JPH1112251A - 4-amino-n,n-dialkylaniline compound, treating composition for photography obtained by using the same, and formation of color image - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject new compound in which a new 1-N-substituted group forms a condensed ring with benzene ring, useful as a coloring development main agent for silver halide color photosensitive materials. SOLUTION: This compound is represented by formula I [R<1> is an alkyl, an aryl or a heterocyclic group; R<2> is a substituent group; R<3> is H or a substituent group; Z is ethylene or trimethylene; L is a bifunctional group binding to carbon atom on ethylene chain or trimethylene chain of Z or single bond; (n) is 1-8; (m) is 0-3], e.g. a compound of formula II. The compound of formula I is obtained by reacting, e.g. amino group of aniline forming a condensed ring with benzene with an alkyl, an aryl or heterocyclic halide or an alkyl or an arylsulfonate, etc., to introduce an alkyl group (R<1> ), then, introducing azicoupling, nitroso or nitro group at para position of amino group and reducing these products.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a novel compound which is useful as a developing agent for silver halide color photography or is expected to be useful as a dye intermediate, a medicine, a pesticide and the like. And a 4-amino-N, N-dialkylaniline compound having an ethyleneoxy group or a polyethyleneoxy group on a substituent of the condensed ring, a treatment composition containing the compound, and the treatment solution. The present invention relates to a color image forming method.

[0002]

2. Description of the Related Art A 4-amino-N, N-dialkylaniline compound is useful as a silver halide color photographic developing agent.
-161061 and JP-A-7-36162.

In recent years, with the increase in over-the-counter processing called mini-labs and the increase in the number of color negative films used in the news photography field, development processing has been completed in a shorter time.
There is a rapidly increasing demand for providing prints to customers or publishing them in newspapers or the like. In particular, there is a particularly high demand for shortening the processing time for processing a color negative film, which requires a longer time than color paper.

Among the processing steps, with respect to shortening of the color developing step, Japanese Patent Application Laid-Open No. 4-45440 discloses a method using a tetrahydroquinoline or dihydroindole derivative as a color developing agent. The use of these compounds as color developing agents is also described in U.S. Pat. Nos. 2,196,739 and 2,566,259. In particular, JP-A-4-45440 discloses that even in a color photographic light-sensitive material mainly containing a silver iodobromide emulsion such as a color negative film, the color developing step can be shortened by using these compounds as a color developing agent. Is described. Further, JP-A-7-2873
No. 70 and EP 670,312 A1 describe that when at least one of the three carbon atoms forming the propylene chain of the tetrahydroquinoline skeleton has no hydrogen atom, the fog density is reduced.

However, it has been found that when a color photographic light-sensitive material is developed with the compounds described in these specifications, the graininess deteriorates. In recent years, with the advancement of color photographic light-sensitive materials and the reduction of the area per frame, a technique for improving graininess has become extremely important. However, there is no description in this specification of a technique for improving graininess when this compound is used for color development.

The above-mentioned Japanese Patent Application Laid-Open No. 4-45440, US Pat. Nos. 2,196,739 and 2,566,259.
JP-A-7-287370, EP 670,3
As a substituent on the condensed ring of the tetrahydroquinoline compound or dihydroindole compound described in No. 12A1, a group having an ethyleneoxy group or a polyethyleneoxy group having two or more repeating units is shown in the text or anywhere in specific compound examples. Not. Further, the use is not limited to a silver halide color photographic developing agent, but a known tetrahydroquinoline compound, dihydroindole compound, etc.
4-amino- wherein the N substituent forms a condensed ring with a benzene ring
In the N, N-dialkylaniline compound, an ethyleneoxy group or a repeating unit 2 is substituted as a substituent on the condensed ring.
There is no such group having a polyethyleneoxy group.

[0007]

Accordingly, an object of the present invention is to provide a 4-amino-N, N-dialkylaniline compound in which a novel 1-N substituent forms a condensed ring with a benzene ring. Another object of the present invention is to provide a novel color developing agent useful for silver halide color photography, a processing solution of a silver halide color photographic light-sensitive material using the developing agent, and a color image forming method. More specifically, it is an object of the present invention to provide a color developing agent having rapid processing suitability and sufficient granularity, a processing solution of a silver halide color photographic light-sensitive material using the developing agent, and a color image forming method.

[0008]

Means for Solving the Problems The above-mentioned problems are as follows: (1) An aniline compound represented by the following general formula (I). General formula (I)

[0009]

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In the formula, R ¹ represents an alkyl group, an aryl group or a heterocyclic group, and R ² represents a substituent. R ³ represents a hydrogen atom or a substituent; Z represents an ethylene group or a trimethylene group; and L represents a divalent group or a single bond bonded to a carbon atom on the ethylene chain or trimethylene chain of Z. n
Represents an integer of 1 to 8, and m represents an integer of 0 to 3. When m is 2 or more, R ² may be the same or different. (2) A color photographic processing composition comprising at least one compound represented by the general formula (I) described in (1). (3) Color image formation, wherein the image-exposed silver halide color photographic material is developed in the presence of at least one compound represented by formula (I) described in (1). Method. The above has been solved by (1) to (3).

The compound of the present invention is prepared by the method described in
No. 45440, JP-A-7-287370, and European Patent No. 670,312A1, which are included in the claims. In the specification, specific compounds corresponding to the compounds of the present invention are described. And it is therefore not possible to predict the structure and performance of the compounds according to the invention from the description.

The 1-N substituent of the present invention forms a condensed ring with a benzene ring, and a 4-amino- group having an ethyleneoxy group or a polyethyleneoxy group on the substituent of the condensed ring.
N, N-dialkylaniline compounds are compounds that can be expected to be useful as pharmaceuticals and agricultural chemicals, in addition to silver halide color photographic color developing agents, dye intermediates for dyeing keratin fibers such as human hair, and the like.

