JPH08220714A - Method for preparing color photographic developing solution - Google Patents

Abstract

PURPOSE: To prevent deterioration due to air oxidation, increase of fog density, deterioration of color reproduction performance, and deterioration of color development density and the like at the time of intermittent use by electrolyzing an aqueous medium containing a composition of a specified color developing agent precursor. CONSTITUTION: The aqueous medium containing the composition of the color developing agent precursor is electrolyzed to form or to release the color developing agent on an electrode and this precursor is represented mainly by formulae I-III in which each of R1 -R6 is an H atom or a substituent; R7 is an alkyl group; R8 is a substituent; X is a group to be allowed to release an NH2 group by the electrolysis; (m) is 0, 1, 2, or 3; each of R9 -R12 is an H atom or a substituent; R13 is a substituent; each of R14 -R21 is an H atom or a substituent; R22 is a substituent; and (p) is 0, 1, 2, 3, or 4.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for preparing a color photographic developing solution, and more particularly to a method for preparing a color developing agent precursor composition.

[0002]

2. Description of the Related Art A p-phenylenediamine derivative is widely used as a developing agent for silver halide color photographic light-sensitive materials. This p-phenylenediamine derivative has the property of being decomposed by oxygen in the air. In order to prevent such air oxidation deterioration, for example, Japanese Patent Laid-Open No. 3-14
There is known a method of adding hydroxylamines described in 4,446 to a color developing bath. on the other hand,
In recent years, the number of in-store processing called minilabs has increased, and the development processing of silver halide color photographic light-sensitive materials such as Copystat AP-5000 manufactured by Fuji Photo Film Co., Ltd. or Finechecker manufactured by the same has become smaller and dispersed. These are often used intermittently or intermittently, rather than developing the photosensitive material continuously.
There is a strong demand today for suppression of air oxidation deterioration of color developers.

As a processing method of such a silver halide color light-sensitive material suitable for intermittent or intermittent development processing, Japanese Patent Laid-Open No. 6-308,676 discloses that silver halide color is applied to electrodes when electrolyzed. A color developer is prepared by electrolyzing an aqueous medium containing a color developer precursor composition that forms or releases a photographic developer.
A method using this has been proposed. According to this method, since the color developing agent precursor composition is stable against air oxidation, it is not necessary to pay attention to the air oxidation deterioration of the developer. It also has the advantage that a preservative is unnecessary for the same reason.

The present inventor has made further studies on the newly proposed method for preparing a color developing solution, and as a result, the fog density is higher than that in the case of using a conventional color developing solution, and the multi-layered structure is used. It has been found that there is a problem that the color reproducibility is deteriorated due to the decrease in the effect. Further, it has been found that there is a problem that a desired image cannot be sufficiently obtained when the intermittent use is repeated.

[0005]

SUMMARY OF THE INVENTION The present invention has been made in view of the above circumstances, and an object of the present invention is to provide the above-mentioned color developing solution in which it is not necessary to make air oxidation deterioration of the color developing solution a problem. While keeping the advantages of the preparation method of
Another object of the present invention is to provide a method for preparing a color photographic developer which solves various problems such as an increase in fog density, deterioration of color reproducibility, and a decrease in color density during intermittent use.

[0006]

Means for Solving the Problems The above-mentioned problems include a color developing agent precursor composition represented by the following general formula (D1), (D2), (D3), (D4) or (D5). It was solved by a method of preparing a silver halide color photographic developer composition by electrolyzing an aqueous medium, preferably immediately before use. General formula (D1)

[0007]

[Chemical 6]

In the formula, R ₁ , R ₂ , R ₃ , R ₄ , R ₅ and R
₆ may be the same or different and each represents a hydrogen atom or a substituent. R ₇ represents an alkyl group. R ₈ represents a substituent. m represents an integer of 0 to 3. X represents a group capable of generating an NH ₂ group by electrolysis. General formula (D2)

[0009]

[Chemical 7]

In the formula, R ₇ has the same meaning as in formula (D1). R ₉ , R ₁₀ , R ₁₁ and R ₁₂ may be the same or different and each represents a hydrogen atom or a substituent. R ₁₃ represents a substituent. n represents an integer of 0 to 3. X is a general formula (D
It has the same meaning as 1). General formula (D3)

[0011]

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In the formula, R ₁₄ , R ₁₅ , R ₁₆ , R ₁₇ , R ₁₈ and R
₁₉ , R ₂₀ and R ₂₁ may be the same or different and each represents a hydrogen atom or a substituent. R ₂₂ represents a substituent. p represents an integer of 0 to 4. X has the same meaning as in formula (D1). General formula (D4)

[0013]

[Chemical 9]

In the formula, R ₂₃ is a linear or branched unsubstituted alkyl group having 1 to 6 carbon atoms, or the main chain has 2 to 6 carbon atoms.
Is a linear or branched hydroxyalkyl group having 2 to 6 carbon atoms. R ₂₄ is a C 2-6 straight-chain or branched unsubstituted alkylene group whose main chain is C 2-6,
The main chain represents a linear or branched hydroxyalkylene group having 3 to 6 carbon atoms and 2 to 6 carbon atoms. R ₂₅ has 1 carbon
4 represents a linear, branched or cyclic alkyl group. X has the same meaning as in formula (D1). General formula (D5)

[0015]

[Chemical 10]

In the formula, R ₂₆ represents a linear or branched alkyl group having 1 to 6 carbon atoms. The main chain of R ₂₇ has 3 to 6 carbon atoms
Is a linear or branched alkylene group having 3 to 6 carbon atoms. R ₂₈ represents a linear or branched alkyl group having 1 to 4 carbon atoms. R ₂₉ represents a linear, branched or cyclic alkyl group having 1 to 4 carbon atoms. X has the same meaning as in formula (D1). Next, in the present invention, R ₁ , R ₂ , R ₃ , R ₄ , R ₅ in the compound represented by the general formula (D1),
R ₆ , R ₈ , m and X will be described in detail. R ₁ , R
₂ , R ₃ and R ₄ may be the same or different and each represents a hydrogen atom or a substituent. More specifically, R ₁ ,
R ₂ , R ₃ and R ₄ are a hydrogen atom or a substituent, and examples of the substituent include a halogen atom, an alkyl group, an aryl group, a heterocyclic group, a cyano group, a nitro group, a hydroxyl group, a carboxy group and a sulfo group. , Alkoxy group, aryloxy group, acylamino group, amino group, alkylamino group, anilino group, ureido group, sulfamoylamino group, alkylthio group, arylthio group, alkoxycarbonylamino group, sulfonamide group, carbamoyl group,
Sulfamoyl group, sulfonyl group, alkoxycarbonyl group, heterocyclic oxy group, azo group, acyloxy group, carbamoyloxy group, silyl group, silyloxy group, aryloxycarbonylamino group, imide group, heterocyclic thio group, sulfinyl group, phosphonyl group , An aryloxycarbonyl group, and an acyl group. These are alkyl groups,
It may be substituted with an alkenyl group, an alkynyl group, an aryl group, a hydroxyl group, a nitro group, a cyano group, a halogen atom or other substituents formed by an oxygen atom, a nitrogen atom, a sulfur atom or a carbon atom.

More specifically, examples of the substituents of R ₁ , R ₂ , R ₃ and R ₄ will be shown. The halogen atom is, for example, a fluorine atom or a chlorine atom. The alkyl group has 1 to 1 carbon atoms
6, preferably a linear, branched or cyclic alkyl group having 1 to 6 carbon atoms, for example, methyl, ethyl, propyl, isopropyl, t-butyl, 2-hydroxyethyl, 3-hydroxypropyl, benzyl, 2- Methanesulfonamidoethyl, 3-methanesulfonamidopropyl, 2-methanesulfonylethyl, 2-methoxyethyl, cyclopentyl, 2-acetamidoethyl, 2-carboxyethyl, 2-carbamoylethyl, 3-carbamoylpropyl, 2,3-dihydroxy. Propyl, 3,
4-dihydroxybutyl, n-hexyl, 2-hydroxypropyl, 4-hydroxybutyl, 2-carbamoylaminoethyl, 3-carbamoylaminopropyl, 4-
Carbamoylaminobutyl, 4-carbamoylbutyl,
2-carbamoyl 1-methylethyl and 4-nitrobutyl.

The aryl group is an aryl group having 6 to 24 carbon atoms, and examples thereof include phenyl, naphthyl and p-methoxyphenyl. The heterocyclic group is a 5-membered or 6-membered saturated or unsaturated heterocyclic ring containing 1 or more oxygen atom, nitrogen atom, or sulfur atom having 1 to 5 carbon atoms, and the number of heteroatoms constituting the ring. The number of the elements may be one or more, and examples thereof include 2-furyl, 2-thienyl, 2-pyrimidinyl, 2-benzotriazolyl, imidazolyl and pyrazolyl. The alkoxy group is an alkoxy group having 1 to 16 carbon atoms, preferably 1 to 6 carbon atoms, and examples thereof include methoxy, ethoxy, 2-methoxyethoxy, and 2-methanesulfonylethoxy. The aryloxy group is an aryloxy group having 6 to 24 carbon atoms, and examples thereof include phenoxy, p-methoxyphenoxy and m- (3
-Hydroxypropionamido) phenoxy. The acylamino group is an acylamino group having 1 to 16 carbon atoms, preferably 1 to 6 carbon atoms, for example, acetamide, 2
-Methoxypropionamide, p-nitrobenzoylamide. Alkylamino group has 1 to 1 carbon atoms
6, preferably an alkylamino group having 1 to 6 carbon atoms, such as dimethylamino, diethylamino and 2-hydroxyethylamino. Anilino group has 6 to 2 carbon atoms
Anilino group 4 is, for example, anilino, m-nitroanilino, N-methylanilino. The ureido group is a ureido group having 1 to 16 carbon atoms, preferably 1 to 6 carbon atoms, and examples thereof include ureido, methylureido, N, N-diethylureido, and 2-methanesulfonamidoethylureido.

The sulfamoylamino group has 0 carbon atoms.
-16, preferably a sulfamoylamino group having 0 to 6 carbon atoms, such as dimethylsulfamoylamino, methylsulfamoylamino and 2-methoxyethylsulfamoylamino. The alkylthio group has 1 to 1 carbon atoms.
16, preferably an alkylthio group having 1 to 6 carbon atoms, such as methylthio, ethylthio and 2-phenoxyethylthio. The arylthio group is an arylthio group having 6 to 24 carbon atoms, and examples thereof include phenylthio, 2-carboxyphenylthio, and 4-cyanophenylthio. The alkoxycarbonylamino group has 2 to 2 carbon atoms.
16, preferably an alkoxycarbonylamino group having 2 to 6 carbon atoms, such as methoxycarbonylamino, ethoxycarbonylamino, and 3-methanesulfonylpropoxycarbonylamino. The sulfonamide group is a sulfonamide group having 1 to 16 carbon atoms, preferably 1 to 6 carbon atoms, and examples thereof include methanesulfonamide, p-toluenesulfonamide, and 2-methoxyethanesulfonamide. The carbamoyl group is a carbamoyl group having 1 to 16 carbon atoms, preferably 1 to 6 carbon atoms, and examples thereof include carbamoyl, N, N-dimethylcarbamoyl and N-ethylcarbamoyl. The sulfamoyl group has 0 to 1 carbon atoms
6, preferably a sulfamoyl group having 0 to 6 carbon atoms, such as sulfamoyl, dimethylsulfamoyl and ethylsulfamoyl. C1 as a sulfonyl group
To 16, preferably an aliphatic or aromatic sulfonyl group having 1 to 6 carbon atoms, and examples thereof include methanesulfonyl, ethanesulfonyl, and 2-chloroethanesulfonyl. The alkoxycarbonyl group is an alkoxycarbonyl group having 1 to 16 carbon atoms, preferably 1 to 6 carbon atoms, and examples thereof include methoxycarbonyl, ethoxycarbonyl and t-butoxycarbonyl. The heterocyclic oxy group has 1 to 1 carbon atoms.
5 is a 5-membered or 6-membered saturated or unsaturated heterocyclic oxy group containing at least one oxygen atom, nitrogen atom, or sulfur atom, and the number of heteroatoms constituting the ring and the kind of element are 1 However, it may be plural, for example, 1-phenyltetrazolyl-5-oxy, 2-tetrahydropyranyloxy, and 2-pyridyloxy.

The azo group is an azo group having 1 to 16 carbon atoms, preferably 1 to 6 carbon atoms, for example, phenylazo, 2-
Hydroxy-4-propanoylphenylazo and 4-sulfophenylazo. The acyloxy group is an acyloxy group having 1 to 16 carbon atoms, preferably 1 to 6 carbon atoms, and examples thereof include acetoxy, benzoyloxy and 4-hydroxybutanoyloxy. The carbamoyloxy group is a carbamoyloxy group having 1 to 16 carbon atoms, preferably 1 to 6 carbon atoms, and examples thereof include N, N-dimethylcarbamoyloxy, N-methylcarbamoyloxy and N-phenylcarbamoyloxy. The silyl group is a silyl group having 3 to 16 carbon atoms, preferably 3 to 6 carbon atoms, such as trimethylsilyl, isopropyldiethylsilyl,
It is t-butyldimethylsilyl. The silyloxy group is a silyloxy group having 3 to 16 carbon atoms, preferably 3 to 6 carbon atoms, and examples thereof include trimethylsilyloxy, triethylsilyloxy and diisopropylethylsilyloxy. The aryloxycarbonylamino group is an aryloxycarbonylamino group having 7 to 24 carbon atoms, and examples thereof include phenoxycarbonylamino, 4-cyanophenoxycarbonylamino and 2,6-dimethoxyphenoxycarbonylamino. The imide group has 4 to 1 carbon atoms
The imide group of 6 is, for example, N-succinimide or N-phthalimide. Heterocyclic thio group has 1 to 5 carbon atoms
Is a 5- or 6-membered saturated or unsaturated heterocyclic thio group containing at least one oxygen atom, nitrogen atom, or sulfur atom, and the number of heteroatoms constituting the ring and the kind of element may be one There may be a plurality, for example, 2-benzothiazolylthio and 2-pyridylthio.

The sulfinyl group has 1 to 16 carbon atoms,
Preferred is a sulfinyl group having 1 to 6 carbon atoms, and examples thereof include methanesulfinyl, benzenesulfinyl, and ethanesulfinyl. The phosphonyl group has 2 to 1 carbon atoms
6, preferably a phosphonyl group having 2 to 6 carbon atoms, for example,
Methoxyphosphonyl, ethoxyphosphonyl and phenoxyphosphonyl. The aryloxycarbonyl group is an aryloxycarbonyl group having 7 to 24 carbon atoms, and examples thereof include phenoxycarbonyl, 2-methylphenoxycarbonyl and 4-acetamidophenoxycarbonyl. The acyl group is an acyl group having 1 to 16 carbon atoms, preferably 1 to 6 carbon atoms, such as acetyl, benzoyl,
It is 4-chlorobenzoyl.

R ₅ and R ₆ represent a hydrogen atom or a substituent, in which case the substituent represents an alkyl group, an aryl group or a heterocyclic group. The details are the same as those described for R ₁ , R ₂ , R ₃ and R ₄ . However, R ₅ , R ₆
Is a heterocyclic group, it is bonded to a carbon atom constituting the heterocycle of the heterocyclic group. R ₇ represents an alkyl group. The details are the same as those described for R ₁ , R ₂ , R ₃ and R ₄ . R ₈ represents a substituent. The details are the same as those described for R ₁ , R ₂ , R ₃ and R ₄ . m represents an integer of 0 to 3.

X represents a group capable of generating an NH ₂ group by electrolysis. More specifically, X is a -NO ₂ group, a -NO group,
NHOH group, -N = N-R ₃₀ group, -NHCOOCH ₂ C
(R ₃₁ ) ₃ group or a group represented by the following formula (PRO1). Expression (PRO1)

[0024]

[Chemical 11]

In the formula, R ₃₀ represents an alkyl group, an aryl group or a heterocyclic group. The details are the same as those described for R ₁ , R ₂ , R ₃ and R ₄ . R ₃₁ may be the same or different and each represents a hydrogen atom or a halogen atom. However, more than one of each R ₃₁ is not a hydrogen atom.

Among the compounds represented by the general formula (D1), the compounds represented by the following general formula (DD1) are particularly preferable. General formula (DD1)

[0027]

[Chemical 12]

Wherein R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R
₆ may be the same or different and each represents a hydrogen atom or a substituent. R ₇ has the same meaning as described above. R ₃₂ represents a hydrogen atom or a substituent. X has the same meaning as described above.

R ₁ , R ₂ , R ₃ in the general formula (DD1),
Preferred combinations of R ₄ , R ₅ , R ₆ , R ₇ , R ₃₂ and X will be described below. R ₃₂ is a hydrogen atom, an alkyl group or an alkoxy group, R ₇ is an alkyl group having 1 to 6 carbon atoms, and R ₁ , R ₂ , R ₃ ,
R ₄ , R ₅ and R ₆ are each a hydrogen atom or an alkyl group, and X is —N═N—R ₃₀ , —NHCOOCH ₂ C (R
₃₁ ) A combination of ₃ groups or formula (PRO1) is preferred. Here, the alkyl group and the alkoxy group include those substituted with other substituents. Among them, R ₁
And R ₂ , R ₃ and R ₄ , and R ₅ and R ₆ in each group, at least one of them is preferably a substituent.

As a more preferable combination, R ₃₂ is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or 1 carbon atom.
A 6 alkoxy group, R ₇ is an oxygen atom, a nitrogen atom, a sulfur atom or 2 carbon atoms having at least one water-soluble group formed from the group consisting of:
An alkyl group of 6, which is R ₁ , R ₂ , R ₃ , R ₄ , R ₅
And R ₆ are each hydrogen atom or an alkyl group having 1 to 3 carbon atoms, X is _{-N = N-R 30, -NHCOOCH} 2 C
A combination of (R ₃₁ ) ₃ groups or formula (PRO1) is preferred. Among them, R ₁ and R ₂ , R ₃ and R ₄ , R
_{In the} group consisting of each combination of ₅ and R ₆ , at least one of them is preferably a substituent.

As a more preferable combination, R ³² is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or 1 carbon atom.
To R 6 are alkoxy groups, wherein R ₇ is a water-soluble group selected from the group consisting of hydroxyl group, sulfonamide group, sulfamoyl group, ureido group, sulfamoylamino group, alkoxy group, carboxy group, sulfo group and sulfonyl group. An alkyl group having 2 to 6 carbon atoms, wherein R ₁ , R ₂ , R ₃ , R ₄ , R ₅ and R ₆ are each a hydrogen atom or an alkyl group having 1 to 3 carbon atoms; is _{-N = N-R 30, -NHCOOCH} 2 C (R 31) combination of preferably a ₃ group or formula (PRO1). Among them, in the group consisting of each combination of R ₁ and R ₂ , R ₃ and R ₄ , and R ₅ and R ₆ , at least one of them is preferably a substituent.

Next, in the present invention, R ₇ , R ₉ , R ₁₀ , R ₁₁ , R ₁₂ in the compound represented by the above general formula (D2),
R ₁₃ , n and X will be described in detail. R ₇ represents an alkyl group. The details are the same as those described for R ₁ , R ₂ , R ₃ and R ₄ . R ₉ and R ¹⁰ may be the same or different and each represents a hydrogen atom or a substituent.
The details are the same as those described for R ₁ , R ₂ , R ₃ and R ₄ . R ₁₁ and R ₁₂ may be the same or different and each represents a hydrogen atom or a substituent, and in this case, the substituent represents an alkyl group, an aryl group or a heterocyclic group. The details are the same as those described for R ₁ , R ₂ , R ₃ and R ₄ . However, when R ₁₁ and R ₁₂ are a heterocyclic group, they are bonded to the carbon atoms constituting the heterocycle of the heterocyclic group. R ₁₃ represents a substituent. For details, see R
It has the same meaning as described in ₁ , R ₂ , R ₃ and R ₄ . n represents an integer of 0 to 3. X has the same meaning as in formula (D1).

Among the compounds represented by the general formula (D2), the compounds represented by the following general formula (DD2) are particularly preferable. General formula (DD2)

[0034]

[Chemical 13]

In the formula, R ₉ , R ₁₀ , R ₁₁ and R ₁₂ may be the same or different and each represents a hydrogen atom or a substituent. R ₇ has the same meaning as described above. R ₃₃ represents a hydrogen atom or a substituent. X has the same meaning as described above. Formula (DD2) _{in, R 9, R 10, R} 11, R 12, R 7, R 33
The preferable combinations of X and X will be described below. R ₃₃ is a hydrogen atom, an alkyl group or an alkoxy group, R ₇ is an alkyl group having 1 to 6 carbon atoms, and R
₉ , R ₁₀ , R ₁₁ and R ₁₂ are each a hydrogen atom or an alkyl group, and X is —N═N—R ₃₀ , —NHCOOCH ₂ C.
A combination of (R ₃₁ ) ₃ groups or formula (PRO1) is preferred. Here, the alkyl group and the alkoxy group include those substituted with other substituents.

