stability and can be produced at a low cost in a short process. By adding the coupler to the light-sensitive material, a silver halide photographic light-sensitive material having excellent color reproducibility and sharpness and good color image fastness can be provided.

Claims (5)

[Claims] 1. A yellow coupler represented by the following general formulas (I) to (IV). [Chemical 1] In the formula, R ¹ is an acyl group which may have a substituent,
Aryl group, heterocyclic residue, alkoxycarbonyl group,
An aryloxycarbonyl group, a carbamoyl group, a sulfamoyl group, an alkylsulfonyl group, an arylsulfonyl group, a cyano group, or a nitro group. R ² is an alkyl group, an aryl group or a heterocyclic residue, each of which may have a substituent. Each R ³ is an aryl group or a heterocyclic residue which may have a substituent. R ⁴ represents a substituent. n represents an integer of 0 or more and 2 or less. When n is 2, a plurality of R ⁴ may be the same or different. L
Represents a divalent linking group. k is an integer of 0 or more, and k is 2
In the above case, L may be the same connecting group or different connecting groups. 2. The coupler represented by the general formula (III) is represented by the following general formula (V).
Yellow coupler described in. [Chemical 2] In the formula, R ⁴ represents a substituent. n represents an integer of 0 or more and 2 or less. When n is 2, a plurality of R ⁴ may be the same or different. R ⁵ represents a hydrogen atom or a substituent. R ⁶ represents a substituent. m represents an integer of 0 or more and 4 or less, and m is 2
In the above case, a plurality of R ⁶ may be the same or different and may form a ring with each other. L represents a divalent linking group. k is an integer of 0 or more, and when k is 2 or more, L may be the same or different linking groups. 3. The yellow coupler according to claim 1, wherein the coupler represented by the general formula (I) is represented by the following general formula (VI). [Chemical 3] In the formula, R ⁴ represents a substituent. n represents an integer of 0 or more and 2 or less. When n is 2, a plurality of R ⁴ may be the same or different. R ⁶ represents a substituent. R ⁵ and R ⁷ represent a hydrogen atom or a substituent. m represents an integer of 0 or more and 4 or less,
When m is 2 or more, a plurality of R ⁶ may be the same or different and may form a ring with each other. L represents a divalent linking group. k is an integer of 0 or more, and when k is 2 or more, L may be the same connecting group or different connecting groups. 4. A coupler represented by the general formula (III) is
A compound represented by the following general formula (VII):
The yellow coupler as described in 1. [Chemical 4] Where R^FourRepresents a substituent. n represents an integer from 0 to 2
You When n is 2, multiple R4s are the same or different
You may stay. R⁶, R⁹Represents a substituent. R^Five, R ⁸Is hydrogen
Represents an atom or a substituent. m represents an integer of 0 or more and 4 or less
And when m is 2 or more, multiple R⁶Are the same or different
They may be formed, or may form a ring with each other. L is 2
Represents a valent linking group. k is an integer of 0 or more, and k is 2 or more
In case of, L is different connecting groups even if they are the same connecting group.
But good. j represents an integer of 0 or more and 3 or less, and j is 2 or more
When multiple R⁹Can be the same or different
Alternatively, they may form a ring with each other. 5. A silver halide color photographic light-sensitive material containing at least one of the yellow couplers represented by formulas (I) to (VII) described in any one of claims 1 to 4.