[0013]

Next, the general formula (I) will be described in detail. R ¹ represents an alkyl group, an aryl group or a heterocyclic group. The alkyl group is a linear, branched or cyclic alkyl group having 1 to 16 carbon atoms, preferably 1 to 6 carbon atoms, such as methyl, ethyl, propyl, isopropyl, t-butyl, 2-hydroxyethyl, 3-hydroxypropyl, benzyl, 2-methanesulfonamidoethyl, 3-methanesulfonamidopropyl, 2-methanesulfonylethyl, 2-methoxyethyl, cyclopentyl, 2-acetamidoethyl, 2-carboxylethyl, 2-carbamoylethyl, 3 -Carbamoylpropyl, 2,3-dihydroxypropyl, 3,4-dihydroxybutyl, methanesulfonamidomethyl, n-hexyl, 2-hydroxypropyl, 4-hydroxybutyl, 2-carbamoylaminoethyl, 3-carbamoylaminopropyl, -Carbamoy Aminobutyl, 4-
Carbamoylbutyl, 2-carbamoyl-1-methylethyl, carbamoylaminomethyl, 4-nitrobutyl,
2- (2-hydroxyethoxy) ethyl, 2- [2-
(2-hydroxyethoxy) ethoxy] ethyl, 2-
(2- [2- (2-hydroxyethoxy) ethoxy] ethyl, 2- [2- (2- [2- (2-hydroxyethoxy) ethoxy] ethoxy) ethoxy] ethyl, 2- (2
-[2- (2- [2- (2-hydroxyethoxy) ethoxy] ethoxy) ethoxy] ethoxy) ethyl, 2-
(2-methoxyethoxy) ethyl, 2- [2- (2-methoxyethoxy) ethoxy] ethyl, 2- (2- [2-
(2-methoxyethoxy) ethoxy] ethoxy) ethyl, 2- [2- (2- [2- (2-methoxyethoxy)
Ethoxy] ethoxy) ethoxy] ethyl, 2- (2-
[2- (2- [2- (2-methoxyethoxy) ethoxy] ethoxy) ethoxy] ethoxy) ethyl. The aryl group is an aryl group having 6 to 24 carbon atoms, such as phenyl, naphthyl, and p-methoxyphenyl. The heterocyclic group is a 5- or 6-membered saturated or unsaturated heterocyclic ring having at least one oxygen atom, nitrogen atom or sulfur atom having 1 to 5 carbon atoms, and The number and the kind of the element may be one or plural, for example, 2-furyl, 2-thienyl, 2-pyrimidinyl, 2-benzotriazolyl, imidazolyl,
Pyrazolyl.

R ¹ is preferably an alkyl group or an aryl group, and more preferably an alkyl group. Preferred examples of R ¹ include, for example, methyl, ethyl, propyl,
Isopropyl, 2-hydroxyethyl, 3-hydroxypropyl, 2-methanesulfonamidoethyl, 3-methanesulfonamidopropyl, 2-methoxyethyl, 2-
Acetamidoethyl, hydroxymethyl, 2-carbamoylethyl, 3-carbamoylpropyl, 2,3-dihydroxypropyl, 3,4-dihydroxybutyl, methanesulfonamidomethyl, 2-hydroxypropyl,
-Hydroxybutyl, 2-carbamoylaminoethyl,
4-carbamoylaminobutyl, 4-carbamoylbutyl, 2-carbamoyl-1-methylethyl, 2- (2-
Hydroxyethoxy) ethyl, 2- [2- (2-hydroxyethoxy) ethoxy] ethyl, 2- (2- [2-
(2-hydroxyethoxy) ethoxy] ethoxy) ethyl, 2- [2- (2- [2- (2-hydroxyethoxy) ethoxy] ethoxy) ethoxy] ethyl, 2- (2
-[2- (2- [2- (2-hydroxyethoxy) ethoxy] ethoxy) ethoxy] ethoxy) ethyl, 2-
(2-methoxyethoxy) ethyl and 2- [2- (2-methoxyethoxy) methoxy] ethyl, more preferably ethyl, propyl, isopropyl, 2-hydroxyethyl, 3-hydroxypropyl, 2-methanesulfonamidoethyl , 2-methoxyethyl, 2-acetamidoethyl, hydroxymethyl, 2-carbamoylethyl,
2,3-dihydroxypropyl, 3,4-dihydroxybutyl, 2-hydroxypropyl, 4-hydroxybutyl, 2-carbamoylaminoethyl, 2- (2-hydroxyethoxy) ethyl, 2- [2- (2-hydroxyethoxy) ) Ethoxy] ethyl, 2- (2- [2- (2-hydroxyethoxy) ethoxy] ethoxy) ethyl, 2-
[2- (2- [2- (2-hydroxyethoxy) ethoxy] ethoxy) ethoxy] ethyl, and more preferably ethyl, 2-hydroxyethyl, 3-hydroxypropyl, 2,3-dihydroxypropyl, 4-dihydroxybutyl, 4-hydroxybutyl, 2- (2-
Hydroxyethoxy) ethyl, 2- [2- (2-hydroxyethoxy) ethoxy] ethyl, 2- (2- [2-
(2-hydroxyethoxy) ethoxy] ethoxy) ethyl.