As a more preferable combination, R ₃₃ is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms or 1 to 3 carbon atoms.
6 is an alkoxy group, R ₇ is an oxygen atom, a nitrogen atom,
It is an alkyl group having 2 to 6 carbon atoms and having at least one water-soluble group formed from a sulfur atom or a combination thereof, wherein R ₉ , R ₁₀ , R ₁₁ and R ₁₂ are each a hydrogen atom or a carbon number. 1-3 is an alkyl group, and X is-
N = N-R _30, combination of preferably -NHCOOCH ₂ C (R ₃₁₎ is a ₃ group or formula (PRO1).
As a more preferable combination, R ₃₃ is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and R ₇ is a hydroxyl group, a sulfonamide group, a sulfamoyl group, a ureido group, a sulfamoylamino group, an alkoxy group or a carboxy group. Is a C2-6 alkyl group having at least one water-soluble group selected from the group consisting of, a sulfo group and a sulfonyl group, wherein R ₉ , R ₁₀ , R ₁₁ and R ₁₂ are each a hydrogen atom or a carbon number 1 ~ 3 alkyl groups, X is -N
= N-R _30, combination of preferably -NHCOOCH ₂ C (R ₃₁₎ is a ₃ group or formula (PRO1).

Next, in the present invention, R ₁₄ , R ₁₅ , R ₁₆ , R ₁₇ , R ₁₈ in the compound represented by the general formula (D3),
R ₁₉ , R ₂₀ , R ₂₁ , R ₂₂ , p and X will be described in detail. R ₁₄ , R ₁₅ , R ₁₆ , R ₁₇ , R ₁₈ , R ₁₉ , R ₂₀ , R ₂₁
May be the same or different and each represents a hydrogen atom or a substituent. The details are the same as those described for R ₁ , R ₂ , R ₃ and R ₄ . R ₂₂ represents a substituent. The details are the same as those described for R ₁ , R ₂ , R ₃ and R ₄ . p represents an integer of 0 to 4. X has the same meaning as in formula (D1). Among the compounds represented by the general formula (D3), the compound represented by the following general formula (DD3) is particularly preferable. General formula (DD3)

[0038]

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In the formula, R ₁₄ , R ₁₅ , R ₁₆ , R ₁₇ , R ₁₈ and R
₁₉ , R ₂₀ and R ₂₁ may be the same or different and each represents a hydrogen atom or a substituent. R ₃₄ represents a hydrogen atom or a substituent. X has the same meaning as described above.

R ₁₄ , R ₁₅ , R ₁₆ in the general formula (DD3),
For R ₁₇ , R ₁₈ , R ₁₉ , R ₂₀ , R ₂₁ , R ₃₄ and X,
The preferable combination will be described below. R ₃₄ is a hydrogen atom, an alkyl group or an alkoxy group,
R ₁₄ , R ₁₅ , R ₁₆ , R ₁₇ , R ₁₈ , R ₁₉ , R ₂₀ and R ₂₁ are each a hydrogen atom or a substituent, and R ₁₄ , R ₁₅ , R ₁₆ ,
At least one of the group consisting of R ₁₇ , R ₁₈ , R ₁₉ , R ₂₀ and R ₂₁ is not a hydrogen atom, and X is a —NO ₂ group, a —NO group,
-N = N-R ₃₀ group, -NHCOOCH ₂ C (R ₃₁₎ combination of the group represented by is preferably ₃ group or formula (PRO1). As a more preferable combination, R ₃₄ is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or 1 carbon atom.
A 6 alkoxy _{group, R 14, R 15, R} 16, R 17,
R ₁₈ , R ₁₉ , R ₂₀ and R ₂₁ are each a hydrogen atom or a substituent and are at least one of the group consisting of R ₁₄ , R ₁₅ , R ₁₆ , R ₁₇ , R ₁₈ , R ₁₉ , R ₂₀ and R _21. Preferred is a combination in which one contains at least one water-soluble group formed from the group consisting of an oxygen atom, a nitrogen atom, a sulfur atom or a combination thereof, and X is a -NO or -NO ₂ group.

As a more preferable combination, R ³⁴ is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or 1 carbon atom.
A 6 alkoxy group, R ₁₄ and R ₂₀ is 1 to carbon atoms
6 is an alkyl group of R ₁₅ , R ₁₆ , R ₁₇ , R ₁₈ , R ₁₉
And R ₂₁ are each a hydrogen atom or a substituent, and R ₁₄ , R
_At least one of the group consisting of ₁₅ , R ₁₆ , R ₁₇ , R ₁₈ , R ₁₉ , R _20, and R ₂₁ is a hydroxyl group, a sulfonamide group, a sulfamoyl group, a ureido group, a sulfamoylamino group, an alkoxy group, or a carboxy group. A combination containing at least one water-soluble group selected from the group consisting of a group, a sulfo group and a sulfonyl group, and X being a -NO or -NO ₂ group is preferable.

Next, in the present invention, R ₂₃ , R ₂₄ , R ₂₅ and X in the compound represented by the general formula (D4) will be described in detail. R ₂₃ represents a straight-chain or branched unsubstituted alkyl group having 1 to 6 carbon atoms, or a straight-chain or branched hydroxyalkyl group having 2 to 6 carbon atoms whose main chain is 2 to 6 carbon atoms. Here, the main chain refers to a connecting group of a nitrogen atom and a hydroxyl group to be connected, and when R ₂₃ has a plurality of hydroxyl groups, it means one having the smallest number of carbon atoms. Specific examples of R ₂₃ include, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, n-hexyl, neopentyl, 3
-Hydroxypropyl, 2-hydroxyethyl, 2-hydroxypropyl, 4-hydroxybutyl, 2,3-dihydroxypropyl, 5-hydroxypentyl, 6-hydroxyhexyl, 4-hydroxypentyl, 3-hydroxybutyl, 4-hydroxy- 4-methylpentyl,
5,6-dihydroxyhexyl, 2,3,4-trihydroxybutyl and the like can be mentioned.

R ₂₄ has 2 carbon atoms whose main chain has 2 to 6 carbon atoms.
It represents a straight-chain or branched unsubstituted alkylene group having 6 to 6 carbon atoms, or a straight-chain or branched hydroxyalkylene group having 2 to 6 carbon atoms in the main chain. Here, the main chain refers to a connecting chain of the nitrogen atom to which it is connected and the hydroxyl group described in the general formula (D4), and when R ₂₄ has one or more hydroxyl groups, from the nitrogen atom side The hydroxyl group bonded on the carbon atom having the smallest number of carbon atoms corresponds to the hydroxyl group described in the general formula (D), and its connecting chain is the main chain. Specific examples of R ₂₄ include, for example, ethylene, trimethylene, tetramethylene, pentamethylene, hexamethylene, 1-methyltrimethylene, 2-methylethylene, 3-hydroxymethylethylene, 2-methyltrimethylene, 3-methyltrimethylene. , 3-methylpentamethylene, 2-methylpentamethylene, 2-ethyltrimethylene, 2-methylpentamethylene, 2-ethyltrimethylene, 3- (2-hydroxyethyl) trimethylene and the like.

R ₂₅ represents a linear, branched or cyclic alkyl group having 1 to 4 carbon atoms. Specific examples of R ₂₅ include methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, t-butyl, cyclopropyl and the like. X has the same meaning as in formula (D1).

Preferred combinations of R ₂₃ , R ₂₄ , R ₂₅ and X in the general formula (D4) are described below. R ₂₃ is a methyl group, an ethyl group, an n-propyl group, 2
-Hydroxyethyl group, 3-hydroxypropyl group, 4
- a hydroxybutyl group, R ₂₄ has its main chain is an alkylene group having 2 to 5 carbon atoms having 2 to 4 carbon atoms, R ₂₅ is a methyl group, an ethyl group, X is -NO or -NO ₂
Combinations that are groups are preferred. As a more preferable combination, R ₂₃ is a methyl group, an ethyl group, an n-propyl group, a 2-hydroxyethyl group, a 3-hydroxypropyl group or a 4-hydroxybutyl group, and R ₂₄ has a main chain of 2 carbon atoms. To C 4 -C 2-4 unsubstituted alkylene group, R ₂₅ is a methyl group, and X is —NO or —NO.
A combination of _two groups is preferred.

Next, in the present invention, R ₂₆ , R ₂₇ , R ₂₈ and X in the compound represented by the general formula (D5) will be described in detail. R ₂₆ represents a linear or branched alkyl group having 1 to 6 carbon atoms. Specific examples thereof include methyl, ethyl, propyl, isopropyl, t-butyl, 2-hydroxyethyl, 3-hydroxypropyl, 2-methanesulfonamidoethyl, 3-methanesulfonamidopropyl, 2-methanesulfonylethyl, 2- Methoxyethyl, cyclopentyl, 2-acetamidoethyl, 2-carboxyethyl, 2-carbamoylethyl, 3-carbamoylpropyl, 2,3-dihydroxypropyl, 3,
4-dihydroxybutyl, n-hexyl, 5-hydroxypentyl, 2-hydroxypropyl, 4-hydroxybutyl, 2-carbamoylaminoethyl, 3-carbamoylaminopropyl, 4-carbamoylaminobutyl,
4-sulfobutyl, 4-carbamoylbutyl, 2-carbamoyl 1-methylethyl, 4-nitrobutyl can be mentioned.

R ₂₇ represents a linear or branched alkylene group having a carbon number of 3 to 6 and a main chain of 3 to 6 carbon atoms. R ₂₇
As specific examples of, for example, trimethylene, tetramethylene, pentamethylene, hexamethylene, 1-methyltrimethylene, 2-methyltrimethylene, 3-methyltrimethylene, 3-methylpentamethylene, 2-methylpentamethylene, 2- Examples include ethyl trimethylene, 2-methylpentamethylene, 2-ethyltrimethylene, 3- (2-hydroxyethyl) trimethylene.

R ₂₈ represents a linear or branched alkyl group having 1 to 4 carbon atoms. Specific examples of R ₂₈ include, for example, methyl, ethyl, propyl, isopropyl, t-butyl, 2
-Hydroxyethyl, 3-hydroxypropyl, 2-methoxyethyl, 2-acetamidoethyl, 2-carboxyethyl, 2-carbamoylethyl and the like can be mentioned.

R ₂₉ represents a linear, branched or cyclic alkyl group having 1 to 4 carbon atoms. Specific examples of R ₂₉ include methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, t-butyl, cyclopropyl and the like. X has the same meaning as in formula (D1).

In the general formula (D5), R ₂₆ , R ₂₇ , R ₂₈ ,
The preferable combinations of R ₂₉ and X will be described below. R ₂₆ is a methyl group, an ethyl group or an n-propyl group, R ₂₇ is a C 3 -C 4 alkylene group whose main chain has 3 or 4 carbon atoms, and R ₂₈ is a methyl group or an ethyl group, A combination in which R ₂₉ is a methyl group or an ethyl group and X is a —NO or —NO ₂ group is preferable. As a more preferable combination, R ₂₆ is a methyl group or an ethyl group, R ₂₇ is a trimethylene group or a tetramethylene group, R ₂₈ is a methyl group and R
^{A combination in which 29} is a methyl group and X is a -NO or -NO ₂ group is preferable. Next, specific examples of typical developing agents represented by formula (D1) in the present invention are shown.
It is not limited by these.

[0051]

[Chemical 15]

[0052]

Embedded image

[0053]

[Chemical 17]

[0054]

Embedded image

Specific examples of typical developing agents represented by formula (D2) in the invention are shown below, but the invention is not limited thereto.

[0056]

[Chemical 19]

[0057]

Embedded image

[0058]

[Chemical 21]

[0059]

[Chemical formula 22]

Specific examples of typical developing agents represented by formula (D3) in the invention are shown below, but the invention is not limited thereto.

[0061]

[Chemical formula 23]

[0062]

[Chemical formula 24]

[0063]

[Chemical 25]

[0064]

[Chemical formula 26]

Specific examples of typical developing agents represented by formula (D4) in the invention are shown below, but the invention is not limited thereto.

[0066]

[Chemical 27]

[0067]

[Chemical 28]

[0068]

[Chemical 29]

[0069]

Embedded image

Specific examples of typical developing agents represented by formula (D5) in the invention are shown below, but the invention is not limited thereto.

[0071]

[Chemical 31]

[0072]

Embedded image

[0073]

[Chemical 33]

[0074]

Embedded image

Next, the general formulas (D1) and (D
The synthesis of the color developing agent precursors represented by 2), (D3), (D4) and (D5) will be described. General formulas (D1), (D2), (D3), (D4) and (D of the present invention
For the synthesis of the color developing agent precursor represented by 5), various known synthesis methods can be used. As an example,
The synthetic method shown in the following schemes 1 to 4 can be mentioned. Scheme 1

[0076]

Embedded image

In Scheme 1, R ₁ , R ₂ , R ₃ , R ₄ ,
R ₅ , R ₆ , R ₇ , R ₈ and m have the same meanings as in formula (D1). X ₁ is a —NO ₂ group, a —NO group, a NHOH group, or —N═ among X in the general formula (D1).
It represents an NR ₃₀ group. X ₂ is X in the general formula (D1).
Of these, a —NHCOOCH ₂ C (R ₃₁ ) ₃ group or a group represented by the formula (PRO1) is represented. Scheme 2

[0078]

Embedded image

In Scheme 2, R ₇ , R ₉ , R ₁₀ , R ₁₁ ,
R ₁₂ , R ₁₃ and n have the same meanings as in formula (D2). X ₁ is -N among X in the general formula (D2).
O ₂ group, represents an -NO group, NHOH group or -N = N-R ₃₀ group. X ₂ is a —NHCOOCH ₂ C (R ₃₁ ) ₃ group or a formula (PRO) among X in the general formula (D2).
It represents a group represented by 1). Scheme 3

[0080]

Embedded image

In Scheme 3, R ₁₄ , R ₁₅ , R ₁₆ , R ₁₇ ,
R ₁₈ , R ₁₉ , R ₂₀ , R ₂₁ , R ₂₂ and p are represented by the general formula (D3).
It means the same as inside. X ₁ represents a —NO ₂ group, a —NO group, a NHOH group or a —N═N—R ₃₀ group among X in the general formula (D3). X ₂ represents a —NHCOOCH ₂ C (R ₃₁ ) ₃ group or a group represented by the formula (PRO1) among X in the general formula (D3). Scheme 4

[0082]

[Chemical 38]

In Scheme 4, R ₂₃ , R ₂₄ and R ₂₅ have the same meanings as in formula (D4). They may be the same or different and each represents an alkyl group having 1 to 4 carbon atoms. X ₁ is a —NO ₂ group among X in the general formula (D4),
NO group, a NHOH group or -N = N-R ₃₀ group. X
₂ is -NHCO among X in the general formula (D4).
It represents an OCH ₂ C (R ₃₁ ) ₃ group or a group represented by the formula (PRO1). Scheme 5

[0084]

[Chemical Formula 39]

In Scheme 5, R ₂₆ , R ₂₇ , R ₂₈ and R ₂₉
Represents the same meaning as in formula (D5). X ₁ is a —NO ₂ group or —NO among X in the general formula (D4).
Represents a group, an NHOH group or a —N═N—R ₃₀ group. X ₂ is —NHCOOC among X in the general formula (D4).
It represents an H ₂ C (R ₃₁ ) ₃ group or a group represented by the formula (PRO1).

The tetrahydroquinoline derivative represented by the general formula (D1-A) in Scheme 1 is, for example, 1,2,
As 3,4-tetrahydroquinoline and the like, commercial products manufactured by Tokyo Chemical Industry Co., Ltd. can be obtained. In addition, the corresponding quinoline was obtained as a commercially available product, which was used as a chemical and pharmaceutical beauty reagent (Chem.
icalPharmaceutical Bulletin) Volume 32, page 2421 (1
(984), the compound represented by formula (D1-A) can be derived. In addition, by using aniline or a derivative having a substituent on the phenyl group, Journal of the Chemical Society Peraction I (Journal of the Chemical S
ociety Perkin Transaction I) page 1635 (1987)
The compound can be derived to the compound represented by the general formula (D1-A) by the method described in (Year). In addition, using organic synthesis collective volume (Organic Synthesis) using aniline or a derivative having a substituent on its phenyl group.
Syntheses Collective Volume) III, page 328, to synthesize a dihydroquinoline derivative, which is then reduced by a conventional method using a conventional hydrogenation catalyst such as palladium carbon to give a compound represented by the general formula (D1-A). It is also possible to obtain the compounds mentioned.

As the indoline derivative represented by the general formula (D2-A) in Scheme 2, for example, indoline, DL-indoline-2-carboxylic acid and the like can be obtained as commercial products manufactured by Tokyo Chemical Industry Co., Ltd. . Further, 2,3,3-trimethylindolenine commercially available from Tokyo Chemical Industry Co., Ltd. is reduced by a conventional method using an ordinary hydrogenation catalyst such as palladium carbon, and is represented by the general formula (D2-A). It is also possible to obtain a compound. In addition, JP-A-52-139,
No. 035 or Journal of Organic Chemistry 55, 58
A 2- (nitroaryl) ethanol derivative was synthesized by the method described on page 0 (1990), and was prepared according to JP-A-63-63.
By the method described in -83,066.
It is also possible to induce the compound represented by A). In addition, Synthetic Communications (Synthetic Comm
Unications 13: 489 (1983), it is also possible to reduce the corresponding indole derivative to an indoline derivative.

Next, the introduction of R ₇ shown in schemes 1 and 2 will be described in detail. Various known methods can be used to introduce R ₇ . For example, the Journal of American Chemical Society (Journa
l of Amrican Chemical Society) 71: 2532, or the method of the Journal of Organic
According to the method described in Chemistry (Journal of Organic Chemistry) Vol. 22, page 1213, after an unsaturated carboxylic acid ester or unsaturated nitrile such as ethyl acrylate, methacrylonitrile or ethyl crotonic acid is added by Michael, if necessary, A desired functional group conversion,
Further, for example, halogens such as ethyl iodide, 3-chloro-1-propanol, ethylene bromohydrin or N- (2-bromoethyl) phthalimide, and 3-bromopropylamine hydrobromide which are commercially available from Tokyo Chemical Industry Co., Ltd. A method in which N-alkylation is performed using a modified alkyl derivative and then a desired functional group conversion is performed, if necessary, can be mentioned. As a specific method of N-alkylation at this time, for example, it can be carried out according to the method described as the synthesis method of Exemplified Compound (D-12) in JP-A-6-161,062.

Next, the general formula (D3) shown in Scheme 3
The synthetic method of the compound represented by will be described in detail. As the compound represented by the general formula (D3-A) in Scheme 3, for example, 4-fluoronitrobenzene is Wako Pure Chemical Industries, Ltd.
Commercially available products can be obtained. In addition, the general formula (D
As the compound represented by 3-B), for example, 3-hydroxypyrrolidine, prolinol and the like can be obtained as commercial products manufactured by Tokyo Chemical Industry Co., Ltd. (D3-A) and (D3-
The reaction with B) is described as a method for synthesizing the exemplary compound (7) in JP-A-4-11,255 or a method for synthesizing the exemplary compound (I-17) in JP-A-4-188,550. It can be performed according to the method. Also, (D3-
The compound represented by C) is, for example, JP-A-4-11,25.
It can be carried out according to the method described as the method for synthesizing the exemplified compound (5) in No. 5.

The compounds represented by the general formula (D4-A) in scheme 4 and the general formula (D5-A) in scheme 5 are as follows:
For example, N-methyl-m-toluidine, N-ethyl-m-
Commercially available products of Tokyo Chemical Industry Co., Ltd. such as toluidine can be obtained. In addition, organic synthesis collective volume (Or) is selected from primary aniline derivatives such as m-ethylaniline and m-isopropylaniline.
ganic Syntheses Collective Volume) IV, page 420. Further, synthetic methods that can be used in the introduction of R ₇ are R ₂₃ and R ₂₆
Can also be used for the introduction of.

The introduction of —R ₂₄ —OH shown in Scheme 4 and the introduction of —R ₂₇ —NH ₂ shown in Scheme 5 can be carried out in the same manner as the introduction of R ₇ . -SO ₂ shown in Scheme 5
The introduction of —R ₂₈ is easy from, for example, methanesulfonyl chloride, chloromethanesulfonyl chloride, and the like, which are commercially available from Tokyo Chemical Industry Co., Ltd., and thus compounds represented by the general formula (D5-B). Can be synthesized.