R ² has 0 to 20 carbon atoms, preferably 0
To 8, more preferably 1 to 3 substituents, and examples of the substituent include a hydroxy group, a halogen atom (for example, a fluorine atom and a chlorine atom), and an alkyl group (preferably having 1 to 8 carbon atoms, for example, methyl , Ethyl, n-propyl, i-propyl, n-butyl, t-butyl, t-pentyl, di-
t-octyl, hydroxymethyl, 1,3-dihydroxy-2-propyl), an aryl group (preferably having 6 to 7 carbon atoms, for example, phenyl, m-hydroxyphenyl),
Heterocyclic group (preferably a 5- or 6-membered saturated or unsaturated heterocyclic ring containing at least one oxygen atom, nitrogen atom or sulfur atom having 1 to 5 carbon atoms, for example, 2-furyl,
2-thienyl, 2-pyrimidinyl, imidazolyl, pyrazolyl), alkoxy group (preferably having 1 to 8 carbon atoms, for example, methoxy, ethoxy, i-propoxy, 2-hydroxyethoxy, 2-methanesulfonylethoxy, 2-
(2-hydroxyethoxy) ethoxy, 2- [2- (2
-Hydroxyethoxy) ethoxy] ethoxy), an aryloxy group (preferably having 6 to 7 carbon atoms, for example, phenoxy, p-hydroxyphenoxy), a carboxy group, an acylamino group (preferably having 1 to 7 carbon atoms, for example, acetamido, 2 -Methoxypropionamide, p-hydroxybenzoylamide), an alkylamino group (having 1 carbon atom)
To 7, preferably dimethylamino, diethylamino, 2-hydroxyethylamino), an anilino group (preferably having 6 to 7 carbon atoms, for example, anilino, m-nitroanilino, m-hydroxyanilino), and a ureido group (carbon number 1 to 7 are preferable, for example, ureido, methylureide, N, N-dimethylureide, 2-methanesulfonamidoethylureide), a sulfamoylamino group (preferably having 0 to 7 carbon atoms, for example, dimethylsulfamoylamino , Methylsulfamoylamino, 2-methoxyethylsulfamoylamino), an alkylthio group (preferably having 1 to 7 carbon atoms, for example, methylthio, ethylthio, benzylthio), and an arylthio group (preferably having 6 to 7 carbon atoms, for example, Phenylthio, 2-carboxyphenylthio, 4-hydrido Hydroxyphenyl thio), an alkoxycarbonylamino group (having 2 to 7 carbon atoms are preferred, e.g., methoxycarbonylamino, ethoxycarbonylamino, 3-methanesulfonyl propoxycarbonyl amino), a sulfonylamino group (1-7 carbon atoms preferably,
For example, methanesulfonamide, p-toluenesulfonamide, 2-methoxyethanesulfonamide), carbamoyl group (preferably having 1 to 7 carbon atoms, for example, carbamoyl, N, N-dimethylcarbamoyl, N-ethylcarbamoyl), sulfamoyl group (Preferably having 0 to 7 carbon atoms, for example, sulfamoyl, dimethylsulfamoyl, ethylsulfamoyl), a sulfonyl group (preferably an aliphatic sulfonyl group having 1 to 5 carbon atoms or an aromatic sulfonyl group having 6 to 7 carbon atoms) For example, methanesulfonyl, ethanesulfonyl, 2-chloroethanesulfonyl), alkoxycarbonyl group (preferably having 1 to 7 carbon atoms, for example, methoxycarbonyl, t-butoxycarbonyl), and heterocyclic oxy group (oxygen having 1 to 5 carbon atoms) At least one atom, nitrogen atom or sulfur atom The number of the heteroatoms and the kind of the element which are a saturated or unsaturated heterocyclic oxy group of a 5- or 6-membered ring and which constitute the ring may be one or more, for example, 1-phenyltetrazole-5 -Yl-oxy, 2-tetrahydropyranyloxy, 2-pyridyloxy), an azo group (preferably having 1 to 7 carbon atoms, for example, phenylazo, 2-hydroxyphenylazo, 4-sulfophenylazo), an acyloxy group (carbon Numbers 1 to 7 are preferable, for example, acetoxy, benzoyloxy, 4-hydroxybutanoyloxy), carbamoyloxy group (preferably having 1 to 7 carbon atoms, for example, N, N-dimethylcarbamoyloxy, N-methylcarbamoyloxy,
N-phenylcarbamoyloxy), a silyl group (preferably having 3 to 7 carbon atoms, for example, trimethylsilyl, isopropyldiethylsilyl, t-butyldimethylsilyl),
Silyloxy group (preferably having 3 to 7 carbon atoms, for example, trimethylsilyloxy, triethylsilyloxy), aryloxycarbonylamino group (preferably having 7 carbon atoms, for example, phenoxycarbonylamino, 4-hydroxyphenoxycarbonylamino), imide group ( It preferably has 4 to 7 carbon atoms, for example, N-succinimide), a heterocyclic thio group (saturated or unsaturated 5- or 6-membered ring containing at least one oxygen atom, nitrogen atom or sulfur atom having 1 to 5 carbon atoms). The number of hetero atoms constituting the ring and the kind of element may be one or more, and may be a saturated heterocyclic thio group, for example, 2-benzothiazolylthio, 2-pyridylthio), a sulfinyl group (carbon number). 1 to 7 are preferable, for example, methanesulfinyl, benzenesulfinyl, ethanesulfinyl) Phosphonyl group (preferably having 2 to 7 carbon atoms, for example, methoxyphosphonyl, ethoxyphosphonyl, phenoxyphosphonyl), aryloxycarbonyl group (preferably having 1 to 7 carbon atoms, for example, phenoxycarbonyl, 3-hydroxyphenoxycarbonyl) ,
An acyl group (preferably having 1 to 7 carbon atoms, for example, acetyl, benzoyl, 4-hydroxybenzoyl) is used.

R ² is preferably an alkyl group, an aryl group, an alkoxy group, an acylamino group, a ureido group, a sulfamoylamino group, a sulfonylamino group, a carbamoyl group or a sulfamoyl group. More preferred are an alkyl group, an alkoxy group, a carbamoyl group, a sulfamoyl group, and a ureido group, and more preferred are an alkyl group and an alkoxy group. Preferred examples of R ² include, for example, methyl, ethyl, n-propyl, i-propyl, n-butyl, t-butyl, t-pentyl, di-t-octyl, hydroxymethyl, 1,3-
Dihydroxy-2-propyl, phenyl, m-hydroxyphenyl, methoxy, ethoxy, i-propoxy, 2
-Hydroxyethoxy, 2-methanesulfonylethoxy, 2- (2-hydroxyethoxy) ethoxy, 2-
[2- (2-hydroxyethoxy) ethoxy] ethoxy), acetamide, 2-methoxypropionamide,
p-hydroxybenzoylamide, ureido, methylureide, N, N-dimethylureide, 2-methanesulfonamidoethylureide, dimethylsulfamoylamino, methylsulfamoylamino, 2-methoxyethylsulfamoylamino, methanesulfonamide , P-toluenesulfonamide, 2-methoxyethanesulfonamide, carbamoyl, N, N-dimethylcarbamoyl,
N-ethylcarbamoyl, sulfamoyl, dimethylsulfamoyl, ethylsulfamoyl, more preferably methyl, ethyl, n-propyl, i-propyl,
t-butyl, methoxy, i-propoxy, acetamido, ureido, methylureido, N, N-dimethylureido, dimethylsulfamoylamino, methylsulfamoylamino, methanesulfonamide, carbamoyl,
N, N-dimethylcarbamoyl, N-ethylcarbamoyl, sulfamoyl, dimethylsulfamoyl,
Still more preferred are methyl, ethyl, i-propyl, methoxy and i-propoxy.

R ³ represents a hydrogen atom or a substituent. The number of carbon atoms of the substituent is preferably 1 to 20, more preferably 1 to 8, and particularly preferably 1 (that is, a methyl group).
It is. Examples of the substituent include an alkyl group (having 1 to 1 carbon atoms).
5 is preferable, for example, methyl, ethyl, n-propyl,
n-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-dodecyl, n-pentadecyl,
Isopropyl, sec-butyl, isobutyl, t-butyl,
3-pentyl, 2-methylbutyl, isopentyl, 2-
Ethylhexyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexylmethyl, t-pentyl, di-t-octyl), an aryl group (preferably having 6 to 7 carbon atoms, for example, phenyl and m-hydroxyphenyl), a heterocyclic group (having a carbon number of A 5- or 6-membered saturated or unsaturated heterocyclic ring containing at least one oxygen atom, nitrogen atom or sulfur atom of 1 to 5 is preferable.
-Thienyl, 2-pyrimidinyl, imidazolyl, pyrazolyl), alkoxycarbonyl group (preferably having 1 to 7 carbon atoms, for example, methoxycarbonyl, t-butoxycarbonyl), silyl group (preferably having 3 to 7 carbon atoms, for example, trimethylsilyl, Isopropyl diethylsilyl,
t-butyldimethylsilyl), an aryloxycarbonyl group (preferably having 1 to 7 carbon atoms, for example, phenoxycarbonyl, 3-hydroxyphenoxycarbonyl), an acyl group (preferably having 1 to 7 carbon atoms, for example, acetyl,
Benzoyl, 4-hydroxybenzoyl).

R ³ is preferably a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group, and more preferably a hydrogen atom or an alkyl group. Preferred examples of R ³ include, for example, a hydrogen atom, methyl, ethyl, n-propyl, n
-Butyl, n-pentyl, phenyl, imidazolyl and pyrazolyl, more preferably a hydrogen atom, methyl, ethyl and n-propyl, and further preferably a hydrogen atom and methyl.

Z has 2 to 20 carbon atoms, preferably 2 to 1 carbon atoms.
Represents 0, more preferably 2 to 6, ethylene or trimethylene groups, which may be substituted by substituents. The substituent is a substituent within the range permitted by R ² , and a preferred substituent is a hydroxy group, a halogen atom, an alkyl group, an alkoxy group, a carboxy group,
Acylamino group, alkylamino group, ureido group, sulfamoylamino group, alkoxycarbonylamino group,
Examples include a sulfonylamino group, a carbamoyl group, a sulfamoyl group, a sulfonyl group, an alkoxycarbonyl group, an acyloxy group, a carbamoyloxy group, and an acyl group. More preferably, a hydroxy group, an alkyl group, a carboxy group, an acylamino group, a ureido group, an alkoxycarbonylamino group, a sulfonylamino group, a carbamoyl group, an acyloxy group, a carbamoyloxy group, and still more preferably a hydroxy group, an alkyl group,
It is a carboxy group. Examples of Z include ethylene, 1-methylethylene, and 1-carbon atom bonded to N atom.
2-methylethylene, 1,2-dimethylethylene, 1,
1,2-trimethylethylene, 1,2,2-trimethylethylene, 1,1,2,2-tetramethylethylene,
-Hydroxymethylethylene, 2-hydroxyethylene, 1-methyl-2-hydroxyethylene, 1,1,2
-Trimethyl-2-carboxyethylene, 1,1,2,2
2-tetraethylethylene, trimethylene, 1,1-dimethyltrimethylene, 2,2-dimethyltrimethylene,
3,3-dimethyltrimethylene, 1,1,3-trimethyltrimethylene, 1,1,3-trimethyl-2-decyltrimethylene, 1,1,3-triethyl-2-methyltrimethylene, 1,1- Diethyltrimethylene, 2,2-
Diethyltrimethylene, 3,3-diethyltrimethylene, 1,1,2,2,3,3-hexaethyltrimethylene, 1,1,3-trimethyl-3-carboxytrimethylene, 1,1,3-trimethyl -2-hydroxytrimethylene, 1,1-dimethyl-2-hydroxy-3-methylidenetrimethylene, 1,1,3-trimethyl-2,3
-Dihydroxytrimethylene, 1,1,3-trimethyl-2-aminotrimethylene, 1,1,3-trimethyl-
2-dimethylaminotrimethylene, 1,1,3-trimethyl-2-bromotrimethylene, 1,1,3-trimethyl-2- (N-pyrazolyl) trimethylene, 1,1-dihydroxymethyl-3-methyltrimethylene , 1,1-
Dimethyl-3-hydroxymethyltrimethylene, 1,1
-Dimethyl-3-formyltrimethylene, 1,1-dimethyl-3-carboxytrimethylene, 1,1-dimethyl-3-carbamoyltrimethylene, 1,1-dimethyl-
3-dimethylcarbamoyl trimethylene, 1,1-dimethyl-3-hydroxymethyl-2,3-dihydroxytrimethylene, 1,1-dimethyl-3-hydroxymethyl-2-hydroxytrimethylene, preferably ethylene, -Methylethylene, 2-methylethylene, 1,
2-dimethylethylene, 1,2,2-trimethylethylene, 1,1,2,2-tetramethylethylene, 2-hydroxyethylene, 1-methyl-2-hydroxyethylene, 1,1-dimethyltrimethylene, 2, 2-dimethyltrimethylene, 3,3-dimethyltrimethylene, 1,
1,3-trimethyltrimethylene, 1,1,3-triethyl-2-methyltrimethylene, 1,1,3-trimethyl-2-hydroxytrimethylene, 1,1,3-trimethyl-2,3-dihydroxytrimethylene Methylene, 1,1-dimethyl-3-hydroxymethyltrimethylene, 1,1-
Dimethyl-3-hydroxymethyl-2-hydroxytrimethylene, more preferably ethylene, 1-methylethylene, 2-methylethylene, 1,2-dimethylethylene, 1,1-dimethyltrimethylene, 2,2-dimethyl Trimethylene, 3,3-dimethyltrimethylene, 1,
1,3-trimethyltrimethylene, 1,1,3-trimethyl-2-hydroxytrimethylene and 1,1-dimethyl-3-hydroxymethyltrimethylene.

L represents a divalent group or a single bond bonded to a carbon atom on the ethylene chain or trimethylene chain of Z, and examples of the divalent group include, for example, an alkylene group (having 1 to 10 carbon atoms).
Are preferred, for example, methylene, ethylene, trimethylene, tetramethylene, pentamethylene, hexamethylene, heptamethylene, octamethylene, methylmethylene, dimethylmethylene, ethylmethylene, benzylmethylene, 1-methylethylene, 2-methylethylene), phenylene group (C6-C8 is preferable, for example, 1,2-
Phenylene, 1,3-phenylene, 1,4-phenylene, 2-hydroxy-1,4-phenylene, 2- (2-
(Hydroxyethoxy) -1,4-phenylene, 5-carboxy-1,2-phenylene), —CO—, —SO ₂ —
It is.