In Schemes 1 to 5, introduction of X ₁ , X
The conversion of _{1 into} a —NH ₂ group and the conversion of X ₂ will be collectively described below. When X ₁ is a -NO group, a specific method for introducing the same is, for example, the method described as the method for synthesizing the exemplified compound (D-12) in JP-A-6-161062. You can Further, a specific method for introducing the arylazo group can be carried out according to the method described as the method for synthesizing the exemplary compound (D1-13) of the present invention described later.

A reduction reaction is generally used for the conversion of X _{1 into} a —NH ₂ group. Examples thereof include reduction with hydrogen using a catalyst such as palladium carbon, reduction with reduced iron, and reduction with sodium hydrosulfite. However, reduction with hydrogen using a catalyst such as palladium carbon is preferable from the viewpoint of the ease of treatment after the reaction, and a specific method thereof is, for example, the exemplified compound (D- in JP-A-6-161062). It can be carried out according to the method described as the synthesis method of 12).

The conversion of the --NH ₂ group to X ₂ is carried out by, for example, 2-
Benzoyl nitrochloride and 2,2,2-trichloroethyl chloroformate are commercially available from Aldrich Corporation in the United States, and (D1-C), (D2-
C), (D3-D), (D4-C) or (D5-
D) can be synthesized more easily. Synthesis Example 1 An exemplary compound (D1-13) of the present invention was synthesized according to the following formula.

[0095]

[Chemical 40]

Synthesis of (b) 105 g of 3-methylcrotonic acid and 200 g of acetonitrile
ml, N, N-dimethylacetamide 80 ml,
Thionyl chloride (80.5 ml) was added dropwise under ice-cooling stirring, and stirring was continued for 1 hour. This is (a) 107g 20
The mixture was added dropwise with stirring at ℃, and then 162 ml of pyridine was added to 18
The solution was added dropwise with stirring at ℃. This was poured into water and the precipitated crystals were collected by filtration to obtain 183 g of (b). Synthesis of (c) Methylene chloride was added to 177 g of (b), and 137 g of aluminum chloride was added with stirring under ice cooling. Further, the reaction system was brought to room temperature, and 137 g of aluminum chloride was added. 30 as it is
After stirring for minutes, the mixture was poured into ice water, extracted with ethyl acetate and concentrated.
The residue was recrystallized from acetonitrile to obtain (c) 49 g. Synthesis of (d) Lithium aluminum hydride 11.6 g THF 150
While stirring under reflux with heating (c), 48.3 g of THF was added to the suspension.
What was melt | dissolved in 200 ml was dripped. Then, after adding ethyl acetate and methanol, saturated sodium sulfate water was added, and the precipitate was filtered off using Celite as a filter aid, and the residue was concentrated.
This was purified by silica gel column chromatography to obtain (d) 38 g.

Synthesis of (e) 38 g of (d) was added with 100 m of N, N-dimethylacetamide.
1 and 54.8 g of sodium hydrogen carbonate were added. this,
The mixture was heated to 120 ° C to 130 ° C, 117 g of ethyl 3-bromopropionate was added dropwise, and the mixture was stirred as it was for 10 hours. Thereafter, 18.3 g of sodium hydrogen carbonate and 39.3 g of ethyl 3-bromopropionate were further added, and the mixture was heated at 150 ° C. for 4 hours. This was added to water, extracted with ethyl acetate, concentrated, and purified by silica gel column chromatography to obtain 44.7 g of a mixture of (e) and (d). Synthesis of (f) 104 g of 2,5-dichloroaniline and 200 g of methanol
0 ml and 121 hydrochloric acid (271 ml) were added, and an aqueous solution prepared by dissolving 44.9 g of sodium nitrite in water was added dropwise while stirring with ice cooling. This was added to a suspension obtained by adding 200 ml of methanol, 400 ml of THF, and 267 g of sodium acetate to 44.7 g of the mixture of (e) and (d) under ice-cooling stirring. Then, this was poured into water, extracted with ethyl acetate, and concentrated. Acetonitrile was added to the residue to remove insoluble matter, and the filtrate was concentrated and purified by silica gel column chromatography.
(G) The precipitated crystals were collected by filtration, dissolved in ethyl acetate, washed with saturated brine, dried over sodium sulfate and concentrated, and then purified by silica gel column chromatography (f) 57.5.
g was obtained. Synthesis of Exemplified Compound (D1-13) (f) To 54.9 g of THF, 450 ml of THF and an aqueous solution prepared by dissolving 21.1 g of sodium hydroxide in 300 ml of water were added.
Stirring was continued for 3 hours at 5 ° C. 12N hydrochloric acid 40.
After adding 9 ml and concentrating, the residue was extracted with ethyl acetate, concentrated and purified by silica gel column chromatography to obtain 49.5 g of Exemplified compound (D1-13).

Synthesis Example 2 Exemplified compound (I-1 in JP-A-5-188,550)
7), the exemplary compound of the present invention (D3
-7) was synthesized. Synthesis Example 3 Exemplified compound (D-1 in JP-A-6-162,062)
As described in the synthesis method of 2), the exemplary compound of the present invention (D4
-9) was synthesized.

Of course, the color developing agent precursor of the present invention may be used alone, or may be used in combination of two or more kinds. Further, they can be used in combination with other known color developing agent precursors as long as the effects of the present invention are not impaired. Representative examples of the compound to be combined are shown below, but the invention is not limited thereto. P-1 N, N-diethyl-p-nitrosoaniline P-2 N-ethyl-N- (2-hydroxyethyl)-
4-nitroaniline P-3 N-ethyl-3-methyl-N- (2-methanesulfonamidoethyl) -4-nitrosoaniline P-4 N, N-dimethyl-4-nitrosoaniline P-5 N, N- Diethyl-4- (2,2,2-trichloroethyloxycarbonylamino) aniline P-6 4- [4- (N, N-dimethylamino) phenylazo] benzenesulfonic acid sodium salt (methyl orange) These compounds are used for the purpose. It is also possible to use two or more types in combination. The amount of the color developing agent precursor used in the present invention is preferably 0.000 per liter of the solution to be electrolyzed.
5 mol to 0.1 mol, more preferably 0.001 mol to
It is 0.05 mol.

The aqueous medium used in the present invention is preferably a liquid medium in which the volume ratio of water before mixing is 80% or more, preferably 90% or more water, and substantially only water. More preferably, it is a medium. The medium to be mixed with water is preferably a solvent that does not separate when mixed with water, such as methanol, ethanol, N, N
-Dimethylformamide, N, N-dimethylacetamide, dimethylsulfoxide, acetonitrile and the like can be mentioned.

The color developer precursor composition used in the present invention preferably contains an ionic salt and is used for a color photographic light-sensitive material to be electrolyzed and then processed. The presence of ionic salts makes the solution more conductive.
Examples of such salts include nitrous acid, nitric acid, acetic acid, sodium salts and potassium salts of formic acid. Further, carbonic acid / bicarbonate sodium salts and potassium salts can also be preferably used, and they also have an advantage of acting as a buffer solution.

When the color photographic developer prepared by the preparation method of the present invention is used in a photosensitive material for printing, chlorine ions are contained in the developer in an amount of 3.0 × 10 ^{-2 to} 1.5 × 10 ^-1 mol / mol.
It is preferable to contain liter. Particularly preferably 3.
It is 5 × 10 ^{-2 to} 1.0 × 10 ^-1 mol / liter. Chloride concentration is 1.5 × 10 ^{-1 to} 1.0 × 10 ^-1 mol /
If it is more than 1 liter, it has the drawback of delaying development,
Not preferred. Further, if it is less than 3.0 × 10 ^-2 mol / liter, it is not preferable for preventing fog. In the present invention, bromine ions are added to the color developer at 0.5 × 10 ^−5.
It is preferable that the content is from mol / liter to 1.0 × 10 ⁻³ mol / liter. More preferably, 3.0 × 10 ⁻⁵ or more
The bromine ion concentration of 5 × 10 ⁻⁴ mol / liter is 1 ×
When it is more than 10 ^-3 mol / liter, development is delayed and the maximum density and sensitivity are lowered. When it is less than 0.5 × 10 ^-5 mol / liter, fog cannot be sufficiently prevented.

Here, the chlorine ion and the bromine ion may be added directly to the color developer precursor composition, or may be eluted from the light-sensitive material into the color developing solution during the development processing. When directly added to the color developer precursor composition, sodium chloride, potassium chloride, chloride ion-providing substances,
Ammonium chloride, lithium chloride, magnesium chloride,
Included is calcium chloride. Further, it may be supplied from the fluorescent whitening agent added to the color developer precursor composition. Sodium bromide as a source of bromide ions,
Examples thereof include potassium bromide, ammonium bromide, lithium bromide, calcium bromide and magnesium bromide. When it is eluted from the light-sensitive material during the development processing, both chlorine ion and bromine ion may be supplied from the emulsion or may be supplied from other than the emulsion.

Others In the color developer precursor composition, various additives described in JP-A-3-144,446 can be used. For example, in addition to the above-mentioned carbonates, phosphoric acid, boric acid, hydroxybenzoic acid, etc. of the same patent page (9) can be used as a buffer for maintaining pH. The color developer precursor composition preferably maintains the pH at 9.0 to 12.5 using these buffers. It is more preferably 9.5 to 11.5, still more preferably 10.
It is 5 to 11.5. Same as antifoggant (10)
The halide ion and the organic antifoggant described on the page can be mentioned. In particular, when the concentration of the color developing agent generated by electrolysis at the time of development is as high as 20 mmol / liter or higher and when the processing is performed at high temperature of 40 ° C. or higher, the bromide ion concentration is preferably high to some extent, and 17 mmol / liter or more and 60 mmol or more. / Liter or less is preferable. If necessary, the halogen can be removed by using an ion exchange resin or an ion exchange membrane to control the concentration within a preferable range. As the chelating agent, aminopolycarboxylic acid, aminopolyphosphonic acid, alkylphosphonic acid,
Phosphonocarboxylic acids are preferably used. For example, ethylenediaminetetraacetic acid, nitrilotriacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, hydroxyethyliminodiacetic acid, 1-hydroxyethylidene-1,1-diphosphonic acid, nitrilo-N, N, N-trimethylenephosphonic acid, Ethylenediamine-N, N, N,
Compounds typified by N-tetramethylenephosphonic acid, ethylenediamine-di (o-hydroxyphenylacetic acid) and salts thereof can be used. As a preferable chelating agent, a compound having biodegradability can be mentioned. Examples of this are Japanese Patent Laid-Open Nos. 63-146,998 and 63-
199,295, JP-A-63-267,750, JP-A-63-267,751, and JP-A-2-229,14.
6, JP-A-3-186,841, German Patent 3,73.
9,610, European Patent 468,325 and the like. Furthermore, development inhibitors such as benzimidazoles, benzothiazoles or mercapto compounds, development accelerators such as benzyl alcohol, polyethylene glycol, quaternary ammonium salts, amines, dye-forming couplers, competitive couplers, 1-phenyl- An auxiliary developing agent such as 3-pyrazolidone, a viscosity imparting agent, or various surfactants such as alkylsulfonic acid, arylsulfonic acid, aliphatic carboxylic acid, and aromatic carboxylic acid may be added as necessary.

If necessary, any development accelerator can be added to the color developer precursor composition. As the development accelerator, Japanese Examined Patent Publication Nos. 37-16,088 and 37-5,987.
No. 38-7, 826, 44-12, 380,
45-9,019 and US Pat. No. 3,813,24.
Thioe compound represented by JP-A No. 7-52, JP-A-52-
49,829 and 50-15,554, p-phenylenediamine compounds, JP-A-50-13.
7,726, JP-B-44-30,074, JP-A-5
6-156,826 and 52-43,429 and the like, quaternary ammonium salts, US Pat.
4,903, 3,218,182, 4,23
0,796, 3,253,919, Japanese Patent Publication No. 41-
11,431, U.S. Pat. Nos. 2,482,546, 2,596,926 and 3,582,346, and the like amine compounds, JP-B-37-16,088,
42-25,201, U.S. Pat. No. 3,128,18.
No. 3, Japanese Patent Publication Nos. 41-11, 431, 42-23, 8
83 and U.S. Pat. No. 3,532,501 and other polyalkylene oxides, and other 1-phenyl-3
-Pyrazolidones, imidazoles, etc. can be added as required.

When a photosensitive material for printing is developed using the color developing solution prepared by the preparation method of the present invention, it is preferable that the developing solution contains substantially no benzyl alcohol. When a photosensitive material for printing is developed using the color developer prepared by the preparation method of the present invention, the developer should contain substantially no sulfite ion (substantially no sulfite ion is included here). An ion concentration of 3.0 × 10 ⁻³ mol / liter or less) is preferable. Sulfite ion is preferably 1.0 × 10 ⁻³ mol / liter or less, and most preferably contains no sulfite ion. It is more preferable that this developer further contains substantially no hydroxylamine (the term "substantially does not contain hydroxylamine" means that the concentration of hydroxylamine is 5.0 × 10 ^-3 mol / liter or less). Most preferably, it contains no hydroxylamine at all.

A perborate such as sodium perboacetate may be added to the developer precursor composition of the present invention. By adding perborate, redox amplification occurs, and higher color density can be obtained as compared with the case of using a developer without perborate. When hydrogen peroxide is used instead of perboric acid, such an effect cannot be obtained.

As the electrode material used in the preparation method of the present invention, known electrode materials can be used. Regarding the cathode material, Weinberg, TECHNIQUE OF ELECTRO ORG
ANIC SYNTHESIS) Part I, p. 14 (John Wiley
And Sons, 1974) or Shigeru Torii, Organic Electrolytic Synthesis, page 12 (Kodansha, 1981). Further, the anode material is described in detail in Weinberg, ibid, page 21 or Part II, page 86 of the same name (John Wiley and Sons, 1975). Also, Hiroshi Yoneyama, Electrochemistry, pp. 12-12
Page 6 (Dainippon Tosho Publishing, 1986) also describes the cathode material in detail.

The voltage for electrolysis is preferably 10 V or less, more preferably 0.5 to 3 V. It goes without saying that the current value at that time takes a specific value at the same time by controlling the voltage. As a device for electrolyzing the color developer precursor composition used in the present invention, a known device can be used. For example, the device described in Shigeru Torii, Organic Electrolytic Synthesis, pages 7 to 10, Weinberg, TECHNIQUE OF ELECTRO ORGANIC SYNTHESI
S) The apparatus described in Part I, pages 58 to 122, etc. can be used.

When a light-sensitive material is continuously developed using the color developer prepared by the preparation method of the present invention, a color developer precursor composition solution is replenished, electrolyzed and developed as necessary. Is also possible. In this case, the replenishing amount is 550 ml per 1 m ^{2 in} the case of a photosensitive material for photography.
The following is preferred, 450 ml or less is more preferred, and 40
Most preferably 0 ml or less and 80 ml or more. The bromide ion concentration in the replenisher can be reduced to 300 ml or less by reducing or not containing it. In the case of a photosensitive material for printing, 20 to 60 per 1 m ^{2 of} the photosensitive material.
0 ml is suitable, preferably 30 to 200 ml, more preferably 40 to 100 ml. In the case of a photographic light-sensitive material, the processing temperature during development is preferably 35 ° C. or higher, more preferably 40 ° C. or higher and 50 ° C. or lower. In the case of a photosensitive material for printing, it is 20 to 50 ° C., preferably 30.
~ 45 ° C, most preferably 37-42 ° C. In the case of a photographic light-sensitive material, the processing time is preferably 30 seconds to 3 minutes and 15 seconds, more preferably 30 seconds to 2 minutes and 30 seconds. In the case of a photosensitive material for printing, it is generally 3 minutes or less,
Seconds to 1 minute are preferable, and 10 seconds to 30 seconds are more preferable.
Here, the processing time (for example, developing time) refers to the time from when the photosensitive material enters the target processing solution to when it enters the next processing solution.

The color developer precursor composition of the present invention, in a state before being subjected to electrolysis, is different from a generally used color developer composition, and positively takes measures to prevent air oxidation. Although not necessary, it is preferable to prevent the air oxidation in consideration of the use form in which the light-sensitive material is continuously processed. Further, it is preferable that the evaporation of the liquid prevent this. The contact area between the photographic processing liquid and air in the processing tank can be represented by the aperture ratio defined below. That is, aperture ratio = [contact area between treatment liquid and air (cm ² )] ÷ [volume of treatment liquid (cm ³ )] The above aperture ratio (cm ⁻¹ ) is preferably 0.05 or less, More preferably, it is 0.0005 to 0.01. As a method of reducing the aperture ratio in this way, in addition to providing a cover such as a floating lid on the photographic processing liquid surface of the processing tank,
The method using a movable lid described in JP-A-1-82,033 and the slit development processing method described in JP-A-63-216,050 can be mentioned. Further, it is preferable that the treatment liquid in the treatment tank is shielded with a high-boiling point organic solvent, a polymer compound or the like to reduce the contact area with air. It is not only the color development process that reduces the aperture ratio,
It can be applied to all the subsequent steps such as bleaching, bleach-fixing, fixing, washing with water and stabilization.

In the present invention, the developer precursor composition may be contained in the color photographic light-sensitive material to be processed. Examples of the layer containing the developer precursor composition include a silver halide-containing layer, a coupler-containing layer, an intermediate layer, an undercoat layer and a protective layer. The developer precursor is preferably water-soluble, but it is also possible to use a water-insoluble precursor by allowing a water-soluble electron transfer agent to exist. When the developer precursor composition is contained in the color photographic light-sensitive material to be processed, it is preferable to add additional water to ensure electrolysis and subsequent development. In this case, it is more preferable to add an alkaline aqueous solution. When the developer precursor composition is contained in the color photographic light-sensitive material to be processed, the color developing agent precursor is preferably substantially colorless, and when the precursor is not substantially colorless, It is preferable that this is contained in the lowermost layer (layer closest to the support) in the light-sensitive material.

When the developer precursor composition is contained in the color photographic light-sensitive material to be processed, and the developing agent precursor is substantially colorless and water-insoluble, it has a low content. In the exposed areas it is possible to partially reduce the precursor to a developing agent to reduce effluent of virgin developer to the environment. When the developer precursor composition is contained in the color photographic light-sensitive material to be processed, a simple carbonate activator can be used to develop the light-sensitive material using a stainless steel drum. In this case, the color developing agent is generated by contact with the stainless steel drum, and then the photosensitive material is removed from the stainless steel drum, and then the unused color developing agent is decomposed or removed from the drum. Specific methods for its decomposition or removal include, for example, a method using a mild oxidizing agent solution, a method using a third electrode on the low potential side, and a method using an appropriate resin for removing the color developing agent from the photosensitive material. Can be mentioned.

The color-developed light-sensitive material is usually desilvered. The desilvering process here basically comprises a bleaching process and a fixing process, but it is constituted by combining a bleach-fixing process in which these processes are performed simultaneously and these processes. Examples of bleaching agents include iron salts; iron (III), cobalt (III)
, Compounds of polyvalent metals such as chromium (IV) and copper (II); peracids; quinones; nitro compounds and the like. Typical bleaching agents are iron chloride; ferricyanide; dichromate; organic complex salts of iron (III) (eg ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, methyliminodiacetic acid, 1,3-diamino). Metal complex salts such as aminopolycarboxylic acids such as propane tetraacetic acid, glycol ether diamine tetraacetic acid); persulfates; bromates; permanganates; nitrobenzenes and the like. Among these, the above-mentioned JP-A-3-
As described in No. 144446 (11), ferric aminopolycarboxylic acid salts or salts thereof are preferably used.
For example, ferric salts such as ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, methyliminodiacetic acid, 1,3-diaminopropanetetraacetic acid and glycol etherdiaminetetraacetic acid can be used.
In addition, as the bleaching agent, complex salts of citric acid, tartaric acid, malic acid and the like can be used. Among these, aminopolycarboxylic acid iron (III) complex salts including ethylenediaminetetraacetic acid iron (III) complex salts and 1,3-diaminopropanetetraacetic acid iron (III) complex salts are particularly preferable. These aminopolycarboxylic acid iron (III) complex salts are particularly useful in both the bleaching solution and the bleach-fixing solution.

In the bleaching solution, the bleach-fixing solution and the prebath thereof, a bleaching accelerator can be used if necessary.
Specific examples of useful bleaching accelerators are described in the following specifications: US Pat. No. 3,893,858, West German Patent 1,290,812, JP-A-53-95630, Research. Disclosure No. 17129 (197
Compounds having a mercapto group or a disulfide bond described in JP-A No. 50-140129; U.S. Pat. No. 3,706,5.
No. 61, a thiourea derivative; JP-A-58-1623.
Iodide salt described in No. 5; West German Patent No. 2,748,430
Compounds described in Japanese Patent Publication No. Sho 45-
The polyamine compound described in No. 8836; bromide ion and the like can be used. Among them, a compound having a mercapto group or a disulfide group is preferable from the viewpoint of a large accelerating effect,
Especially US Pat. No. 3,893,858, West German Patent No. 1,
Compounds described in JP-A No. 290,812 and JP-A No. 53-95630 are preferable. Further, US Pat. No. 4,552,8
The compounds described in No. 34 are also preferable. These bleaching accelerators may be added to the light-sensitive material. These bleaching accelerators are particularly effective when bleach-fixing a color photographic material for photography.

In the desilvering bath, in addition to the bleaching agent, JP-A 3-1
No. 44446 (12), rehalogenating agent,
pH buffers and known additives can be used. The bleaching solution and the bleach-fixing solution preferably contain an organic acid in order to prevent bleaching stain in addition to the above compounds. Particularly preferred organic acids are compounds having an acid dissociation constant (pka) of 2 to 6, specifically, acetic acid, propionic acid, hydroxyacetic acid succinic acid, maleic acid, glutaric acid, fumaric acid, malonic acid, adipic acid, etc. However, succinic acid, maleic acid and glutaric acid are particularly preferable. The pH of the bleaching solution or the bleach-fixing solution is usually 4.0 to 8.0, but a lower pH can be used for speeding up the processing.

Examples of the fixing agent used in the fixing solution and the bleach-fixing solution include thiosulfates, thiocyanates, thioether compounds, thioureas and a large amount of iodide salts. It is commonly used, especially ammonium thiosulfate being the most widely used. Further, the combined use of thiosulfate with thiocyanate, thioether compound, thiourea and the like is also preferable. As a preservative for the fixing solution and the bleach-fixing solution, sulfites, bisulfites, carbonyl bisulfite adducts or sulfinic acid compounds described in EP 294769A are preferable. Further, for the purpose of stabilizing the liquid, it is preferable to add various aminopolycarboxylic acids and chelating agents such as organic phosphonic acids. Preferred chelating agents include 1-hydroxyethylidene-1,1-diphosphonic acid, ethylenediamine-N, N, N ', N'-tetrakis (methylenephosphonic acid), nitrilotrimethylenephosphonic acid, ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, cyclohexane. Diamine tetraacetic acid, 1,2
Mention may be made of propylenediaminetetraacetic acid. Among these, 1-hydroxyethylidene-1,1-diphosphonic acid and ethylenediaminetetraacetic acid are particularly preferable. The fixing solution and the bleach-fixing solution have a pKa of 6.
It is preferable to contain a compound of 0 to 9.0. For example, it is preferable to add imidazoles such as imidazole, 1-methylimidazole, 1-ethylimidazole, and 2-methylimidazole in an amount of 0.1 to 10 mol / liter. The imidazole compound represents imidazole and derivatives thereof, and preferable substituents of imidazole include an alkyl group, an alkenyl group, an alkynyl group, an amino group, a nitro group, a halogen atom and the like.
The alkyl group, alkenyl group and alkynyl group may be further substituted with an amino group, a nitro group, a halogen atom or the like. The preferred total carbon number of the substituents of the imidazole is 1 to 6, and the most preferred substituent is the methyl group.

Specific examples of the imidazole compound are shown below, but the invention is not limited thereto. Imidazole, 1-methylimidazole, 2-methylimidazole, 4-methylimidazole, 4- (2-hydroxyethyl) -imidazole, 2-ethylimidazole, 2-
Vinyl imidazole, 4-propyl imidazole, 4-
(2-Aminoethyl) imidazole, 2,4-dimethylimidazole, 2-chloroimidazole. Of these,
Preferred compounds are imidazole, 2-methyl-imidazole, 4-methyl-imidazole, most preferred compounds are imidazole.

The fixing solution and the bleach-fixing solution may further contain various fluorescent whitening agents, defoaming agents, surfactants, polyvinylpyrrolidone, methanol and the like. When a replenishing system is adopted in the processing, the replenishing amount of the fixing solution or the bleach-fixing solution is 100 to 300 per 1 m ² of the light-sensitive material.
0 ml is preferable, but 300 to 1800 is more preferable.
ml. The replenishment of the bleach-fixing solution may be conducted as a bleach-fixing replenishing solution, or as described in JP-A-61-143755 and Japanese Patent Application No. 2-216389, an overflow solution of a bleaching solution and a fixing solution is used. May be. The total processing time of the desilvering step, which is a combination of bleaching, bleach-fixing and fixing of the photographic light-sensitive material, is preferably 30 seconds to 3 minutes, more preferably 45 seconds to 2 minutes. The processing temperature is 30 to 6
The temperature is 0 ° C, preferably 35 to 55 ° C.

A processing solution having a bleaching ability is particularly preferably subjected to aeration at the time of processing because the photographic performance is kept extremely stable. Means known in the art can be used for the aeration, and blowing of air into the processing liquid having a bleaching ability or absorption of air using an ejector can be performed. At the time of blowing air, it is preferable to discharge the air into the liquid through an air diffusing tube having fine pores. Such an air diffuser is widely used as an aeration tank in activated sludge treatment. Regarding aeration, Z-1 issued by Eastman Kodak Company
21, Youth Process C-41 3rd Edition (198)
2 years), and the matters described on pages BL-1 to BL-2 can be used. In the processing using the processing solution having a bleaching ability of the present invention, it is preferable that the stirring is intensified. To carry out this, page 8, upper right column, line 6 of JP-A-3-33847. ~ The contents described in the lower left column, second line can be used as they are.

A processing solution having a fixing ability can be subjected to silver recovery by a known method, and a regenerating solution subjected to such silver recovery can be used. The silver recovery method includes an electrolysis method (described in French Patent No. 2,299,667), a precipitation method (Japanese Patent Laid-Open No. 52-73037, and German Patent No. 2,331.
No. 220), ion exchange method (JP-A-51-1711).
4, described in German Patent No. 2,548,237) and the metal substitution method (described in British Patent No. 1,353,805) are effective. These silver recovery methods are preferable when they are carried out in-line from the tank solution because the suitability for rapid processing is further improved. Further, the processing solution having a bleaching ability can be reused after recovering the overflow solution after use in the processing, adding the components to correct the composition. Such usage is usually called regeneration, but the present invention can also favor such regeneration. Regarding the details of the reproduction, the matters described on pages 39 to 40 of Fuji Film Processing Manual, Fuji Color Negative Film, CN-16 processing (revised August 1990), published by Fuji Photo Film Co., Ltd. can be applied. The kit for adjusting the processing liquid having the bleaching ability of the present invention may be a liquid or a powder, but when the ammonium salt is excluded, most of the raw materials are supplied as a powder, and since the hygroscopicity is also small, Makes powder easier. From the viewpoint of reducing the amount of waste liquid, the regenerating kit is preferably a powder because it can be added directly without using excess water.

Regarding the regeneration of the processing solution having the bleaching ability,
In addition to the aeration mentioned above, "Basics of photographic engineering-silver salt photography-" (edited by the Photographic Society of Japan, published by Corona Publishing Co., 1979)
Year)) etc. can be used. Specifically, in addition to electric field regeneration, there is a method for regenerating bleaching solution with bromic acid, zincic acid, bromine, bromine precursor, persulfate, hydrogen peroxide, hydrogen peroxide using catalyst, bromic acid, ozone, etc. Can be mentioned.
In electrolytic regeneration, the cathode and the anode are put in the same bleaching bath, or the anode bath and the cathode bath are regenerated by using a diaphragm to separate the baths. The fixing solution can be reprocessed at the same time. The fixing solution and the bleach-fixing solution are regenerated by electrolytically reducing accumulated silver ions. Other,
It is also preferable to remove accumulated halogen ions with an anion exchange resin in order to maintain the fixing performance.

In the desilvering step, it is preferable that the stirring is strengthened as much as possible. As a concrete method for strengthening the stirring, there is a method described in JP-A-62-183460, in which a jet of a processing solution is made to collide with the emulsion surface of a light-sensitive material, and JP-A-6-62.
No. 183,461 rotating means to improve the stirring effect, and further, by moving the light-sensitive material while bringing the wiper blade provided in the liquid into contact with the emulsion surface to make the emulsion surface turbulent There are a method of improving the effect and a method of increasing the circulation flow rate of the whole processing solution. Such a stirring improving means is effective in any of a bleaching solution, a bleach-fixing solution and a fixing solution. It is considered that the improvement of the stirring speeds up the supply of the bleaching agent and the fixing agent into the emulsion film, and consequently the desilvering rate. Further, the above-mentioned stirring improving means is more effective when a bleaching accelerator is used, and it is possible to remarkably increase the accelerating effect and eliminate the fixing inhibiting effect of the bleaching accelerator. The automatic developing machine used for the light-sensitive material of the present invention is disclosed in JP-A-60-191257 and 60-19.
It is preferable to have the photosensitive material conveying means described in Nos. 1258 and 60-191259. As described in the above-mentioned JP-A-60-191257, such a conveying means can remarkably reduce the carry-in of the treatment liquid from the front bath to the rear bath, and is highly effective in preventing the performance deterioration of the treatment liquid. Such an effect is particularly effective for reducing the processing time in each step and reducing the replenishing amount of the processing solution.

After the desilvering process, a washing process is generally performed. A stable process may be performed instead of the water washing process. In such stabilization treatment, Japanese Patent Laid-Open No. 57-8543
All known methods described in Nos. 58-14834 and 60-220345 can be used. Also,
A water washing step-stabilization step may be performed in which a stabilizing bath containing a dye stabilizer and a surfactant is used as a final bath. The water washing solution and the stabilizing solution may contain a hard water softening agent such as inorganic phosphoric acid, polyaminocarboxylic acid, or organic aminophosphonic acid.

The amount of water in the rinsing step depends on the characteristics of the light-sensitive material (for example, depending on the material used such as a coupler), the application, the liquid temperature, the number of tanks (number of stages), replenishment methods such as countercurrent and forward current, and various other types. It can be set in a wide range depending on the conditions. The number of stages is preferably 2 to 4. The replenishment amount is 1 to 50 times, preferably 1 to 30 times the amount brought in from the previous bath per unit area.
Times, more preferably 1 to 10 times. Further, as a method of efficiently reducing the replenishment amount, a so-called multi-chamber washing process in which the washing tank or stabilizing bath is divided by partition walls and the photosensitive material is processed in the liquid without passing through the slit portion of the wiper blade or the like into the air Alternatively, stabilizing treatment is preferably used.

According to the multi-stage countercurrent system or the multi-chamber washing system described above, the amount of washing water can be greatly reduced, but due to the increase in the residence time of water in the tank, bacteria propagate and the suspended matter produced is exposed to light. Problems such as adhesion to the material occur. In the processing of the color light-sensitive material of the present invention, as a solution to such a problem, the method of previously reducing calcium ion and magnesium ion described in JP-A-62-288,838 can be used very effectively. It is also effective to use water that has been sterilized in advance with a sterilizing agent such as sodium chlorinated isocyanurate. Further, for washing water, etc., isothiazolone compounds and siabendazoles described in JP-A-57-8,542, known chlorine-based bactericides, and other benzotriazoles, etc., Hiroshi Horiguchi "Chemistry of Antibacterial and Antifungal Agents"
(1986) Sankyo Publishing, Sanitary Technology Association, "Microbial Sterilization, Sterilization, and Antifungal Technology" (1982) Industrial Technology Association, Japan Society of Antimicrobial and Antifungal Activities, "Encyclopedia of Antimicrobial and Antifungal Agents" (1986) The bactericides described can also be used.

The washing water and the stabilizing solution have a pH of 4 to 9, preferably 5 to 8. Also, the temperature and time can be variously set depending on the characteristics of the photosensitive material, application, etc.
10 to 10 minutes at 5 to 45 ° C, preferably 25 to 40 ° C
The range of 15 seconds to 5 minutes is selected with. Further, the light-sensitive material of the present invention can be directly processed with a stabilizing solution instead of the above washing with water. In such stabilization treatment, all known methods described in JP-A-57-8543, JP-A-58-14834 and JP-A-60-220345 can be used.

In the stabilizing solution, compounds that stabilize the dye image, such as formalin, benzaldehydes such as m-hydroxybenzaldehyde, formaldehyde bisulfite adduct, hexamethylenetetramine and its derivatives, hexahydrotriazine and its derivatives, Examples include N-methylol compounds such as dimethylol urea and N-methylol pyrazole, organic acids and pH buffering agents. The addition amount of these compounds is preferably 0.001 to 0.02 mol per liter of the stabilizing solution, but the lower the free formaldehyde concentration in the stabilizing solution is, the less the formaldehyde gas is scattered, which is preferable. From this point of view, examples of the dye image stabilizer include m-hydroxybenzaldehyde, hexamethylenetetramine, N-methylolpyrazole, N-methylolazoles described in JP-A-4-270344, N, N'-bi (1 , 2,4-Triazol-1-ylmethyl) piperazine, etc.
Azolylmethylamines described in 3753 are preferred.
Particularly, azoles such as 1,2,4-triazole described in JP-A-4-359249 (corresponding to European Patent Publication No. 519190A2) and 1,4-bis (1,2,4-triazol-1-ylmethyl). ) The combined use of azolylmethylamine and its derivatives such as piperazine is preferable because of high image stability and low formaldehyde vapor pressure.
In addition, if necessary, ammonium compounds such as ammonium chloride and ammonium sulfite, metal compounds such as Bi and Al, optical brighteners, hardeners, US Pat.
It is also preferable to contain an alkanolamine described in JP-A-6,583 or a preservative that can be contained in the fixing solution or the bleach-fixing solution, for example, a sulfinic acid compound described in JP-A No. 1-231051. .

Various surfactants may be contained in the washing water and the stabilizing solution in order to prevent unevenness of water droplets during drying of the processed light-sensitive material. Among these, it is preferable to use a nonionic surfactant, and an alkylphenol ethylene oxide adduct is particularly preferable. Octyl, nonyl, dodecyl and dinonylphenol are particularly preferable as the alkylphenol, and 8 to 14 are particularly preferable as the number of moles of ethylene oxide added. Further, it is also preferable to use a silicon-based surfactant having a high defoaming effect.

Various chelating agents are preferably contained in the washing water and the stabilizing solution. Preferred chelating agents include aminopolycarboxylic acids such as ethylenediaminetetraacetic acid and diethylenetriaminepentaacetic acid, 1-hydroxyethylidene-1,1-diphosphonic acid, N, N, N'-trimethylenephosphonic acid and diethylenetriamine-N, N,
Examples thereof include organic phosphonic acids such as N ', N'-tetramethylenephosphonic acid, and hydrolyzates of maleic anhydride polymers described in European Patent 345,172A1.

The overflow solution accompanying the above washing with water and / or supplementation of the stabilizing solution can be reused in other steps such as the desilvering step. In the processing using an automatic processor, etc., when the above processing solutions are concentrated by evaporation,
In order to correct the concentration by evaporation, it is preferable to replenish an appropriate amount of water or a correction solution or a processing replenishing solution. The specific method for replenishing water is not particularly limited, but among them, a monitor water tank different from the bleaching tank described in JP-A-1-254959 and 1-254960 is installed, and water in the monitor water tank is installed. The amount of water vaporized in the bleaching tank is calculated from the amount of water vaporized in the bleaching tank, and the bleaching tank is replenished with water in proportion to the amount of water vaporized.
Nos. 3,249,644, 3,249,645, and 3,249,646, the evaporation correction method using a liquid level sensor and an overflow sensor are preferable.
As the water for correcting the evaporation of each treatment liquid, tap water may be used, but deionized water or sterilized water which is preferably used in the above washing step is preferably used.

Washing and / or stabilizing water treated with a reverse osmosis membrane can be effectively used. As the material of the reverse osmosis membrane, cellulose acetate, crosslinked polyamide, polyether, polysulfone, polyacrylic acid, polyvinylene carbonate, etc. can be used. The liquid feeding pressure in the use of these membranes is preferably ^{2 to} 10 kg / cm ² , and particularly preferably 3 to 7 kg / cm ^{2 because} of the stain prevention effect and the prevention of reduction of the amount of permeated water.

The treatment with the reverse osmosis membrane is preferably carried out on the water from the second tank onward of such multi-stage countercurrent washing and / or stabilization. Specifically, in the case of a two-tank configuration, the water in the second tank is treated and permeated with a reverse osmosis membrane in the second or third tank in the case of a three-tank configuration and the water in the third or fourth tank in a four-tank configuration. Same water tank (Tank for collecting water for reverse osmosis membrane treatment; hereinafter referred to as “collection tank”)
Alternatively, it is carried out by returning to a washing and / or stabilizing tank located thereafter. Furthermore, concentrated washing and /
Alternatively, one of the measures is to return the stabilizing solution to the bleach-fixing bath upstream of the sampling tank.

Various treatment liquids are preferably used at 10 ° C to 50 ° C. Normally, a temperature of 33 ° C to 38 ° C is standard, but a higher temperature accelerates the processing to shorten the processing time, and a lower temperature lowers the image quality to improve the stability of the processing liquid. be able to.

Each processing solution can be commonly used for processing two or more kinds of photosensitive materials. For example, by treating the color negative film and the color paper with the same treatment liquid, it is possible to reduce the cost of the processor and simplify the treatment.

It 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 Patent Publication 2-32615 and Actual Examination 3-39784
It is also suitable for the lens-fitted film unit described in.

The light-sensitive material may have at least one light-sensitive layer provided on a support. As a typical example, a silver halide photographic light-sensitive material having on a support at least one light-sensitive layer consisting 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 a color sensitivity to any of blue light, green light, and red light. In a light-sensitive material for photographing a multilayer silver halide color photograph, the unit photosensitive layer is generally used. The arrangement is such that the red-sensitive layer, the green-sensitive layer and the blue-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 plural silver halide emulsion layers constituting each unit photosensitive layer are composed of two layers, a high-sensitivity emulsion layer and a low-sensitivity emulsion layer, as described in DE 1,121,470 or GB 923,045.
It is preferable to arrange them so that the photosensitivity becomes lower toward the support. Further, JP-A-57-112751, 62-200350,
As described in JP-A Nos. 62-206541 and 62-206543, 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 photosensitive layer (BL) / high-sensitivity blue photosensitive layer (BH) / high-sensitivity green photosensitive layer (GH) / low-sensitivity green photosensitive layer (GL) / High-sensitivity red photosensitive layer (RH) / Low-sensitivity red photosensitive layer (RL), or BH / BL / GL / GH / RH / RL, or BH / BL / GH / GL / RL / RH It can be installed in the order of. Further, as described in JP-B-55-34932, from the side farthest from the support, the blue-sensitive layer / GH / RH / GL
It can also be arranged in the order of / RL. In addition, JP-A-56-2573
8 and 62-63936, the blue-sensitive layer / GL / RL / GH / RH may be arranged in this order from the side farthest from the support.

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 a layer more sensitive 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 three layers having different sensitivities, the method of
As described in 59-202464, in the same color-sensitive layer, a medium-speed emulsion layer / high-speed emulsion layer / low-speed emulsion layer may be arranged in this order from the side remote from the support. Other,
They 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. To improve color reproducibility, US
4,663,271, 4,705,744, 4,707,436, JP-A-62-1
60448, 63-89850, and a donor layer (CL) having a multilayer effect, which has a spectral sensitivity distribution different from that of the main photosensitive layer such as BL, GL, and RL, is arranged adjacent to or in proximity to the main photosensitive layer. Is preferred.

In a general light-sensitive material for printing (color photographic paper), silver halide emulsion grains are spectrally sensitized by blue-sensitive, green-sensitive and red-sensitive spectral sensitizing dyes in the order of the above-mentioned color forming layers, and It can be formed by coating on a support in the order described above. However, the order may be different from this. In other words, from the viewpoint of rapid processing, it is preferable that the photosensitive layer containing the largest silver halide grains having the average grain size comes to the uppermost layer, or from the viewpoint of storage stability under light irradiation, the lowermost layer is the magenta color photosensitive layer. In some cases it may be preferable to do so. Further, the light-sensitive layer and the color-developing hue may not have the above correspondence, and at least one infrared-sensitive silver halide emulsion layer can be used.

A preferred silver halide used in a photographic light-sensitive material is a silver iodobromide containing about 30 mol% or less of silver iodide.
It is silver iodochloride or silver iodochlorobromide. Particularly preferred is silver iodobromide or silver iodochlorobromide containing from about 2 mol% to about 10 mol% silver iodide. Silver halide grains in photographic emulsions have regular crystals such as cubes, octahedra and tetradecahedrons, grains having irregular crystal forms such as spheres and plates, twin planes, etc. It may have a crystal defect of, or a composite form thereof. The grain size of the silver halide may be fine grains of about 0.2 μm or less or large grains having a projected area diameter of up to about 10 μm, and may be a polydisperse emulsion or a monodisperse emulsion. Dispersion coefficient 15% or less, 1
Monodisperse particles of 0% or less are preferable. Silver halide photographic emulsions are, for example, Research Disclosure (hereinafter,
RD) 17643 (December 1978), pp. 22-23, "I.
Emulsion preparation and types ", ibid. 18716 (November 1979), p. 648, ibid. 307105 (1989).
November), pages 863-865, and the like.