L is preferably an alkylene group or a single bond, and more preferably an alkylene group. Preferred examples of L include, for example, methylene, ethylene, trimethylene, tetramethylene, pentamethylene, hexamethylene, a single bond, more preferably methylene, ethylene, trimethylene, a single bond, and further preferably methylene, ethylene, It is a single bond and most preferably methylene.

As a combination of R ¹ , R ² , R ³ , Z, L, m and n, R ¹ is preferably an alkyl group,
R ² is an alkyl group or an alkoxy group, R ³ is a hydrogen atom, and Z is an unsubstituted or hydroxy group having 2 to 6 carbon atoms, an alkyl group, an ethylene chain having a carboxy group as a substituent, or It is a trimethylene chain, L is methylene, m is 0 or 1, and n is an integer of 2 to 5.

Next, specific examples of the compound represented by formula (I) of the present invention will be shown below, but it should not be construed that the invention is limited thereto.

[0024]

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[0025]

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[0026]

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[0027]

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[0028]

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[0029]

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[0030]

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The compounds of the general formula (I) are very unstable when stored as free amines,
In general, it is preferable to produce and store the salt as a salt of an inorganic acid or an organic acid, and to use the salt as a free amine only at the time of use, that is, for example, when added to a treatment solution. General formula (I)
Examples of the inorganic and organic acids that form the salt of the compound (a) include hydrochloric acid, sulfuric acid, phosphoric acid, p-toluenesulfonic acid, methanesulfonic acid, and naphthalene-1,5-disulfonic acid. Among these, sulfuric acid, p-toluenesulfonic acid,
The salt is preferably a naphthalene-1,5-disulfonic acid salt, and most preferably a salt of sulfuric acid.

The 4- (N, N-dialkylamino) aniline compounds are described, for example, in Journal of the American Chemical Society 73, 3100 (1951).
Year)). Further, the following synthesis method or a method similar thereto can also be used.

[0033]

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In the synthesis, for example, as described above, first, an alkyl group is introduced into the amino group of aniline which has formed a condensed ring with benzene. That is, R ¹ is first introduced by reaction with an alkyl or aryl or heterocyclic halide, an alkyl or aryl sulfonate, or the like. Next, azo coupling or nitroso group at the para position of the amino group,
By introducing a nitro group and reducing these products (hydrogen catalytic reduction, reduction with zinc under acidic conditions, reduction with reduced iron, etc.), the desired product can be obtained.

In the alkylation reaction, for example, the corresponding alkyl halide (chloride, bromide, iodide), alkyl sulfonate (mesylate, tosylate, etc.), alkyl ester (acetate,
1 to 5 equivalents, preferably 1 to 3 equivalents, per alkylation, and organic (triethylamine, diazabicycloundecene, etc.) or inorganic (sodium hydrogen carbonate, sodium carbonate, potassium carbonate, Sodium hydroxide, potassium hydroxide, etc.) in an amount of 1 to 5 equivalents, preferably 1 to 3 equivalents per alkylation.
Water, amide solvents (N, N-dimethylacetamide, N, N-dimethylformamide, 1-methyl-2-pyrrolidone, etc.), sulfone solvents (sulfolane, etc.), sulfoxide solvents Dimethylsulfoxide, etc.), ureide solvents (tetramethylurea, etc.), ether solvents (dioxane, etc.), alcohol solvents (isopropyl alcohol, butanol, etc.)
For 10 minutes to 72 hours, preferably 30 minutes to 12 hours at a reaction temperature of 0 to 200 ° C, preferably 80 to 170 ° C, in the absence of a catalyst or in the presence of a catalyst (such as sodium iodide). The reaction is performed within the reaction time range.

Next, azo coupling or introduction of a nitroso group or a nitro group is performed at the para position of the amino group. The azo coupling is carried out, for example, by using a substituted or unsubstituted aniline in the presence of an acid (organic or inorganic acid such as hydrochloric acid, sulfuric acid, methanesulfonic acid, acetic acid), without solvent, in water, or with an organic solvent (methanol, ethanol, isopropyl). Alcohol solvents such as alcohol, N, N-dimethylacetamide,
Amide solvents such as N, N-dimethylformamide and 1-methyl-2-pyrrolidone; sulfone solvents such as sulfolane; sulfoxide solvents such as dimethyl sulfoxide; ureide solvents such as tetramethylurea);
Degrees, preferably in a reaction temperature range of -20 to 30 degrees,
The diazonium salt is converted into a diazonium salt within a reaction time of 5 minutes to 5 hours, preferably 5 minutes to 1 hour.
To 5 equivalents, preferably 1 to 2 equivalents without solvent, in water, or in an organic solvent (an alcohol solvent such as methanol, ethanol, isopropyl alcohol, N, N-dimethylacetamide, N, N-dimethylformamide,
Amide solvents such as 1-methyl-2-pyrrolidone, sulfone solvents such as sulfolane, sulfoxide solvents such as dimethyl sulfoxide, and ureide solvents such as tetramethylurea) in the range of -78 to 40 degrees, preferably -20 to 30 degrees. 5 minutes to 5 hours, preferably 5 minutes to
Coupling with N, N-dialkylaniline within a reaction time of 1 hour. The coupling reaction system is preferably under a weakly acidic to weakly basic condition. The nitrosation is carried out, for example, in the presence of an acid (organic or inorganic acid such as hydrochloric acid, sulfuric acid, methanesulfonic acid, acetic acid) in the presence of an organic (isoamyl nitrite or the like) or inorganic (sodium nitrite or the like) nitrosating agent by 1-5. Equivalent, preferably 1 to 2 equivalents, no solvent or water as a solvent or an inorganic solvent (an alcohol solvent such as methanol, ethanol, isopropyl alcohol, N, N-
Amide solvents such as dimethylacetamide, N, N-dimethylformamide, 1-methyl-2-pyrrolidone, sulfone solvents such as sulfolane, sulfoxide solvents such as dimethylsulfoxide, ureide solvents such as tetramethylurea), and -78. The reaction is carried out at a reaction temperature of -40 to 40 degrees, preferably -20 to 30 degrees, for a reaction time of 5 minutes to 5 hours, preferably 5 minutes to 1 hour. The nitration can be performed, for example, without solvent, in water, or in an organic solvent (an alcoholic solvent such as methanol, ethanol, or isopropyl alcohol; an organic acid such as acetic acid; an organic acid anhydride such as acetic anhydride or trifluoroacetic anhydride; Amide solvents such as N, N-dimethylacetamide, N, N-dimethylformamide, 1-methyl-2-pyrrolidone, sulfone solvents such as sulfolane, sulfoxide solvents such as dimethyl sulfoxide, and ureide solvents such as tetramethylurea) ,
Various concentrations of nitric acid (60 to 98%) are used in an amount of 1 to 5 equivalents, preferably 1 to 1.5 equivalents, alone or in the presence of various activators such as sulfuric acid, sulfuric anhydride, acetic anhydride, and trifluoroacetic anhydride. , -78 to 100 degrees, preferably -20 to 30
5 minutes to 5 hours, preferably 5 minutes in the range of reaction temperature.
The reaction is performed in a reaction time range of minutes to 1 hour.