Further, tabular grains having an aspect ratio of about 3 or more can be used in the present invention. Tabular grains are described in Gutoff, Photographic Science and Engineering (Gutoff, Photographic Science and E).
14: 248-257 (1970), US 4,43
It can be easily prepared by the method described in 4,226, GB 2,112,157. The crystal structure may be uniform, may have different halogen compositions inside and outside, or may have a layered structure. Silver halides having different compositions may be joined by epitaxial joining, and may be joined with a compound other than silver halide such as silver rhodanide and lead oxide. Also, a mixture of particles having various crystal forms may be used. The above emulsion may be either 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, but a negative type emulsion. It is necessary to be.
Among the internal latent image type, the core / shell type internal latent image type emulsion described in JP-A-63-264740 may be used, and the preparation method is described in JP-A-59-133542. The thickness of the shell of this emulsion varies depending on development processing 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 ripened and spectrally sensitized. Additives used in such a process are described in RD17643, RD 18716 and RD 307105, and the corresponding portions are summarized in the table below. In the light-sensitive material of 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 photosensitive silver halide emulsion are mixed in the same layer. Can be used. US Pat. No. 4,082,553, the surface of which has been fogged, the silver halide particles, US 4,626,498, JP-A-59-214852, the inside of which has been fogged the silver halide particles, and colloidal silver as a photosensitive silver halide emulsion layer and It is / or preferably applied to a substantially light-insensitive hydrophilic colloid layer. The fogged silver halide grain inside or on the surface means a silver halide grain capable of developing uniformly (non-imagewise) regardless of the unexposed portion and exposed portion of the light-sensitive material. . 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. Examples of the silver halide whose inside or surface is fogged include silver chloride, silver chlorobromide,
Both silver iodobromide and silver chloroiodobromide can be used. The average grain size of these fogged silver halide grains is preferably 0.01 to 0.75 .mu.m, more preferably 0.05 to 0.6 .mu.m. The grain shape may be regular grain or polydisperse emulsion, but monodisperse grain is preferable.

Non-photosensitive fine grain silver halide can also be used. Non-photosensitive fine grain silver halide is silver halide fine grains that are not exposed during imagewise exposure to obtain a dye image and are not substantially developed in the developing process, and are preferably not fogged in advance. . Fine grain silver halide has a silver bromide content of 0 to 10
It is 0 mol% and may contain silver chloride and / or silver iodide, if necessary. 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) of 0.01 to 0.5μ.
m is preferable, and 0.02 to 0.2 μm is more preferable. The fine grain silver halide does not need to be optically sensitized nor spectrally sensitized. However, prior to adding this to the coating liquid, it is preferable to add a known stabilizer such as a triazole-based, azaindene-based, benzothiazolium-based, mercapto-based compound or zinc compound in advance. Colloidal silver can be contained in the fine silver halide grain-containing layer. The silver coating amount of the light-sensitive material for photographing is preferably 3 to 10 g / m ² or less, and 4 to 4
Most preferably 7 g / m ² or less.

In the light-sensitive material for printing, it is preferable to use silver chloride, silver chlorobromide or silver chloroiodobromide grains having silver chloride of 95 mol% or more as silver halide grains. In particular, in order to accelerate the development processing time, a silver chlorobromide or silver chloride containing substantially no silver iodide can be preferably used. The term "substantially free of silver iodide" as used herein means that the silver iodide content is 1 mol% or less, preferably 0.2 mol% or less. On the other hand, for the purpose of enhancing high illuminance sensitivity, spectral sensitization sensitivity, or enhancing stability over time of a light-sensitive material, 0.01 to 3 mol% on the emulsion surface as described in JP-A-3-84545. In some cases, high silver chloride grains containing silver iodide are preferably used. The halogen composition of the emulsion may be different or the same between grains, but if an emulsion having the same halogen composition among grains is used, it is easy to make the properties of each grain uniform. Regarding the halogen composition distribution inside the silver halide emulsion grains, the so-called uniform structure grains having the same composition in any part of the silver halide grains, or the core inside the silver halide grains and the shell surrounding it. (shell)
Particles having a so-called laminated structure having a different halogen composition with [one or more layers], or a structure having a portion having a different halogen composition in a non-layer form inside or on the surface of the particle (edges, corners or surfaces of the particles when present on the surface of the particle) Particles having a structure in which portions having different compositions are bonded to each other can be appropriately selected and used. In order to obtain high sensitivity, it is advantageous to use either of the latter two rather than the particles having a uniform structure, and it is also preferable from the viewpoint of pressure resistance. When the silver halide grains have the above structure, the boundary between different portions in the halogen composition is an unclear boundary because a mixed crystal is formed due to the composition difference even if the boundary is clear. Alternatively, it may be one that positively has a continuous structural change.

The high silver chloride emulsion preferably has a structure having a localized silver bromide phase in the inside and / or on the surface of the silver halide grain in a layered or non-layered manner as described above. The halogen composition of the localized phase preferably has a silver bromide content of at least 10 mol%, and preferably 20 mol%.
It is more preferable that the number exceeds. These localized phases can be present inside the particles, on the edges, corners, or on the surface of the particles, and one preferable example thereof is that epitaxially grown on the corners of the particles. It is also effective to further increase the silver chloride content of the silver halide emulsion for the purpose of reducing the replenishment amount of the developing solution. In such a case, the silver chloride content is 9
An emulsion of substantially pure silver chloride such as 8 mol% to 100 mol% is also preferably used.

Average grain size of silver halide grains contained in the silver halide emulsion (the grain size is defined by the diameter of a circle equivalent to the projected area of the grain, and the number average thereof is taken).
Is preferably 0.1 μm to 2 μm. Further, the particle size distribution thereof is preferably a so-called monodisperse coefficient of variation of 20% or less (standard deviation of particle size distribution divided by average particle size), preferably 15% or less, more preferably 10% or less. . At this time, for the purpose of obtaining a wide latitude, it is also preferable to use the above monodispersed emulsion by blending it in the same layer, or to perform multi-layer coating. The shape of silver halide grains contained in a photographic emulsion is one having a regular crystal form such as a cube, a tetradecahedron or an octahedron, an irregular shape such as a sphere or a plate.
Those having a gular) crystal form or those having a composite form thereof can be used. It may also be a mixture of materials having various crystal forms. In the present invention, it is preferable that 50% or more, preferably 70% or more, and more preferably 90% or more of the particles having the above-mentioned regular crystal form are contained in the present invention. In addition to these, an emulsion in which tabular grains having an average aspect ratio (diameter in terms of circle / thickness) of 5 or more, preferably 8 or more exceeds 50% of all grains as a projected area can also be preferably used.

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

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

The silver halide emulsion is usually chemically and spectrally sensitized. Regarding the chemical sensitization method, chemical sensitization using a chalcogen sensitizer (specifically, sulfur sensitization represented by the addition of an unstable sulfur compound, selenium sensitization with a selenium compound, tellurium sensitization with a tellurium compound is performed. Noble metal sensitization typified by gold sensitization, reduction sensitization and the like can be used alone or in combination. Regarding compounds used for chemical sensitization, see Japanese Patent Application Laid-Open No.
Those described in the lower right column of page 18 to the upper right column of page 22 of JP-A 2-215272 are preferably used. The effect of the constitution of the light-sensitive material of the present invention is more remarkable than when the gold-sensitized high silver chloride emulsion is used. The emulsion used in the present invention is a so-called surface latent image type emulsion in which a latent image is mainly formed on the grain surface.

Various compounds or their precursors are added to the silver halide emulsion for the purpose of preventing fog during the production process of the light-sensitive material, storage or photographic processing, or stabilizing photographic performance. You can As specific examples of these compounds, those described on pages 39 to 72 of the above-mentioned JP-A No. 62-215272 are preferably used. Further, a 5-arylamino-1,2,3,4-thiatriazole compound described in EP 0447647 (wherein the aryl residue has at least one electron-withdrawing group) is also preferably used.

Spectral sensitization is carried out for the purpose of imparting spectral sensitivity in a desired light wavelength region to the emulsion of each layer in the light-sensitive material. Examples of spectral sensitizing dyes used for spectral sensitization in the blue, green, and red regions include FM Harmer's Heterocyclic co
mpounds-Cyanine dyes and related compounds (John W
iley & Sons New York, London, 1964). Examples of specific compounds and the spectral sensitization method are described in the above-mentioned JP-A-62-21.
Those described on page 22, upper right column to page 38 of Japanese Patent No. 5272 are preferably used. Further, as the red-sensitive spectral sensitizing dye for silver halide emulsion grains having a particularly high silver chloride content, the spectral sensitizing dye described in JP-A-3-123340 is stable, has strong adsorption, and has an exposure temperature. It is very preferable from the viewpoint of dependency.

For efficient spectral sensitization in the infrared region, JP-A-3-15049, page 12, upper left column to page 21, lower left column, or JP-A-3-20730, page 4, lower left column to page 15, lower left column, European Patent EP0. , 420, 011 page 4, lines 21-6
Page 54 line, EP 0,420,012, page 4, 12
Lines-10 pages 33 lines, European patent EP 0,443,466
And the sensitizing dyes described in US Pat. No. 4,975,362 are preferably used.

The time at which these spectral sensitizing dyes are added to the emulsion may be any stage of emulsion preparation known to be useful so far. In other words, before preparing the silver halide emulsion grains, during grain formation, immediately after grain formation, before entering the washing step, before chemical sensitization, during chemical sensitization, immediately after chemical sensitization, until the emulsion is cooled and solidified. You can choose from either. Most commonly, it is carried out after the completion of chemical sensitization and before the application, but is described in US Pat.
It is also possible to add spectral sensitization simultaneously with chemical sensitization by adding it at the same time as the chemical sensitizer as described in JP-A No. 628969 and No. 4225666.
It can be carried out prior to chemical sensitization as described in No. 28, or it can be added before the completion of silver halide grain precipitation to initiate spectral sensitization. It is also possible to add the spectral sensitizing dyes separately, as taught in U.S. Pat. No. 4,225,666, i.e. adding some prior to chemical sensitization and the rest after chemical sensitization. It is possible and can be at any time during silver halide grain formation, including the method taught in US Pat. No. 4,183,756. Of these, it is particularly preferable to add a sensitizing dye before the step of washing the emulsion with water or before the chemical sensitization.

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

In the light-sensitive material, a hydrophilic colloid layer is used for the purpose of preventing irradiation and halation, and improving safety of safelight, and European Patent EP03374.
Dyes which can be decolorized by treatment (in particular, oxonol dyes and cyanine dyes) described on pages 27 to 76 of the specification of 90A2 can be added. Some of these water-soluble dyes deteriorate the color separation and safelight safety when the amount used is increased. As the dyes that can be used without deteriorating the color separation, the water-soluble dyes described in Japanese Patent Application No. 03-310143, Japanese Patent Application No. 03-310189 and Japanese Patent Application No. 03-310139 are preferable.

Instead of the water-soluble dye or in combination with the water-soluble dye, a colored layer which can be decolorized by treatment is used. The coloring layer that can be decolorized by the treatment used may be in direct contact with the emulsion layer, or may be disposed so as to be in contact with the emulsion layer via an intermediate layer containing a treatment color mixing inhibitor such as gelatin or hydroquinone. This colored layer is preferably provided in the lower layer (support side) of the emulsion layer that develops a primary color of the same kind as the colored color. It is possible to install all the colored layers corresponding to each primary color individually, or to selectively install only a part of them. It is also possible to provide a colored layer that is colored corresponding to a plurality of primary color gamuts. The optical reflection density of the colored layer is the wavelength range used for exposure (visible light range of 400 nm to 700 nm in normal printer exposure, wavelength of scanning exposure light source used in scanning exposure).
It is preferable that the optical density value at the wavelength having the highest optical density is 0.2 or more and 3.0 or less. More preferably 0.5 to 2.5, especially 0.8 to 2.0
The following are preferred.

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

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

When the photosensitive material for printing is exposed to a printer, it is preferable to use the band stop filter described in US Pat. No. 4,880,726. As a result, light color mixture is removed, and color reproducibility is significantly improved.

The photographic additives that can be used are also described in RD, and the relevant portions are described in the table below. Types of additives RD17643 RD18716 RD307105 1. Chemical sensitizer page 23 page 648 page right column page 866 2. Sensitivity enhancer 648, right column 3. Spectral sensitizer, pages 23 to 24, 648 right column, pages 866 to 868, supersensitizer to 649, right column 4. Whitening agent, page 24, 647, right column, 868, page 5 Light absorber, pages 25 to 26, page 649, right column, page 873, filter, page 650, left column, dye, ultraviolet absorber 6. Binder, page 26, page 651, left column, pages 873 to 874 7. Plasticizer, page 27, page 650, right Column 876 Lubricants 8. Coating aids, 26-27 Pages 650 Right column 875-876 Pages Surfactant 9. Static 27 pages 650 Page 876 Right columns 876-877 Inhibitors 10. Matting agents 878-879

Although various dye-forming couplers can be used in the light-sensitive material, the following couplers are particularly preferable. 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); Japanese Patent Application No. 4 -134523 represented by the general formula (I) of claim 1; US 5,066,576, column 1, lines 45 to 55; the coupler represented by the general formula (I); JP-A-4-274425, paragraph 0008; Couplers of the formula I); couplers according to claim 1 of EP 498,381A1 on page 40 (in particular D-35 on page 18); formulas of page 4 of EP 447,969A1
A coupler represented by (Y) (especially Y-1 (page 17), Y-54 (41
)); US 4,476,219, column 7, lines 36-58, formulas (II)-(I
V) couplers (especially II-17, 19 (column 17), II
-24 (column 19)). Acyl acetanilide type couplers, in particular, pivaloyl acetanilide type couplers having a halogen atom or an alkoxy group at the ortho position of the anilide ring,
European Patent EP 044969A, JP-A-5-1077
No. 01, JP-A-5-113642 and the like, acylacetanilide type couplers in which the acyl group is a 1-substituted cycloalkanecarbonyl group, European Patent EP-042525.
52A, EP-0524540A and the like, malondianilide type couplers.

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); EP 486,
965, M-4, -6 (page 26), M-7 (page 27); Japanese Patent Application No. 4-234120, paragraph 0024, M-45; Japanese Patent Application No. 4-36917, paragraph 0036, M-1; Kaihei
The M-22.5-pyrazolone magenta coupler of Paragraph 0237 of 4-362631 is the arylthio-releasing 5-pyrazolone magenta coupler described in International Publication Nos. WO92 / 18901, WO92 / 18902 and WO92 / 18903. As a pyrazoloazole type coupler, Japanese Patent Laid-Open No.
Pyrazoloazole couplers containing a sulfonamide group in the molecule, as described in JP-A 1-65246, Japanese Patent Laid-Open No.
Pyrazoloazole couplers having an alkoxyphenyl sulfonamide ballast group as described in JP-A 1-147254 and EP Nos. 226,849A and 29.
A pyrazoloazole coupler having an alkoxy group or an aryloxy group at the 6-position as described in No. 4,785A.

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 Japanese Patent Application No. 4-236333. Polymer coupler: JP-A-2-44345, P-1, P-5 (page 11).
Phenol-based couplers and naphthol-based couplers, diphenylimidazole-based cyan couplers described in JP-A-2-33144, 3-hydroxypyridine-based cyan couplers described in European Patent EP 0333185A2, and JP-A-64-32260. Cyclic active methylene cyan couplers described, European patent EP04562
26A1 specification, pyrrolopyrazole type cyan coupler, European Patent EP0484909, pyrroloimidazole type cyan coupler, European Patent EP0488.
The pyrrolotriazole type cyan couplers described in 248 and EP 0491197A1.

As couplers in which the color forming dye has an appropriate diffusibility, 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 a coupler) which reacts with an oxidized product of a developing agent to release a photographically useful compound residue include the following. Development inhibitor releasing compound: EP 37
Compounds represented by formulas (I), (II), (III) and (IV) described on page 11 of 8,236A1 (particularly T-101 (page 30), T-104 (page 31), T-113 ( 36
Page), T-131 (page 45), T-144 (page 51), T-158 (page 58)), EP436, 93
Compounds represented by formula (I) on page 7 of 8A2 (especially D-4
9 (page 51)), a compound represented by the formula (1) of Japanese Patent Application No. 4-134523 (particularly (23) in paragraph 0027), and formulas (I) and (II in EP 440,195A2 on pages 5 to 6). ), (III) (particularly I- (1) on page 29); Bleach accelerator releasing compounds: EP 310,125A2-5
Compounds represented by formulas (I) and (I ') on page (especially (60) on page 61,
(61)) and a compound represented by the formula (I) in claim 1 of Japanese Patent Application No. 4-325564 (particularly (7) in paragraph 0022); a ligand-releasing compound: LIG-X described in claim 1 of US 4,555,478. Compounds represented (especially compounds on lines 21 to 41 of column 12); Leuco dye releasing compounds: compounds 1 to 6 of columns 3 to 8 of US 4,749,641; fluorescent dye releasing compounds: COUP-DYE of claim 1 of US 4,774,181 Compounds represented (especially columns 7-10)
Compounds 1 to 11); development accelerator or fogging agent releasing compounds: compounds represented by formulas (1), (2) and (3) of column 3, US Pat. No. 4,656,123 (particularly (I-22) of column 25) and EP 450,6
ExZK-2, 37A2, page 75, lines 36-38; compounds that release a dye group only upon leaving: a compound of formula (I) in claim 1 of US 4,857,447 (especially Y- in columns 25-36). 1 ~
Y-19).

The following additives are preferable as additives other than the coupler. 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 Pat. ) (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: I-1 to II-15 on pages 5 to 24 of EP 411324A, 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 support used for the light-sensitive material for printing may be any support such as glass, paper and plastic film as long as it can be coated with a photographic emulsion layer, but the most preferred is a reflection type support. The "reflective support" used in the present invention refers to one which enhances the reflectivity to make the dye image formed on the silver halide emulsion layer clear, and such a reflective support is a support. Those coated with a hydrophobic resin containing a light-reflecting substance such as titanium oxide, zinc oxide, calcium carbonate, or calcium sulfate dispersed therein, or those using the hydrophobic resin itself containing a dispersed light-reflecting substance as a support. Is included. For example polyethylene coated paper,
Polyethylene terephthalate-coated paper, polypropylene-based synthetic paper, a transparent support provided with a reflective layer or used in combination with a reflective material, for example, glass plate, polyethylene terephthalate, polyester film of cellulose triacetate or cellulose nitrate, polyamide film, polycarbonate There are films, polystyrene films, vinyl chloride resins, etc. The reflective support used in the present invention is a paper support whose both surfaces are coated with a water resistant resin layer,
It is preferable that at least one of the waterproof resin layers contains fine white pigment particles.

The water-resistant resin of the reflective support is a resin having a water absorption rate (% by weight) of 0.5, preferably 0.1 or less, and examples thereof include polyolefins such as polyethylene, polypropylene and polyethylene-based polymers, vinyl polymers and the like. The copolymer (polystyrene, polyacrylate and its copolymer), polyester (polyethylene terephthalate, polyethylene isophthalate etc.) and its copolymer. Polyethylene and polyester are particularly preferable. As the polyethylene, high density polyethylene, low density polyethylene, linear low density polyethylene and blends of these polyethylenes can be used. The melt flow rate (hereinafter abbreviated as MFR) before processing of these polyethylene resins is preferably 1.2 g / 10 minutes to 12 g / 10 minutes in a value measured under condition 4 of JIS K 7210, Table 1. The MFR of the polyolefin resin before processing referred to here is the M of the resin before kneading the bluing agent and the white pigment.
Indicates FR.

The weight ratio of the water resistant resin to the white pigment is 98/2 to 30/70 (water resistant resin / white pigment), preferably 95/5 to 50/50, particularly preferably 90/10. It is 60/40. 2% by weight of white pigment
If it is less than 70% by weight, the contribution to whiteness is insufficient, and if it exceeds 70% by weight, the surface smoothness of the photographic support is insufficient, and a photographic support having excellent glossiness is obtained. I can't. These water resistant resin layers are 2 to 200
It is preferable to coat the substrate with a thickness of μm, and more preferably 5 to 80 μm. If it is thicker than 200 μm, the brittleness of the resin is emphasized, causing physical problems such as cracking. When the thickness is less than 2 μm, the original waterproofing property of the coating is impaired, the whiteness and the surface smoothness cannot be satisfied at the same time, and the physical properties become too soft, which is not preferable. The thickness of the resin or resin composition with which the surface of the substrate other than the photosensitive layer-coated surface is coated is 5 to 100.
μm is preferable, and more preferably 10 to 50 μm. When the thickness exceeds this range, the brittleness of the resin is emphasized, and problems such as cracking occur in physical properties. If it is less than this range, the waterproof property which is the original purpose of the coating is impaired and the physical properties become too soft, which is not preferable.

In the reflective support, the water-resistant resin coating layer on the photosensitive layer coating side is a reflective support comprising two or more water-resistant resin coating layers having different contents of white pigments. In some cases, it may be more preferable from the viewpoint of production suitability and the like. In this case, among the water-resistant resin coating layers having different white pigment contents, the white pigment content of the water-resistant resin coating layer closest to the substrate is at least one of the water-resistant resin coating layers above this layer. It is preferably lower than the content of the white pigment. As a further preferred embodiment, among the water resistant resin coating layers having different contents of white pigment of the reflective support, the reflective support having the highest content of white pigment of the water resistant resin coating layer closest to the photosensitive layer, or the reflective support The support is composed of at least three water-resistant resin coating layers, and any one of intermediate layers other than the water-resistant resin coating layer closest to the photosensitive layer of the multi-layer water-resistant resin layer and the substrate. The reflective support has the highest content of the white pigment in.

The content of the white pigment in each layer in the multilayer waterproof resin layer is 0% by weight to 70% by weight, preferably 0% by weight.
˜50% by weight, more preferably 0% to 40% by weight. The content of the layer having the highest content of white pigment in the multilayer waterproof resin layer is 9% by weight to 70% by weight, preferably 15% by weight to 50% by weight, and more preferably 20% by weight to 40% by weight. Is. If the content of the white pigment in this layer is less than 9% by weight, the sharpness of the image is low, and if it exceeds 70% by weight, the melt-extruded film is cracked. The thickness of each layer of the multilayer waterproof resin layer is 0.5 μm to 5 μm.
0 μm is preferable. For example, in the case of a multilayer waterproof resin layer having a two-layer structure, the thickness of each layer is preferably 0.5 μm to 50 μm, and the total thickness of the layers combined is in the range (2 to 200).
μm) is preferable. In the case of a three-layer structure, the uppermost layer has a thickness of 0.5 μm to 10 μm, and the intermediate layer has a thickness of 5 μm.
˜50 μm, the thickness of the lower layer (layer closest to the substrate) is 0.5
It is preferably 10 μm. The film thickness of the top and bottom layers is 0.5
When it is at most μm, die lip streaks are likely to occur due to the action of the highly filled white pigment in the intermediate layer. On the other hand, if the thickness of the uppermost layer and the lowermost layer, especially the uppermost layer, is 10 μm or more, the sharpness is lowered.

It is preferable that the white pigment fine particles are uniformly dispersed in the reflective layer without forming an aggregate of particles.
The size of the distribution can be obtained by measuring the occupied area ratio (%) (Ri) of the fine particles projected on the unit area. The variation coefficient of the occupied area ratio (%) can be obtained by the ratio s / R of the standard deviation s of Ri to the average value (R) of Ri. In the present invention, the coefficient of variation of the occupied area ratio (%) of the fine particles of the pigment is preferably 0.15 or less, more preferably 0.12 or less. 0.08 or less is particularly preferable. A support having a second type diffusely reflective surface can be used. The second-class diffuse reflectivity was obtained by giving unevenness to a surface having a mirror surface and dividing it into fine mirror surfaces facing different directions, and dispersing the directions of the divided fine surfaces (mirror surface). Refers to diffuse reflectivity. The unevenness of the surface of the second-class diffuse reflection has a three-dimensional average roughness of 0.1 to 2 μm, preferably 0.1 to 1.2 μm with respect to the center plane. The frequency of the surface irregularities is preferably 0.1 to 2000 cycles / mm for irregularities having a roughness of 0.1 μm or more, and more preferably 50 to 600 cycles / mm. For more information on such supports, see
It is described in JP-A-2-239244.

Suitable supports for the light-sensitive material are described, for example, in RD. 17643, page 28, 18716, page 647, right column, 648
It is described in the left column of the page and 879105, page 879.

In the light-sensitive material for photographing, the total thickness of all hydrophilic colloid layers on the emulsion layer side is preferably 23 μm or less, more preferably 20 μm or less, and 13 to 17 μm.
Is particularly preferable. The film swelling speed T1 / 2 is preferably 5 to 15 seconds. T1 / 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. Define.
T1 / 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 150-350%
Is preferred. 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 photosensitive material may be 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 preferably contains the above-mentioned light absorber, filter dye, ultraviolet absorber, antistatic agent, hardener, binder, plasticizer, lubricant, coating aid, and surface active agent. The swelling ratio of the back layer is preferably 150 to 500%.

The silver halide photographic material carrying magnetic recording used in the present invention is described in JP-A-6-35118 and JP-A-6-6-1.
No. 7528, JIII Journal of Technical Disclosure No. 94-6023, a thin layer support of preheated polyester described in detail, for example, polyethylene aromatic dicarboxylate type polyester support, 50 μm to 300 μm, preferably 50 μm 200 μm, more preferably 80 to 11
Heat treatment (annealing) of 5 .mu.m, particularly preferably 85 to 105 .mu.m, at a temperature of 40.degree. C. or more and a glass transition temperature or less for 1 to 1500 hours is carried out to obtain Japanese Patent Publication Nos. 43-2603, 43-2604 and 45-3828. UV irradiation described in JP-B-48-5043, JP-A-51-131
576, etc., corona discharge, Japanese Patent Publication No. 35-7578.
Surface treatment such as glow discharge described in JP-B-46-43480, undercoating described in USP 5,326,689, and if necessary an undercoat layer described in USP 2,761,791. The ferromagnetic particles described in JP-A-59-23505, JP-A-4-195726, and JP-A-6-59357 may be applied. The magnetic layer described above is disclosed in JP-A-4-124642 and JP-A-4-124645.
The stripe shape described in No. may be used.

[0175] Further, if necessary, Japanese Patent Laid-Open No. 4-62543.
The product which has been subjected to the antistatic treatment of No. 1 and which is finally coated with a silver halide emulsion is used. The silver halide emulsions used here are those disclosed in JP-A-4-166932, JP-A-3-41436 and JP-A-3-41437. It is preferable that the light-sensitive material thus produced is manufactured by the manufacturing control method described in Japanese Patent Publication No. 4-86817, and the manufacturing data is recorded by the method described in Japanese Patent Publication No. 6-87146. After that, or before that, JP-A-4-4-1
In accordance with the method described in 25560, the conventional 135
Cut into a film narrower than the size, and perforate two holes per side per small format screen to match the smaller format screen smaller than conventional. The film thus produced is described in JP-A-4-157459.
No. 5 cartridge of US Pat. No. 5,210,202, or the cartridge shown in FIG.
Film Patrone of No. 1,479 and USP 4,83
4,308, US 4,834,366, USP5
It is used by putting it in the cartridge described in US Pat. No. 226,613 and USP 4,846,418.

The film cartridge or film cartridge used here is USP 4,848,893, U.
A type capable of accommodating a tongue such as SP5,317,355 is preferable from the viewpoint of light shielding properties. Furthermore, USP5
A cartridge having a lock mechanism such as 296,886, a cartridge displaying a usage state described in USP 5,347,334, and a cartridge having a double exposure preventing function are preferable. In addition, JP-A-6-85128
It is also possible to use a cartridge in which the film is easily attached by simply inserting the film into the cartridge as described in No. The film cartridge produced in this way can be used for the purpose of photographing, developing, and enjoying various photographs by using a camera, a developing machine, and a laboratory device described below. For example, a simple loading type camera described in JP-A-6-8886 and JP-A-6-99908 or JP-A-6-57398.
No. 6-101135, an automatic roll-up type camera described in JP-A-6-101135, and a camera described in JP-A-6-205690 in which film types can be taken out and replaced during shooting,
No. 293138 and Japanese Patent Application Laid-Open No. 5-283382, a camera capable of magnetically recording information on film, for example, panoramic shooting, high-vision shooting, normal shooting (magnetic recording with selectable print aspect ratio) and Japanese Patent Laid-Open No. If the camera having the double exposure prevention function described in JP-A-101194 or the camera having the usage status display function for the film described in JP-A-5-150577 is used, the function of the film cartridge (patrone) can be sufficiently exhibited. .

The film thus photographed is processed by an automatic developing machine described in JP-A-6-222514 and JP-A-6-222545, or before or during processing or after JP-A-6-95265. The method of utilizing magnetic recording on a film described in JP-A-4-123054 may be used, or the aspect ratio selection function described in JP-A-5-19364 may be used. In the case of cine type development, the splicing is performed by the method described in JP-A-5-119461. In addition, during or after the development process, the attach and detach processes described in JP-A-6-148805 are performed. After processing in this way, Japanese Patent Laid-Open No. 2-184835
JP-A-4-186335 and JP-A-6-79968.
Back print on color paper by the method described in No.
Film information may be converted into prints through front printing. Further, it may be returned to the customer together with the index print and return cartridge described in JP-A-5-11353 and JP-A-5-232594.

[0178]

EXAMPLES The present invention will be described in more detail with reference to examples below, but the present invention is not limited thereto. Example 1 On a subbed cellulose triacetate film support,
Each layer having the composition shown below was applied in multiple layers to prepare Sample 101, which is a multilayer color light-sensitive material. (Photosensitive layer composition) The main materials used for each layer are classified as follows; ExC: Cyan coupler UV: UV absorber ExM: Magenta coupler HBS: High boiling point organic solvent ExY: Yellow coupler H: Gelatin Curing agent ExS: Sensitizing dye The numbers corresponding to the respective components indicate the coating amount expressed in units of g / m ² , and for silver halide, the coating amount in terms of silver. However, with respect to the sensitizing dye, the coating amount is shown in mol unit per mol of silver halide in the same layer.

(Sample 101) First layer (antihalation layer) Black colloidal silver Silver 0.09 Gelatin 1.60 ExM-1 0.12 ExF-1 2.0 × 10 ^-3 Solid disperse dye ExF-2 0.030 Solid disperse dye ExF-3 0.040 HBS- 1 0.15 HBS-2 0.02

Second layer (intermediate layer) Silver iodobromide emulsion M Silver 0.065 ExC-2 0.04 Polyethyl acrylate latex 0.20 Gelatin 1.04

Third Layer (Low Sensitivity Red Sensitive Emulsion Layer) Silver iodobromide emulsion A Silver 0.25 Silver iodobromide emulsion B Silver 0.25 ExS-1 6.9 × 10 ^-5 ExS-2 1.8 × 10 ^-5 ExS-3 3.1 × 10 ^-4 ExC-1 0.17 ExC-3 0.030 ExC-4 0.10 ExC-5 0.020 ExC-6 0.010 Cpd-2 0.025 HBS-1 0.10 Gelatin 0.87

Fourth Layer (Medium Sensitivity Red Sensitive Emulsion Layer) Silver Iodobromide Emulsion C Silver 0.70 ExS-1 3.5 × 10 ^-4 ExS-2 1.6 × 10 ^-5 ExS-3 5.1 × 10 ^-4 ExC-1 0.13 ExC-2 0.060 ExC-3 0.0070 ExC-4 0.090 ExC-5 0.015 ExC-6 0.0070 Cpd-2 0.023 HBS-1 0.10 Gelatin 0.75

Fifth layer (high-sensitivity red-sensitive emulsion layer) Silver iodobromide emulsion D Silver 1.40 ExS-1 2.4 × 10 ^-4 ExS-2 1.0 × 10 ^-4 ExS-3 3.4 × 10 ^-4 ExC-1 0.10 ExC-3 0.045 ExC-6 0.020 ExC-7 0.010 Cpd-2 0.050 HBS-1 0.22 HBS-2 0.050 Gelatin 1.10

Sixth layer (intermediate layer) Cpd-1 0.090 Solid disperse dye ExF-4 0.030 HBS-1 0.050 Polyethyl acrylate latex 0.15 Gelatin 1.10

Seventh Layer (Low Sensitivity Green Sensitive Emulsion Layer) Silver iodobromide emulsion E Silver 0.15 Silver iodobromide emulsion F Silver 0.10 Silver iodobromide emulsion G Silver 0.10 ExS-4 3.0 × 10 ^-5 ExS-5 2.1 × 10 ^-4 ExS-6 8.0 × 10 ^-4 ExM-2 0.33 ExM-3 0.086 ExY-1 0.015 HBS-1 0.30 HBS-3 0.010 Gelatin 0.73 Eighth layer (medium sensitive green emulsion layer) Silver iodobromide emulsion H Silver 0.80 ExS-4 3.2 × 10 ^-5 ExS-5 2.2 × 10 ^-4 ExS-6 8.4 × 10 ^-4 ExC-8 0.010 ExM-2 0.10 ExM-3 0.025 ExY-1 0.018 ExY-4 0.010 ExY-5 0.040 HBS-1 0.13 HBS-3 4.0 × 10 ^-3 Gelatin 0.80

Ninth layer (high-sensitivity green-sensitive emulsion layer) Silver iodobromide emulsion I Silver 1.25 ExS-4 3.7 × 10 ^-5 ExS-5 8.1 × 10 ^-5 ExS-6 3.2 × 10 ^-4 ExC-1 0.010 ExM-1 0.020 ExM-4 0.025 ExM-5 0.040 Cpd-3 0.040 HBS-1 0.25 Polyethyl acrylate latex 0.15 Gelatin 1.33

10th layer (yellow filter layer) Yellow colloidal silver Silver 0.015 Cpd-1 0.16 Solid disperse dye ExF-5 0.060 Solid disperse dye ExF-6 0.060 Oil-soluble dye ExF-7 0.010 HBS-1 0.60 Gelatin 0.60

Eleventh layer (low-sensitivity blue-sensitive emulsion layer) Silver iodobromide emulsion J Silver 0.09 Silver iodobromide emulsion K Silver 0.09 ExS-7 8.6 × 10 ^-4 ExC-8 7.0 × 10 ^-3 ExY-1 0.050 ExY-2 0.22 ExY-3 0.50 ExY-4 0.020 Cpd-2 0.10 Cpd-3 4.0 × 10 ^-3 HBS-1 0.28 Gelatin 1.20

12th layer (high-sensitivity blue-sensitive emulsion layer) Silver iodobromide emulsion L Silver 1.00 ExS-7 4.0 × 10 ^-4 ExY-2 0.10 ExY-3 0.10 ExY-4 0.010 Cpd-2 0.10 Cpd-3 1.0 × 10 ^-3 HBS-1 0.070 Gelatin 0.70

Thirteenth layer (first protective layer) UV-1 0.19 UV-2 0.075 UV-3 0.065 HBS-1 5.0 × 10 ^-2 HBS-4 5.0 × 10 ^-2 gelatin 1.8

Fourteenth layer (second protective layer) Silver iodobromide emulsion M Silver 0.10 H-1 0.40 B-1 (diameter 1.7 μm) 5.0 × 10 ^-2 B-2 (diameter 1.7 μm) 0.15 B-3 0.05 S-1 0.20 Gelatin 0.70

Further, in order to improve storage stability, processability, pressure resistance, antifungal / antibacterial property, antistatic property and coatability, W-1 to W-3, B-4 to B- may be appropriately added to each layer. 6, F
-1 to F-17 and iron salt, lead salt, gold salt, platinum salt,
It contains a palladium salt, an iridium salt, and a rhodium salt.

[0194]

[Table 1]

In Table 1, (1) Emulsions J to L were prepared according to the examples of JP-A-2-91938.
It is reduction-sensitized during grain preparation using thiourea dioxide and thiosulfonic acid. (2) Emulsions A to I were prepared according to the examples of JP-A-3-237450.
Gold sensitization, sulfur sensitization and selenium sensitization are performed in the presence of the spectral sensitizing dye described in each photosensitive layer and sodium thiocyanate. (3) For the preparation of tabular grains, low molecular weight gelatin is used according to the examples of JP-A 1-158426. (4) Dislocation lines as described in JP-A-3-237450 are observed in the tabular grains by using a high voltage electron microscope. (5) Emulsion L is a double structure grain containing an internal high iodine core described in JP-A-60-143331.

Preparation of Dispersion of Organic Solid Disperse Dye ExF-2 shown below was dispersed by the following method. That is, water 21.7
3 ml of 5% sodium p-octylphenoxyethoxyethoxyethane sulfonate and 5% aqueous solution
0.5 g of an aqueous solution of p-octylphenoxypolyoxyethylene ether (degree of polymerization: 10) was put in a 700 ml pot mill, and 5.0 g of dye ExF-2 and 500 ml of zirconium oxide beads (diameter 1 mm) were added. The contents were dispersed for 2 hours. A BO type vibrating ball mill manufactured by Chuo Koki was used for this dispersion. After the dispersion, the contents were taken out, added to 8 g of a 12.5% gelatin aqueous solution, and the beads were removed by filtration to obtain a gelatin dispersion of the dye. The average particle size of the dye particles is 0.44
μm.

Similarly, solid dispersions of ExF-3, ExF-4 and ExF-6 were obtained. The average particle diameters of the dye fine particles were 0.24 μm, 0.45 μm and 0.52 μm, respectively.
ExF-5 is a microprecipitation described in Example 1 of European Patent Application Publication (EP) 549,489A.
It was dispersed by the dispersion method. The average particle size was 0.06 μm.

[0198]

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[0199]

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[0200]

[Chemical 43]

[0201]

[Chemical 44]

[0202]

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[0203]

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[0204]

[Chemical 47]

[0205]

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[0206]

[Chemical 49]

[0207]

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[0208]

[Chemical 51]

[0209]

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[0210]

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[0211]

[Chemical 54]

[0212]

[Chemical 55]

[0213]

[Chemical 56]

The color photographic light-sensitive material as described above was subjected to wedge exposure with blue light and then processed by the method described below. (Processing method) Processing time Processing temperature Color development 3 minutes 15 seconds 38 ℃ Bleaching 1 minute 00 seconds 38 ℃ Bleaching fixing 3 minutes 15 seconds 38 ℃ Water washing (1) 40 seconds 35 ℃ Water washing (2) 1 minute 00 Second 35 ℃ Stability 40 seconds 38 ℃ Dry 1 minute 15 seconds 55 ℃

Next, the composition of the processing liquid will be described. (Color developer) (Unit: g) Diethylenetriaminepentaacetic acid 1.0 1-Hydroxyethylidene-1,1-diphosphonic acid 2.0 Sodium sulfite 4.0 Potassium carbonate 30.0 Potassium bromide 1.4 Potassium iodide 1.5 mg Hydroxylamine sulfate 2.4 4- [N- Ethyl-N- (β-hydroxyethyl) amino] -2-methylaniline sulfate (PPD-1) 4.5 Water was added to 1.0 liter pH (adjusted with potassium hydroxide and sulfuric acid) 10.05

(Bleaching Solution) (Unit: g) Ethylenediaminetetraacetic acid ammonium ferric dihydrate 120.0 Ethylenediaminetetraacetic acid disodium salt 10.0 Ammonium bromide 100.0 Ammonium nitrate 10.0 Bleaching accelerator 0.005 mol (CH ₃ ) ₂ N-CH _{2- CH 2 -SS-CH 2 -CH 2} -N (CH 3) 2 · 2HCl aqueous ammonia (27%) was added to 15.0 ml water 1.0 l pH (adjusted with aqueous ammonia and nitric acid) 6.3

(Bleaching Fixing Solution) (Unit: g) Ethylenediaminetetraacetic acid ammonium ferric dihydrate 50.0 Ethylenediaminetetraacetic acid disodium salt 5.0 Sodium sulfite 12.0 Ammonium thiosulfate aqueous solution (700 g / liter) 240.0 mL Ammonia water (27%) 6.0 1.0 liter pH by adding milliliter water (adjusted with ammonia water and acetic acid) 7.2

(Washing Solution) Tap water was used as an H-type strongly acidic cation exchange resin (Amberlite IR-produced by Rohm and Haas).
120B) and an OH type anion exchange resin (Amberlite IR-400) were passed through the column to treat calcium and magnesium ions at a concentration of 3 mg / liter or less, and then isocyanuric dichloride. Sodium 20 mg / liter and sodium sulfate 0.15 g / liter were added. The pH of this liquid was in the range of 6.5 to 7.5.

(Stabilizer) (Unit: g) Sodium p-toluenesulfinate 0.03 Polyoxyethylene-p-monononylphenyl ether (Average degree of polymerization: 10) 0.2 Ethylenediaminetetraacetic acid disodium salt 0.05 1,2,4-triazole 1.3 1,4-bis (1,2,4-triazol-1-ylmethyl) piperazine 0.75 Water was added to 1.0 liter pH 8.5

The sample obtained by this treatment was treated with (STN-
1). Further, (PPD-1) in the color developing solution is shown below (PPD-2), (PPD-3) and (PPD).
-4) The same processing was performed except that each was changed.
However, the time of color development was adjusted so that the same optical density of 1.8 could be obtained with the exposure amount that gives an optical density of 1.8 for the yellow image of the sample (STN-1).