Finally, these products are reduced (hydrogen catalytic reduction, reduction with zinc under acidic conditions, reduction with reduced iron, etc.)
By doing so, the desired product is obtained. Hydrogen catalytic reduction is carried out, for example, in the presence of a catalyst (palladium-carbon, Raney-nickel, etc.) in the absence of a solvent, or in water, or an organic solvent (an alcohol solvent such as methanol, ethanol, isopropyl alcohol, N, N-dimethylacetamide, Amide solvents such as N, N-dimethylformamide and 1-methyl-2-pyrrolidone; sulfone solvents such as sulfolane; sulfoxide solvents such as dimethyl sulfoxide; ureide solvents such as tetramethylurea); Pressure,
Preferably in the range of 1 to 200 atmospheres, 0 to 150 degrees,
Preferably, the reaction temperature is in the range of 0 to 50 ° C. and 5 minutes to 7 minutes.
The reaction is carried out for a reaction time of 2 hours, preferably 1 to 8 hours. Reduction with reduced iron can be performed, for example, without solvent, in water, or in an organic solvent (alcohol-based solvent such as methanol, ethanol, isopropyl alcohol, N, N-
Amide-based solvents such as dimethylacetamide, N, N-dimethylformamide and 1-methyl-2-pyrrolidone, sulfone-based solvents such as sulfolane, sulfoxide-based solvents such as dimethylsulfoxide, and ureide-based solvents such as tetramethylurea). Using 10 equivalents, preferably 4 to 6 equivalents of reduced iron, 0.0001 to 1 equivalent, preferably 0.00
An acid (an inorganic acid such as hydrochloric acid or sulfuric acid or an organic acid such as acetic acid or methanesulfonic acid) or an acid salt (ammonium chloride, sodium chloride, sodium sulfate or the like) alone or in combination with 1 to 0.1 equivalent is used. ~ 150 degrees, preferably 50
30 minutes to 72 hours in a reaction temperature range of １００100 ° C.,
The reaction is preferably performed within a reaction time of 1 to 8 hours. To perform reduction with zinc under acidic conditions, for example, 3 to
Using 10 equivalents, preferably 3 to 6 equivalents of zinc dust, in the presence of an acid (an organic acid such as acetic acid or methanesulfonic acid, an inorganic acid such as hydrochloric acid or sulfuric acid), in the absence of a solvent or in water, or in an organic solvent (methanol , Alcoholic solvents such as ethanol and isopropyl alcohol, organic acids such as acetic acid, N, N-dimethylacetamide, N, N-dimethylformamide,
Amide solvents such as 1-methyl-2-pyrrolidone, sulfone solvents such as sulfolane, sulfoxide solvents such as dimethyl sulfoxide, ureide solvents such as tetramethylurea,
Organic acid solvents such as acetic acid, propionic acid, and methanesulfonic acid) in a reaction temperature range of 0 to 150 degrees, preferably 0 to 100 degrees, for 5 minutes to 72 hours, preferably 30 minutes to 3 hours. The reaction is performed within the reaction time of

The products obtained by these reactions can be processed according to the usual post-treatment of an organic synthesis reaction and then purified or used without purification. That is, for example, the product released from the reaction system can be used without purification or by performing an operation of purifying by recrystallization, column chromatography, or the like, alone or in combination. Alternatively, after the completion of the reaction, the reaction solvent is distilled off, or the mixture is neutralized by pouring it into water or ice without being distilled off, or the product released without neutralization is purified without purification, or recrystallized. After performing the operation of purifying by chromatography or the like singly or in combination, it can be provided. Alternatively, after the completion of the reaction, the reaction solvent is distilled off,
Alternatively, neutralize with water or ice without distilling off, or neutralize or extract with an organic solvent without neutralization, or purify by crystallization or column chromatography alone. Alternatively, they can be provided after being combined. Next, examples of the synthesis of various anilines having an ethyleneoxy group or a polyethyleneoxy group on the ethylene or trimethylene chain forming a condensed ring with a benzene ring will be described.

[0039]

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[0040]

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The dihydroindole skeleton can be obtained by carrying out Fischer's indole synthesis using arylhydrazine as a raw material as described above, and reducing the obtained indole compound or indolenine compound.

[0042]

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As described above, the journal of the
Organic Chemistry 55, 580 (199
A hydroxymethyl group may be introduced at the benzyl position according to the method described in (0), and after chlorination, it may be condensed with the amino group at the 2-position on the benzene ring.

[0044]

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[0045]

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The tetrahydroquinoline skeleton is Organic Syn
In accordance with the method described in Thesis Collective Volume III, page 328, aniline and acetone are dehydrated and condensed, and then reduced to obtain the corresponding 2,2,4-trimethyltetrahydroquinoline. In this case, as described above, dihydroquinoline, which is a dehydration condensation product of aniline and acetone, is converted to the corresponding allyl alcohol or allyl bromide with selenium dioxide, NBS or the like, followed by an etherification reaction to form a tetrahydroquinoline skeleton. A compound in which a polyethyleneoxymethyl group is substituted at the 4-position can be synthesized. Further, a polyethyleneoxy group can be introduced into the 3-, 3-, or 4-position of the tetrahydroquinoline skeleton by utilizing the reaction of epoxidation of dihydroquinoline with m-chloroperbenzoic acid.

[0047]

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As described above, the corresponding tetrahydroquinoline can be obtained from N-allylaniline and zinc (II) chloride according to the method described in the journal of the Chemical Society of Japan, p. 1043 (1981).

[0049]

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Further, as described above, the Journal of the
It can be obtained by Friedel-Crafts reaction of α, β-unsaturated amide and reduction of amide according to the method described in American Chemical Society, Vol. 62, p. 778 (1940).

In the above-described formulas, R ⁴ and R ⁵ may contain a polyethyleneoxy group, or may contain a hydroxy group, a halogen atom, a sulfonate, an acyloxy group, or the like, and may be induced to an ether group later. As a result, various dihydroindole compounds and tetrahydroquinoline compounds having different substitution positions of the polyethyleneoxy group can be synthesized.