[0221]

[Chemical 57]

(Preparation of Color Developer Precursor Composition) 4
250 ml of an ethanol solution of Comparative Compound 1 below having a concentration of 7.6 mmol / liter was prepared, and a buffer solution having the following composition was added thereto in an amount of 1.2 liter. (Buffer solution composition) (Unit: gram) Diethylenetriaminepentaacetic acid 1.0 1-Hydroxyethylidene-1,1-diphosphonic acid 2.0 Sodium sulfite 4.0 Potassium carbonate 30.0 Potassium bromide 1.4 Potassium iodide 1. Add 5 mg water to 1.0 liter pH (adjusted with potassium hydroxide and sulfuric acid) 10.05

(Preparation of Color Developer) This is described by Hiroshi Yoneyama,
In addition to the cathode side of the device described in Electrochemistry, page 6 (Dainippon Tosho Publishing, 1986), the above buffer solution was added to the anode side. Next, a voltage of 2 to 3 V was applied between both electrodes and electrolysis was performed for 15 minutes. Incidentally, stainless steel was used for both the positive and negative electrodes.

Sample 101 was processed in exactly the same manner as the above-mentioned processing method except that this was used as a color developing solution. However, the time of color development was adjusted so that the same optical density of 1.8 could be obtained with the exposure amount that gives an optical density of 1.8 for the yellow image of the sample (STN-1). Next, a similar color developer precursor composition was prepared except that Comparative Compound 1 in the color developer precursor composition was changed to Comparative Compound 2 and Comparative Compound 3 shown below and the compounds of the present invention shown in Table 101. Each sample was obtained by preparing and performing the same operation. The yellow fog density of the obtained sample was compared with that of (STN-1), and the increase is shown in Table 101. Comparative color developing agent precursor composition

[0225]

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Table 101

[0227]

[Table 2]

As is clear from Table 101, when a color developing solution prepared by electrolysis using Comparative Compounds 1, 2 and 3 is used, a marked increase in fog density of a yellow image is observed. However, this phenomenon is a color developing agent produced by electrolysis from Comparative Compound 1 (PPD
-2), a color developing agent produced by electrolysis from Comparative Compound 2 (PPD-3) and a color developing agent produced by electrolysis from Comparative Compound 3 (PPD-).
Not seen in 4). That is, the fog does not depend on the structure of the color developing agent, but is a problem specific to generating the color developing agent by electrolysis. It is also clear from Table 101 that the fog density of a yellow image can be suppressed to a low level by using the color developing agent precursor compound of the present invention. The problem of such fog on the yellow image is not pointed out in JP-A-6-308,676, and the problem is solved only by using the color developing agent precursor compound of the present invention. What can be done is quite amazing and is far from expected.

Example 2 The sample 101 in Example 1 was exposed to uniform green light,
The sample which was subjected to the treatment using (PPD-1) in Example 1 as a color developing agent and the exposure amount was adjusted so that the magenta density was 1.5 was exposed to red light and imagewise ( Wedge) After exposure, development processing was performed. The sample obtained by this treatment is designated as (STN-2). Further, (PPD-1) in the color developing solution is replaced with (PPD-
Except for changing 2) and (PPD-5), the same treatment was performed. However, the time for color development is the sample (STN
-2) was adjusted so that the same optical density 2.1 could be obtained with the exposure amount that gives the optical density 2.1 of the cyan image.

(Preparation of Color Developer Precursor Composition) 3
200 ml of an ethanol solution of 5.0 mmol / l of the comparative compound 4 was prepared, and a buffer solution having the following composition was added to the solution to make a volume of 2.2 liters. (Buffer Solution Composition) (Unit: Gram) Diethylenetriaminepentaacetic acid 1.0 1-Hydroxyethylidene-1,1-diphosphonic acid 2.0 Sodium sulfite 4.0 Potassium carbonate 27.0 Potassium bromide 1.2 Potassium iodide 1. Add 5 mg water to 1.0 liter pH (adjusted with potassium hydroxide and sulfuric acid) 10.05

(Preparation of Color Developer) This was electrolyzed in the same manner as in Example 1. Sample 101 was processed in exactly the same manner as the above-described processing method except that this was used as a color developing solution. However, the color development time was adjusted so that the same optical density 2.1 could be obtained with the exposure amount that gives the optical density 2.1 of the cyan image in the sample (STN-2). Next, a similar color developer precursor composition was prepared, except that the comparative compound 4 in the color developer precursor composition was changed to the comparative compound 1 and the compound of the present invention shown in Table 201, and the same operation was performed. Each sample was obtained by carrying out. The interlayer effect of each obtained sample was evaluated as follows. That is, the density difference (ΔDG =) between the magenta density (Da) in the exposed area where the cyan image density of each sample is 2.1 and the magenta density (Db) in the substantially unexposed area where the cyan image density gives the fog density. Db-Da) was used as a measure of the interlayer effect, and the difference was evaluated. Further, the results are shown in Table 2 for the color developing agent precursor compound represented by the general formula (D1) of the present invention.
Shown in 01. Table 201

[0232]

[Table 3]

As is clear from Table 201, when the color developers prepared by electrolysis using Comparative Compounds 1 and 4 are used, the interlayer effect is remarkably reduced. This reduction in the interlayer effect leads to an increase in the color turbidity, which is a factor that deteriorates the color reproducibility. However, this phenomenon is a color developing agent produced by electrolysis from Comparative Compound 1 (PPD-2) and a color developing agent produced by electrolysis from Comparative Compound 4 (PPD-5).
Not seen in. That is, the reduction of the interlayer effect does not depend on the structure of the color developing agent, but is a problem specific to generating the color developing agent by electrolysis. It is also clear from Table 201 that by using the color developing agent precursor compound of the present invention, an effect substantially similar to the interlayer effect seen in (STN-2) can be obtained. Such a problem of reduction of interlayer effect is not pointed out in JP-A-6-308,676, and the problem is solved only by using the color developing agent precursor compound of the present invention. What can be done is quite amazing and is far from expected.

Example 3 A surface of a paper support laminated on both sides with polyethylene was subjected to a corona discharge treatment, and then a gelatin subbing layer containing sodium dodecylbenzenesulfonate was provided, and various photographic constituent layers were further coated to prepare the following. A multilayer color photographic paper (Sample 301) having the layer structure shown was produced. The coating liquid was prepared as follows.

Preparation of coating solution for first layer Yellow coupler (ExY) 153.0 g, color image stabilizer (Cpd-1) 15.0 g, color image stabilizer (Cpd-2)
7.5 g, color image stabilizer (Cpd-3) 16.0 g, solvent (Solv-1) 25 g, solvent (Solv-2) 25 g
And 180 cc of ethyl acetate, and this solution was emulsified and dispersed in 1000 g of a 10% aqueous gelatin solution containing 60 cc of 10% sodium dodecylbenzenesulfonate and 10 g of citric acid to prepare an emulsified dispersion A. On the other hand, a silver chlorobromide emulsion A (a cube, a 3: 7 mixture of a large size emulsion A having an average grain size of 0.88 μm and a small size emulsion A having a grain size of 0.70 μm (silver mole ratio). The variation coefficient of the grain size distribution is , 0.08 and 0.10 respectively, and silver bromide 0.3 for each size emulsion
Mol% localized on a portion of the surface of the silver chloride-based grain) was prepared. In this emulsion, the blue-sensitizing dyes A and B shown below were 2.0 × 10 ⁻⁴ mol per mol of silver for the large-sized emulsion A, and respectively for the small-sized emulsion A. 2.5 × 10 ⁻⁴ mol is added. The chemical ripening of this emulsion was performed by adding a sulfur sensitizer and a gold sensitizer. The above emulsified dispersion A and this silver chlorobromide emulsion A were mixed and dissolved to prepare a coating solution for the first layer having the following composition. The emulsion coating amount indicates a coating amount equivalent to silver.

Coating solutions for the second to seventh layers were prepared in the same manner as the coating solution for the first layer. 1-Oxy-3,5-dichloro-s-triazine sodium salt was used as a gelatin hardening agent for each layer. Also, Cpd-14 and C are added to each layer.
The total amount of pd-15 is 25.0 mg / m ² and 50.0, respectively.
It was added to be mg / m ² . The following spectral sensitizing dyes were used for the silver chlorobromide emulsion of each photosensitive emulsion layer. Blue-sensitive emulsion layer

[0237]

Embedded image

(2.0 × 10 ^-4 mol each for large size emulsion and 2.5 × 10 ^-4 mol each for small size emulsion per mol of silver halide) Green-sensitive emulsion layer

[0239]

Embedded image

(Per mol of silver halide, 4.0 × 10 ^-4 mol for large-sized emulsion, 5.6 × 10 ^-4 mol for small-sized emulsion) and

[0241]

[Chemical formula 61]

(7.0 × 10 ⁻⁵ mol for large size emulsion and 1.0 × 10 ⁻⁴ mol for small size emulsion per mol of silver halide) Red-sensitive emulsion layer

[0243]

Embedded image

(Per mol of silver halide, 0.9 × 10 ⁻⁴ mol for large size emulsion and 1.1 × 10 ⁻⁴ mol for small size emulsion)

Further, the following compounds were added in an amount of 2.6 × 10 ^-3 mol per mol of silver halide.

[0246]

[Chemical formula 63]

For the blue-sensitive emulsion layer, the green-sensitive emulsion layer and the red-sensitive emulsion layer, 1- (5-methylureidophenyl)-
5-Mercaptotetrazole to silver halide 1
8.5 × 10 ^-5 moles, 7.7 × 10 ^-4 moles per mole,
2.5 × 10 ^-4 mol was added. Further, 4-hydroxy-6-methyl-1,
3,3a, 7-Tetrazaindene was added at 1 × 10 ⁻⁴ mol and 2 × 10 ⁻⁴ mol per mol of silver halide, respectively. Further, in order to prevent irradiation, the following dye (the amount in parentheses represents the coating amount) was added to the emulsion layer.

[0248]

[Chemical 64]

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

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

First layer (blue-sensitive emulsion layer) Silver chlorobromide emulsion A 0.27 Gelatin 1.36 Yellow coupler (ExY) 0.79 Color image stabilizer (Cpd-1) 0.08 Color image stabilization Agent (Cpd-2) 0.04 Color image stabilizer (Cpd-3) 0.08 Solvent (Solv-1) 0.13 Solvent (Solv-2) 0.13

Second Layer (Color Mixing Prevention Layer) Gelatin 1.00 Color mixing inhibitor (Cpd-4) 0.06 Solvent (Solv-2) 0.25 Solvent (Solv-3) 0.25 Solvent (Solv-7) 0.03

Third Layer (Green Sensitive Emulsion Layer) Silver chlorobromide emulsion (cubic, 1: 3 mixture of large size emulsion B having an average grain size of 0.55 μm and small size emulsion B having a grain size of 0.39 μm (Ag mol) The coefficient of variation of the grain size distribution was 0.10 and 0.08, respectively, and 0.8 mol% of AgBr was locally contained in a part of the grain surface based on silver chloride in each size emulsion. ) 0.13 gelatin 1.45 magenta coupler (ExM) 0.16 color image stabilizer (Cpd-2) 0.03 color image stabilizer (Cpd-5) 0.15 color image stabilizer (Cpd-6) 0 .01 color image stabilizer (Cpd-7) 0.01 color image stabilizer (Cpd-8) 0.08 solvent (Solv-3) 0.50 solvent (Solv-4) 0.15 solvent (Solv-5) 0.15

Fourth Layer (Color Mixing Prevention Layer) Gelatin 0.70 Color mixing inhibitor (Cpd-4) 0.04 Solvent (Solv-2) 0.18 Solvent (Solv-3) 0.18 Solvent (Solv-7) 0.02

Fifth Layer (Red Sensitive Emulsion Layer) Silver chlorobromide emulsion (cubic, 1: 4 mixture of large size emulsion C having an average grain size of 0.50 μm and small size emulsion C of 0.41 μm (Ag mol) The coefficient of variation of the grain size distribution is 0.09 and 0.11, and 0.8 mol% of AgBr in each size emulsion was locally contained in a part of the grain surface based on silver chloride). 20 Gelatin 0.85 Cyan coupler (ExC) 0.33 Ultraviolet absorber (UV-2) 0.18 Color image stabilizer (Cpd-1) 0.33 Color image stabilizer (Cpd-6) 0.01 Color image Stabilizer (Cpd-8) 0.01 Color image stabilizer (Cpd-9) 0.01 Color image stabilizer (Cpd-10) 0.01 Color image stabilizer (Cpd-11) 0.01 Solvent (Solv- 1) 0.01 solvent (Solv-6) 0.22

Sixth Layer (Ultraviolet Absorbing Layer) Gelatin 0.55 Ultraviolet Absorber (UV-1) 0.38 Color Image Stabilizer (Cpd-5) 0.02 Color Image Stabilizer (Cpd-12) 0.15

Seventh Layer (Protective Layer) Gelatin 1.13 Acrylic Modified Copolymer of Polyvinyl Alcohol (Modification Degree 17%) 0.05 Liquid Paraffin 0.02 Surfactant (Cpd-13) 0.01

[0258]

Embedded image

[0259]

[Chemical formula 66]

[0260]

Embedded image

[0261]

[Chemical 68]

[0262]

[Chemical 69]

[0263]

Embedded image

The above light-sensitive material was exposed through an optical wedge and then processed in the next step. Treatment process Temperature Time Color development 38.5 ℃ 45 seconds Bleach-fix 35 ℃ 45 seconds Rinse (1) 35 ℃ 30 seconds Rinse (2) 35 ℃ 30 seconds Rinse (3) 35 ℃ 30 seconds Dry 80 ℃ 60 seconds (rinse is ( The 3 tank countercurrent method from 3) to (1) was adopted.)

The composition of each processing solution is as follows. [Color developer] Water 800 ml Ethylenediaminetetraacetic acid 3.0 g 4,5-Dihydroxybenzene-1,3-disulfonic acid disodium salt 0.5 g Triethanolamine 12.0 g Potassium chloride 6.5 g Potassium bromide 0.03 g Potassium carbonate 27.0 g Fluorescent brightener (WHITEX 4 manufactured by Sumitomo Chemical) 1.0 g Sodium sulfite 0.1 g Disodium-N, N-bis (sulfonate ethyl) hydroxylamine 5.0 g Triisopropylnaphthalene (β) sulfone Sodium acid salt 0.1 g N-ethyl-N- (β-methanesulfonamidoethyl) -3-methyl-4-aminoaniline / 3/2 sulfuric acid monohydrate (PPD-5) 5.0 g Water was added 1000 Milliliter pH (25 ° C / adjusted with potassium hydroxide and sulfuric acid) 10.00

[Bleach-fixing solution] Water 600 ml Ammonium thiosulfate (750 g / liter) 93 ml Ammonium sulfite 40 g Ethylenediaminetetraacetic acid iron (III) ammonium 55 g Ethylenediaminetetraacetic acid 5 g Nitric acid (67%) 30 g Water is added to 1000 ml pH ( 25 ℃ / adjusted with acetic acid and ammonia water) 5.8

[Rinse Solution] Sodium chlorinated isocyanurate 0.02 g Deionized water (conductivity 5 μs / cm or less) 1000 ml pH 6.5

The sample obtained by this treatment was treated with (STN-
3). (Preparation of Color Developer Precursor Composition) 200 ml of an ethanol solution of Comparative Compound 4 having a concentration of 35.0 mmol / liter was prepared, and a buffer solution having the following composition was added thereto in an amount of 2.2 liter. . (Buffer Solution Composition) (Unit: Gram) Ethylenediaminetetraacetic acid 3.0 4,5-Dihydroxybenzene-1,3-disulfonic acid disodium salt 0.5 Triethanolamine 12.0 Potassium carbonate 27.0 Potassium chloride 6.5 Potassium bromide 0.03 Optical brightener (WHITEX 4 manufactured by Sumitomo Chemical Co., Ltd.) 1.0 Sodium sulfite 0.1 Sodium triisopropylnaphthalene (β) sulfonate 0.1 Water was added to 1.0 liter pH (25 ° C / Adjusted with potassium hydroxide and sulfuric acid) 10.00

(Preparation of Color Developer) This was electrolyzed in the same manner as in Example 1. Here, in order to evaluate the performance when the electrolytic cell was repeatedly used, the following operation was further performed. That is, in the above-described preparation of the color developing solution, the color developer precursor composition is added to the electrolytic bath to prepare the color developing solution, and the prepared developing solution is discarded without being used.
This was repeated 10 times, and the sample 301 was processed in exactly the same manner as the above-mentioned processing method except that the developing solution prepared in the 11th time was used as the color developing solution.

Next, a similar color developer precursor composition was prepared except that the comparative compound 4 in the color developer precursor composition was changed to comparative compound 1, comparative compound 3 and the compounds of the present invention shown in Table 301. Each sample was obtained by preparing and performing the same operation including the above-mentioned repeated operation. With respect to the obtained image, the magenta density of each sample was measured with (STN-3) at an exposure amount that gives an optical density of 2.0 for the magenta image. As for the yellow density of each sample, as described above, the color development time is adjusted so that the same yellow density can be obtained with the same exposure amount with respect to (STN-3). Therefore, in order to obtain a desired image, the optical density of the magenta image is 2.0 in STN-3 even in the magenta density.
The same magenta density of 2.0 is required for the exposure amount that gives .DELTA. Table 301 shows the result of evaluating this point. Table 301

[0271]

[Table 4]

As is clear from Table 301, the desired magenta density of 2.0 cannot be obtained when the color developers prepared after repeatedly using the electrolytic cells with Comparative Compounds 1, 3 and 4 are used. . On the other hand, by using the color developing agent precursor compound of the present invention, it is possible to suppress the decrease in magenta concentration even when the electrolytic cell is repeatedly used. The problem of such a decrease in magenta density is not pointed out in JP-A-6-308,676, and the problem can be solved only by using the color developing agent precursor compound of the present invention. It's totally amazing and never expected.

Example 4 N-Ethyl-3-methyl-N- (2-methylsulfonamidoethyl) in a color developer precursor composition according to the description of Example 2 in JP-A-6-308,676. -4-
Instead of nitrosoaniline, equimolar amounts of the compounds (D1-2), (D2-5), (D3-1), (D4-) of the present invention.
When a similar experiment was performed using 8) and (D5-6), an amplified image could be obtained.

Example 5 N-Ethyl-3-methyl-N- (2-methylsulfonamidoethyl) in a color developer precursor composition according to the description of Example 3 in JP-A-6-308,676. -4-
Instead of nitrosoaniline, equimolar amounts of the compounds (D1-11), (D2-1), (D3-3), (D4) of the present invention.
When the same experiment was performed using (9) and (D5-1), it was confirmed that development occurred.

Example 6 1) Support The support used in this example was prepared by the following method. 100 parts by weight of commercially available polyethylene-2,6-naphthalate polymer and Tinuvin P.326 as an ultraviolet absorber.
2 parts by weight of Ciba-Geigy (manufactured by Ciba-Geigy) was dried by a conventional method, melted at 300 ° C., extruded from a T-die and longitudinally stretched 3.0 times at 140 ° C., and then 13
The film was transversely stretched 3.0 times at 0 ° C. and further heat set at 250 ° C. for 6 seconds to obtain a PEN film having a thickness of 90 μm. Further, a part thereof was wound around a stainless steel core having a diameter of 20 cm and subjected to a heat history of 110 ° C. for 48 hours. 2) Coating of undercoat layer The above-mentioned support is subjected to corona discharge treatment, UV discharge treatment, glow discharge treatment, and flame treatment on both sides thereof,
An undercoat liquid having the following composition was applied to each surface, and an undercoat layer was provided on the high temperature surface side during stretching. Pillar Pill for corona discharge treatment
A solid state corona processor 6KVA model manufactured by ar Co. is used to treat a 30 cm wide support at 20 m / min. At this time, the object to be processed is 0.37 from the readings of current and voltage.
Processing of 5 KV · A · min / m ² was performed. The discharge frequency during the treatment was 9.6 KHz, and the gap clearance between the electrode and the dielectric roll was 1.6 mm. UV discharge treatment is 7
Discharge treatment was performed while heating at 5 ° C. Further, the glow discharge treatment was performed by irradiating with a cylindrical electrode at 3000 W for 30 seconds. Gelatin 3 g Distilled water 25 ml Sodium α-sulfo-di-2-ethylhexyl succinate 0.05 g Formaldehyde 0.02 g Salicylic acid 0.1 g Diacetyl cellulose 0.5 g p-Chlorophenol 0.5 g Resorcin 0.5 g Cresol 0 0.5 g (CH ₂ = CHSO ₂ CH ₂ CH ₂ NHCO) ₂ CH ₂ 0.2 g Aziridine 3-fold molar adduct of trimethylolpropane 0.2 g Trimethylolpropane-toluene diisocyanate 3-fold molar adduct 0.2 g Methanol 15 ml Acetone 85 ml Formaldehyde 0.01 g Acetic acid 0.01 g Concentrated hydrochloric acid 0.01 g

3) Coating of Back Layer On one surface of the above-mentioned support after undercoating, an antistatic layer having the following composition, a magnetic recording layer and a sliding layer were coated as a back layer. 3-1) Coating of antistatic layer 3-1-1) Preparation of conductive fine particle dispersion liquid (tin oxide-antimony oxide composite dispersion liquid) 230 parts by weight of stannic chloride hydrate and antimony trichloride 2
3 parts by weight was dissolved in 3000 parts by weight of ethanol to obtain a uniform solution. A 1N aqueous sodium hydroxide solution was added dropwise to this solution until the pH of the solution reached 3, to obtain a coprecipitate of colloidal stannic oxide and antimony oxide. The obtained coprecipitate was left at 50 ° C. for 24 hours to obtain a reddish brown colloidal precipitate.