Next, the case where the compound of the present invention is used as a color developing agent will be described. The compound of the present invention as a color developing agent can be used alone or in combination with other known p-phenylenediamine derivatives. Representative examples of the compounds to be combined are shown below, but are not limited thereto. N, N-diethyl-p-phenylenediamine (P-1), 4-amino-3-methyl-N, N-
Diethylaniline (P-2), 4-amino-3-methyl-N-ethyl-N- (3-hydroxypropyl) aniline (P-3), 4-amino-N-ethyl-N- (2-hydroxyethyl ) Aniline (P-4), 4-amino-3
-Methyl-N-ethyl-N- (2-hydroxyethyl)
Aniline (P-5), 4-amino-3-methyl-N-ethyl-N- (2-methanesulfonamidoethyl) aniline (P-6), N- (2-amino-5-N, N-diethylamino Phenylethyl) methanesulfonamide (P-
7), N, N-dimethyl-p-phenylenediamine (P
-8), 4-amino-3-methyl-N-ethyl-N-
(2-methoxyethyl) aniline (P-9), 4-amino-3-methyl-N-ethyl-N- (4-hydroxybutyl) aniline (P-10), 4-amino-3-methyl-
N-ethyl-N- (2-butoxyethyl) aniline (P
−11). Of the above p-phenylenediamine derivatives as compounds to be combined, particularly preferred are P-3, P-5,
P-6 or P-10. Further, these p-phenylenediamine derivatives and sulfates, hydrochlorides, sulfites,
p-toluenesulfonate, nitrate, naphthalene-1,
It is commonly used in salts such as 5-disulfonate. The treatment composition may be liquid or solid (eg, powder, granule, tablet). These compounds can be used in combination of two or more depending on the purpose.
Amount of aromatic primary amine developing agent used is color developer 1
Preferably 0.001 mol to 0.2 mol per liter,
More preferably, it is 0.005 mol to 0.1 mol.

For color development using the compound of the present invention, the compound of the present invention or a precursor thereof is contained in a light-sensitive material in addition to including the compound of the present invention in a processing solution. There are methods for generating compounds. In these cases, the content is 1 to 30 times, preferably 1 to 10 times, more preferably 1 to 4 times the coupler.

In the color developer, compounds described in JP-A-63-5341, JP-A-63-106655 or JP-A-4-144446 may be used as compounds for directly preserving the aromatic primary amine color developing agent. Various hydroxylamines, hydroxamic acids described in JP-A-63-43138, hydrazines and hydrazides described in JP-A-63-146041, 63-44657 and 63-58.
No. 443, α-hydroxyketones and α-aminoketones described in JP-A-63-44656, and various sugars described in JP-A-63-36244. Also, in combination with the above compounds, JP-A-63-4235, JP-A-63-24254 and JP-A-63-24
Nos. 1647, 63-146040, 63-278
Monoamines described in No. 41 and No. 63-25654, No. 63-30845, No. 63-14640,
Diamines described in JP-A-63-43139 and the like;
Nos. 21647, 63-26655 and 63-4
Polyamines described in No. 4655, and 63-53551.
No. 63-43140.
Alcohols described in JP-A-63-53549, oximes described in JP-A-63-56654, and alcohols described in JP-A-63-56654.
The tertiary amines described in 239,47 can be used. Other preservatives include JP-A-57-44148.
And various metals described in JP-A-57-53749; salicylic acids described in JP-A-59-180588;
Alkanolamines described in No. 3582, 56-9
If necessary, polyethyleneimines described in No. 4349, aromatic polyhydroxy compounds described in U.S. Pat. No. 3,746,544, and the like may be contained. In particular, when hydroxylamines are used, the above-mentioned alkanolamines and aromatic polyhydroxy compounds are preferably used in combination.
Particularly preferred preservatives are described in JP-A-3-144446.
And hydroxylamines represented by the general formula (I), and among them, compounds having a methyl group, an ethyl group, a sulfo group or a carboxy group are preferable. These preservatives may be added in an amount of 20 to 200 mmol, preferably 30 to 150 mmol per liter of color developer.
Millimoles.

It is preferable that the developer of the photosensitive material for printing contains chlorine ions in an amount of 3.0 × 10 ^{-2 to} 1.5 × 10 ^-1 mol / l. Particularly preferably 3.5 × 10
^{−2 to} 1.0 × 10 ⁻¹ mol / l. If the chloride ion concentration is more than 1.5 × 10 ^{-1 to} 1.0 × 10 ^-1 mol / l, it has the disadvantage of delaying the development, and in order to achieve the object of the present invention, which is rapid and has a high maximum concentration. Not preferred. On the other hand, if it is less than 3.0 × 10 ⁻² mol / l, it is not preferable in preventing fog. In the present invention, the color developer preferably contains 0.5 × 10 ⁻⁵ mol / L to 1.0 × 10 ⁻³ mol / L of bromine ions. More preferably, it is 3.0 × 10 ^{−5 to} 5 × 10 ⁻⁴ mol / l. When the bromine ion concentration is higher than 1 × 10 ⁻³ mol / l, the development is delayed, and the maximum concentration and sensitivity are reduced. When the bromide ion concentration is lower than 0.5 × 10 ⁻⁵ mol / l, fog is sufficiently prevented. Can not.

Here, the chlorine ions and bromine ions may be directly added to the color developer, or may be eluted from the photosensitive material into the color developer during the development processing. When directly added to a color developer, examples of the chloride ion supplying material include sodium chloride, potassium chloride, ammonium chloride, lithium chloride, magnesium chloride, and calcium chloride. Further, it may be supplied from a fluorescent whitening agent added to the color developer. As a bromine ion supply substance,
Examples include sodium bromide, potassium bromide, ammonium bromide, lithium bromide, calcium bromide, and magnesium bromide. When eluted from the light-sensitive material during the development processing, both chlorine ions and bromine ions may be supplied from the emulsion, or may be supplied from sources other than the emulsion.