The reddish brown colloidal precipitate was separated by centrifugation. To remove excess ions, water was added to the precipitate and washed by centrifugation. This operation was repeated 3 times to remove excess ions. 200 parts by weight of the colloidal precipitate from which excess ions have been removed is redispersed in 1500 parts by weight of water, and 650
The powder was sprayed in a firing furnace heated to ℃ to obtain fine powder of tin oxide-antimony oxide composite having a bluish average particle size of 0.005 μm. The specific resistance of this fine particle powder was 5 Ω · cm. A mixed solution of 40 parts by weight of the above fine particle powder and 60 parts by weight of water was adjusted to pH 7.0 and roughly dispersed by a stirrer, and then a horizontal sand mill (trade name: Dynomill: WILLYA.BACHOFENAG).
(Manufactured by Mfg. Co., Ltd.) and dispersed until the residence time reached 30 minutes.
At this time, the average particle size of the secondary aggregate was about 0.04 μm.

3-1-2) Coating of Conductive Layer A conductive layer having the following formulation was coated so that the dry film thickness would be 0.2 μm, and dried at 115 ° C. for 60 seconds. Conductive fine particle dispersion prepared in 3-1-1) 20 parts by weight Gelatin 2 parts by weight Water 27 parts by weight Methanol 60 parts by weight p-Chlorophenol 0.5 parts by weight Resorcinol 2 parts by weight Polyoxyethylene nonylphenyl ether 0. 01 parts by weight The resistance of the obtained conductive film was 10 ^8.0 (100 V), and it had an excellent antistatic property. 3-2) Coating of magnetic recording layer Magnetic substance Co-deposited γ-Fe ₂ O ₃ (long axis 0.14 μm, single axis 0.
Needle-shaped 03μm, specific surface area 41m ² / g, saturation magnetization 89em
u / g, the surface is treated with 2% by weight of Fe ₂ O ₃ with aluminum oxide and silicon oxide respectively, coercive force 930 Oe, Fe ⁺²
/ Fe ⁺³ ratio was 6/94) 1100 g, water 220 g and poly (polymerization degree 16) oxyethylenepropyltrimethoxysilane silane coupling agent 150 g were added, and well kneaded in an open kneader for 3 hours. The roughly dispersed viscous liquid was dried at 70 ° C. for one day to remove water,
Surface-treated magnetic particles were prepared by heating at 110 ° C. for 1 hour. Further, the following formulation was used, and the mixture was kneaded again in an open kneader.

The above-mentioned surface-treated magnetic particles 1000 g Diacetyl cellulose 17 g Methyl ethyl ketone 100 g Cyclohexanone 100 g Furthermore, 200 with a sand mill (1/4 G) with the following formulation.
Finely dispersed at rpm for 4 hours. Kneaded product 100 g Diacetyl cellulose 60 g Methyl ethyl ketone 300 g Cyclohexanone 300 g Furthermore, diacetyl cellulose and a triple-cell adduct of trimethylolpropane-toluene diisocyanate as a curing agent were added to the binder in an amount of 20 wt%. The resulting liquid was diluted with equal amounts of methyl ethyl ketone and cyclohexanone so that the viscosity was about 80 cp. Also, the application is
The thickness is 1.2μm on the above conductive layer with a barter.
It was done so that The amount of the magnetic substance was applied so as to be 62 mg / m ² . Further, silica particles (0.
3 [mu] m) and aluminum oxide abrasives (0.5 [mu] m) were respectively added in an amount of 10 mg / m ^2. Drying at 115 ° C,
It was carried out for 6 minutes (the temperature of the rollers and the conveying device in the drying zone are 115 ° C.). X-light status M
The increase in the D ^B color density of the magnetic recording layer was about 0.1 when the blue filter was used. The saturation magnetization moment of the magnetic recording layer is 4.2 emu / m ² , and the coercive force is 923.
The Oe and the squareness ratio were 65%.

3-3) Preparation of Sliding Layer The following prescription liquid was applied so that the coating amount of the solid content of the compound was as follows, and dried at 110 ° C. for 5 minutes to obtain a sliding layer. Diacetyl cellulose 25 mg / m ² C ₆ H ₁₃ CH (OH) C ₁₀ H ₂₁ COOC ₄₀ H ₈₁ (Compound a) 6 mg / m ² C ₅₀ H ₁₀₁ O (CH ₂ CH ₂ O) ₁₆ H (Compound b) 9 mg / m ² Compound a / Compound b (6: 9) was xylene and propylene glycol monomethyl ether (volume ratio 1:
1) Heat and dissolve in a solvent at 105 ° C., and add 10 volumes of this solution to propylene glycol monomethyl ether (25
C.) to give a fine dispersion. After further diluting in 5 times the amount of acetone, it was redispersed with a high-pressure homogenizer (200 atm) to form a dispersion (average particle diameter 0.01 μm), which was then added and used. The performance of the obtained sliding layer is such that the dynamic friction coefficient is 0.06 (5 mmφ stainless hard ball, load 100).
g, speed 6 cm / minute), static friction coefficient 0.07 (clip method), and excellent properties. The sliding property with respect to the emulsion surface, which will be described later, also had a dynamic friction coefficient of 0.12.

4) Coating of Sensitive Material Layer Next, on the opposite side of the back layer obtained above, each layer having the following composition was multilayer coated to prepare a color negative film.
This is designated as Sample 601. (Photosensitive layer composition) The main materials used for each layer are classified as follows; ExC: Cyan coupler UV: UV absorber ExM: Magenta coupler HBS: High boiling point organic solvent ExY: Yellow coupler H: Gelatin Curing agent ExS: Sensitizing dye The numbers corresponding to the respective components indicate the coating amount expressed in units of g / m ² , and for silver halide, the coating amount in terms of silver. However, with respect to the sensitizing dye, the coating amount is shown in mol unit per mol of silver halide in the same layer.

(Sample 101) First layer (antihalation layer) Black colloidal silver Silver 0.09 Gelatin 1.60 ExM-1 0.12 ExF-1 2.0 × 10 ^-3 Solid disperse dye ExF-2 0.030 Solid disperse dye ExF-3 0.040 HBS- 1 0.15 HBS-2 0.02

Second layer (intermediate layer) Silver iodobromide emulsion M Silver 0.065 ExC-2 0.04 Polyethyl acrylate latex 0.20 Gelatin 1.04

Third Layer (Low Sensitivity Red Sensitive Emulsion Layer) Silver iodobromide emulsion A Silver 0.25 Silver iodobromide emulsion B Silver 0.25 ExS-1 6.9 × 10 ^-5 ExS-2 1.8 × 10 ^-5 ExS-3 3.1 × 10 ^-4 ExC-1 0.17 ExC-3 0.030 ExC-4 0.10 ExC-5 0.020 ExC-6 0.010 Cpd-2 0.025 HBS-1 0.10 Gelatin 0.87

Fourth Layer (Medium Sensitivity Red Sensitive Emulsion Layer) Silver Iodobromide Emulsion C Silver 0.70 ExS-1 3.5 × 10 ^-4 ExS-2 1.6 × 10 ^-5 ExS-3 5.1 × 10 ^-4 ExC-1 0.13 ExC-2 0.060 ExC-3 0.0070 ExC-4 0.090 ExC-5 0.015 ExC-6 0.0070 Cpd-2 0.023 HBS-1 0.10 Gelatin 0.75

Fifth layer (high-sensitivity red-sensitive emulsion layer) Silver iodobromide emulsion D Silver 1.40 ExS-1 2.4 × 10 ^-4 ExS-2 1.0 × 10 ^-4 ExS-3 3.4 × 10 ^-4 ExC-1 0.10 ExC-3 0.045 ExC-6 0.020 ExC-7 0.010 Cpd-2 0.050 HBS-1 0.22 HBS-2 0.050 Gelatin 1.10

Sixth layer (intermediate layer) Cpd-1 0.090 Solid disperse dye ExF-4 0.030 HBS-1 0.050 Polyethyl acrylate latex 0.15 Gelatin 1.10

Seventh Layer (Low Sensitivity Green Sensitive Emulsion Layer) Silver iodobromide Emulsion E 0.15 Silver iodobromide Emulsion F Silver 0.10 Silver iodobromide Emulsion G Silver 0.10 ExS-4 3.0 × 10 ^-5 ExS-5 2.1 × 10 ^-4 ExS-6 8.0 × 10 ^-4 ExM-2 0.33 ExM-3 0.086 ExY-1 0.015 HBS-1 0.30 HBS-3 0.010 Gelatin 0.73

Eighth Layer (Medium-Sensitivity Green Sensitive Emulsion Layer) Silver Iodobromide Emulsion H Silver 0.80 ExS-4 3.2 × 10 ^-5 ExS-5 2.2 × 10 ^-4 ExS-6 8.4 × 10 ^-4 ExC-8 0.010 ExM-2 0.10 ExM-3 0.025 ExY-1 0.018 ExY-4 0.010 ExY-5 0.040 HBS-1 0.13 HBS-3 4.0 × 10 ^-3 Gelatin 0.80

Ninth layer (high-sensitivity green-sensitive emulsion layer) Silver iodobromide emulsion I Silver 1.25 ExS-4 3.7 × 10 ^-5 ExS-5 8.1 × 10 ^-5 ExS-6 3.2 × 10 ^-4 ExC-1 0.010 ExM-1 0.020 ExM-4 0.025 ExM-5 0.040 Cpd-3 0.040 HBS-1 0.25 Polyethyl acrylate latex 0.15 Gelatin 1.33

10th layer (yellow filter layer) Yellow colloidal silver Silver 0.015 Cpd-1 0.16 Solid disperse dye ExF-5 0.060 Solid disperse dye ExF-6 0.060 Oil-soluble dye ExF-7 0.010 HBS-1 0.60 Gelatin 0.60

11th layer (low-sensitivity blue-sensitive emulsion layer) Silver iodobromide emulsion J Silver 0.09 Silver iodobromide emulsion K Silver 0.0 ExS-7 8.6 × 10 ^-4 ExC-8 7.0 × 10 ^-3 ExY-1 0.050 ExY-2 0.22 ExY-3 0.50 ExY-4 0.020 Cpd-2 0.10 Cpd-3 4.0 × 10 ^-3 HBS-1 0.28 Gelatin 1.20

Twelfth layer (high-sensitivity blue-sensitive emulsion layer) Silver iodobromide emulsion L Silver 1.00 ExS-7 4.0 × 10 ^-4 ExY-2 0.10 ExY-3 0.10 ExY-4 0.010 Cpd-2 0.10 Cpd-3 1.0 × 10 ^-3 HBS-1 0.070 Gelatin 0.70

Thirteenth layer (first protective layer) UV-1 0.19 UV-2 0.075 UV-3 0.065 HBS-1 5.0 x 10 ^-2 HBS-4 5.0 x 10 ^-2 Gelatin 1.8

Fourteenth layer (second protective layer) Silver iodobromide emulsion M Silver 0.10 H-1 0.40 B-1 (diameter 1.7 μm) 5.0 × 10 ^-2 B-2 (diameter 1.7 μm) 0.15 B-3 0.05 S-1 0.20 Gelatin 0.70

Further, in order to improve the storability, processability, pressure resistance, antifungal / antibacterial property, antistatic property and coating property of each layer, W-1 to W-3, B-4 to B- may be used. 6, F
-1 to F-17 and iron salt, lead salt, gold salt, platinum salt,
It contains a palladium salt, an iridium salt, and a rhodium salt.

[0297]

[Table 5]

In Table-B, (1) Emulsions J to L were prepared according to the examples of JP-A-2-91938.
It is reduction-sensitized during grain preparation using thiourea dioxide and thiosulfonic acid. (2) Emulsions A to I were prepared according to the examples of JP-A-3-237450.
Gold sensitization, sulfur sensitization and selenium sensitization are performed in the presence of the spectral sensitizing dye described in each photosensitive layer and sodium thiocyanate. (3) For the preparation of tabular grains, low molecular weight gelatin is used according to the examples of JP-A 1-158426. (4) Dislocation lines as described in JP-A-3-237450 are observed in the tabular grains by using a high voltage electron microscope. (5) Emulsion L is a double structure grain containing an internal high iodine core described in JP-A-60-143331.

Preparation of Dispersion of Organic Solid Disperse Dye ExF-2 shown below was dispersed by the following method. That is, water 21.7
3 ml of 5% sodium p-octylphenoxyethoxyethoxyethane sulfonate and 5% aqueous solution
0.5 g of an aqueous solution of p-octylphenoxypolyoxyethylene ether (degree of polymerization: 10) was put in a 700 ml pot mill, and 5.0 g of dye ExF-2 and 500 ml of zirconium oxide beads (diameter 1 mm) were added. The contents were dispersed for 2 hours. A BO type vibrating ball mill manufactured by Chuo Koki was used for this dispersion. After the dispersion, the contents were taken out, added to 8 g of a 12.5% gelatin aqueous solution, and the beads were removed by filtration to obtain a gelatin dispersion of the dye. The average particle size of the dye particles is 0.44
μm.

In the same manner, solid dispersions of ExF-3, ExF-4 and ExF-6 were obtained. The average particle diameters of the dye fine particles were 0.24 μm, 0.45 μm and 0.52 μm, respectively.
ExF-5 is a microprecipitation described in Example 1 of European Patent Application Publication (EP) 549,489A.
It was dispersed by the dispersion method. The average particle size was 0.06 μm.

[0301]

Embedded image

[0302]

Embedded image

[0303]

Embedded image

[0304]

[Chemical 74]

[0305]

[Chemical 75]

[0306]

[Chemical 76]

[0307]

Embedded image

[0308]

Embedded image

[0309]

Embedded image

[0310]

Embedded image

[0311]

[Chemical 81]

[0312]

[Chemical formula 82]

[0313]

[Chemical 83]

[0314]

[Chemical 84]

[0315]

Embedded image

[0316]

[Chemical 86]

The light-sensitive material prepared as described above is used for 24 mm
The width is cut into 160 cm, and two 2 mm square perforations are provided at a distance of 5.8 mm at a position 0.7 mm from one side in the length direction of the photosensitive material. The two sets were provided at intervals of 32 mm to produce US Pat.
6,887, FIG. 1-FIG. It was housed in the plastic film cartridge described in 7.
The head gap 5 was applied to this sample from the coated surface side of the magnetic recording layer.
Using a head capable of inputting and outputting of μm and number of turns of 2000, 100 mm between the perforations of the photosensitive material
The FM signal was recorded at a feed rate of / s. After the FM signal was recorded, the emulsion surface was subjected to a uniform exposure of 1000 cms over the whole area, each processing was carried out by the method described below, and then the emulsion was stored again in the original plastic film cartridge. This sample 601 was used as a color developer precursor compound instead of the comparative compound 4 in an equimolar amount of the compound (D1-1) of the present invention,
(D2-12), (D3-5), (D4-2) and (D
5-4) was electrolyzed in the same manner as in Example 2 and treated with a color developer obtained to obtain a desired image.

[Procedure amendment]

[Submission date] July 12, 1995

[Procedure Amendment 1]

[Document name to be amended] Statement

[Correction target item name] 0071

[Correction method] Change

[Correction content]

[0071]

[Chemical 31]

[Procedure Amendment 2]

[Document name to be amended] Statement

[Correction target item name] 0084

[Correction method] Change

[Correction content]

[0084]

[Chemical Formula 39]

[Procedure 3]

[Document name to be amended] Statement

[Correction target item name] 0233

[Correction method] Change

[Correction content]

As is clear from Table 201, when the color developers prepared by electrolysis using Comparative Compounds 1 and 4 are used, the interlayer effect is remarkably reduced. This reduction in the interlayer effect leads to an increase in the color turbidity, which is a factor that deteriorates the color reproducibility. However, this phenomenon is not seen in the color developing agent (PPD-2) which is produced by electrolysis from Comparative Compound 1 and the color developing agent (PPD-5) which is produced by electrolysis from Comparative Compound 4. That is, the reduction of the interlayer effect does not depend on the structure of the color developing agent, but is a problem specific to generating the color developing agent by electrolysis. It is also clear from Table 201 that by using the color developing agent precursor compound of the present invention, an effect substantially similar to the interlayer effect seen in (STN-2) can be obtained. Such a problem of reduction of interlayer effect is not pointed out in JP-A-6-308,676, and the problem is solved only by using the color developing agent precursor compound of the present invention. What can be done is quite amazing and is far from expected. ─────────────────────────────────────────────────── ───

[Procedure amendment]

[Submission date] August 7, 1995

[Procedure Amendment 1]

[Document name to be amended] Statement

[Correction target item name] 0215

[Correction method] Change

[Correction content]

Next, the composition of the processing liquid will be described. (Color developer) (Unit: g) Diethylenetriaminepentaacetic acid 1.0 1-Hydroxyethylidene-1,1-diphosphonic acid 2.0 Sodium sulfite 4.0 Potassium carbonate 30.0 Potassium bromide 1.4 Potassium iodide 1.5 mg Hydroxylamine sulfate 1.2 Disodium N, N -Bis (sulfonate ethyl) hydroxylamine 2.2 4- [N-ethyl-N- (β-hydroxyethyl) amino] -2-methylaniline sulfate (PPD-1) 4.5 Water was added to 1.0 liter pH (hydroxylation Adjusted with potassium and sulfuric acid) 10.05

Claims (1)

[Claims] 1. A silver halide color developing agent is formed or released on an electrode when electrolyzed.
1), (D2), (D3), (D4) or (D5) An aqueous medium containing a color developing agent precursor composition represented by (D5) is electrolyzed to prepare a color photographic developer. Method. General formula (D1) In the formula, R ₁ , R ₂ , R ₃ , R ₄ , R ₅ and R ₆ may be the same or different and each represents a hydrogen atom or a substituent. R ₇ represents an alkyl group. R ₈ represents a substituent. m
Represents an integer of 0 to 3. X represents a group capable of generating an NH ₂ group by electrolysis. General formula (D2) In the formula, R ₇ has the same meaning as in formula (D1). R ₉ ,
R ₁₀ , R ₁₁ and R ₁₂ may be the same or different and each represents a hydrogen atom or a substituent. R ₁₃ represents a substituent. n
Represents an integer of 0 to 3. X has the same meaning as in formula (D1). General formula (D3) In the formula, R ₁₄ , R ₁₅ , R ₁₆ , R ₁₇ , R ₁₈ , R ₁₉ , R ₂₀ , and R
₂₁ may be the same or different and each represents a hydrogen atom or a substituent. R ₂₂ represents a substituent. p represents an integer of 0 to 4. X has the same meaning as in formula (D1). General formula (D4) In the formula, R ₂₃ represents a straight-chain or branched unsubstituted alkyl group having 1 to 6 carbon atoms, or a straight-chain or branched hydroxyalkyl group having 2 to 6 carbon atoms whose main chain has 2 to 6 carbon atoms. . R ₂₄ is a C 2-6 straight-chain or branched unsubstituted alkylene group whose main chain is C 2-6, a C 3-6 straight-chain or branched chain whose main chain is C 2-6 Represents a hydroxyalkylene group. R ₂₅ is a straight chain having 1 to 4 carbon atoms,
Represents a branched or cyclic alkyl group. X is a general formula (D
It has the same meaning as 1). General formula (D5) In the formula, R ₂₆ represents a linear or branched alkyl group having 1 to 6 carbon atoms. R ₂₇ represents a linear or branched alkylene group having a carbon number of 3 to 6 and a main chain of 3 to 6 carbon atoms. R ₂₈
Represents a linear or branched alkyl group having 1 to 4 carbon atoms.
R ₂₉ represents a linear, branched or cyclic alkyl group having 1 to 4 carbon atoms. X has the same meaning as in formula (D1).