Other color developing solutions include those described in
Various additives described in No. 144446 can be used. For example, carbonic acids, phosphoric acids, boric acids, hydroxybenzoic acids, etc. described in page (9) of the same patent can be used as a buffer for maintaining pH. It is preferable that the pH of the color developer is maintained at 9.0 to 12.5 using these buffers. More preferably, it is 9.5 to 11.5. Examples of the antifoggant include halide ions and organic antifoggants described on page (10). In particular, when the concentration of the developing agent in the color developer is as high as 20 mmol / L or more, or when high-temperature processing is performed at 40 ° C. or more, the bromide ion concentration is preferably somewhat high, and is preferably 17 mmol / L.
It is preferably from liter to 60 mmol. If necessary, halogen can be removed using an ion-exchange resin or an ion-exchange membrane to control the concentration in a preferable range. As a chelating agent, aminopolycarboxylic acid,
Aminopolyphosphonic acid, alkylphosphonic acid and phosphonocarboxylic acid 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, N-tetramethylenephosphonic acid, ethylenediamine-di (o-hydroxyphenylacetic acid) and salts thereof as representative examples. The following compounds can be used. Preferred chelating agents include compounds having biodegradability. Examples of this are disclosed in JP-A-63-146998 and JP-A-63-19929.
5, JP-A-63-267750, JP-A-63-26
No. 7751, JP-A-2-229146, JP-A-3-3-1
No. 86841, German patent 3739610, European patent 46
No. 8325 and the like. Further, 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- If necessary, 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.

An optional development accelerator can be added to the color developer if necessary. As a development accelerator, JP-B-37
-16088, 37-5987 and 38-782
Thioether compounds represented by JP-A-6-49829, JP-A-52-49829 and JP-A-50-49829;
P-phenylenediamine compounds represented by JP-A-15554, JP-A-50-137726, JP-B-44-3
0074, JP-A-56-156826 and JP-A-52-286.
Quaternary ammonium salts represented by 43429 and the like; U.S. Pat. Nos. 2,494,903 and 3,128,182
Nos. 4,230,796 and 3,253,919
No., JP-B-41-11431, U.S. Pat. No. 2,48
Nos. 2,546, 2,596,926 and 3,58
No. 2,346, etc .;
No. 16088, No. 42-25201, U.S. Pat.
128,183, JP-B-41-11431, 42
Polyalkylene oxides described in U.S. Pat. No. 23883 and U.S. Pat. No. 3,532,501, and other 1-phenyl-3-pyrazolidones, imidazoles, and the like can be added as necessary.

[0059] replenishing amount of color developer in the case of photographic light-sensitive material is preferably not more than 1 m ² per 550 ml, 450 ml
The following are more preferable, and the 400 ml or less and the 80 ml or more are most preferable. By reducing or not including the bromide ion concentration in the replenisher, it can be reduced to 300 ml or less. In the case of a photosensitive material for printing, the replenishment amount of the color developing solution is suitably from 20 to 600 ml, preferably from 30 to 200 ml, more preferably from 40 to 100 ml, per m ^{2 of} the photosensitive material. The processing temperature of the color developer is preferably 35 ° C. or higher, and more preferably 40 ° C. or higher and 50 ° C. or lower in the case of a photographic material. In the case of a photosensitive material for printing, the processing temperature of the color developer is 20 to 50 ° C., preferably 30 to 50 ° C.
45 ° C, most preferably 37-42 ° C. The processing time of the color developer is preferably 30 seconds to 3 minutes and 15 seconds, and more preferably 30 seconds to 2 minutes and 30 seconds in the case of a photosensitive material for photography. The processing time of the color developer is generally 3 minutes or less for a photosensitive material for printing, but is preferably 10 seconds to 1 minute, more preferably 10 seconds to 30 seconds. Here, the processing time (for example, development time) refers to the time from when the photosensitive material enters the target processing solution to when it enters the processing solution in the next bath.

It is preferable that the developer of the photosensitive material for printing contains substantially no benzyl alcohol. The developer of the photosensitive material for printing must contain substantially no sulfite ion in order to suppress fluctuations in photographic characteristics due to continuous processing and to achieve the effects of the present invention. , And a sulfite ion concentration of 3.0 × 10 ⁻³ mol / liter or less). Preferably, it contains no sulfite ion at 1.0 × 10 ⁻³ mol / l or less, most preferably no sulfite ion at all. Here, however, a very small amount of sulfite ion used for preventing oxidation of the processing agent kit in which the developing agent is concentrated before preparing the working solution is excluded. In order to suppress fluctuations in photographic properties due to fluctuations in the concentration of hydroxylamine, the developer should be substantially free of hydroxylamine (here, substantially not containing a hydroxylamine concentration of 5.0 × 1).
0 is ^-3 mol / l or less. Is more preferred. Most preferably it contains no hydroxylamine.

It is preferable to prevent evaporation of the liquid and air oxidation. The contact area between the photographic processing solution 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 )] ÷ [capacity of treatment liquid (cm ³ )] The above-mentioned aperture ratio (cm ⁻¹ ) is preferably 0.05 or less, more preferably Preferably it is 0.0005-0.01.
As a method of reducing the aperture ratio in this way, in addition to providing a shield such as a floating lid on the photographic processing liquid surface of the processing tank, a method using a movable lid described in JP-A-1-82033,
A slit developing method described in JP-A-63-216050 can be exemplified. Further, it is preferable that the processing solution in the replenishment tank of the color developer or the processing layer is shielded with a high boiling point organic solvent or a high molecular compound to reduce the contact area with air. Particularly, liquid paraffin, organosiloxane and the like are preferable. Reducing the aperture ratio can be applied not only to both color development and black-and-white development, but also to all subsequent steps such as bleaching, bleach-fixing, fixing, washing, stabilization, and the like. The developer can be regenerated and used. Regeneration of the developing solution means that the used developing solution is subjected to anion exchange resin or electrodialysis, or the activity of the developing solution is increased by adding a processing chemical called a regenerating agent, and used again as a processing solution. . In this case, the regeneration rate (the percentage of overflow in the replenisher)
It is preferably at least 70%, particularly preferably at least 90%.

The color-developed photosensitive material is usually subjected to a desilvering process. The desilvering process referred to here basically comprises a bleaching process and a fixing process, but is constituted by a bleach-fixing process in which these processes are performed simultaneously and a combination of these processes. Examples of the bleaching agent include iron salts; iron (III), cobalt (III)
And compounds of polyvalent metals such as chromium (IV) and copper (II); peracids; quinones; and nitro compounds. Representative bleaching agents include iron chloride; ferricyanide; dichromate; organic complex salts of iron (III) (eg, ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, methyliminodiacetic acid, 1,3-diamino acid) Metal complex salts such as aminopolycarboxylic acids such as propanetetraacetic acid and glycol ether diaminetetraacetic acid); persulfates; bromates; permanganates; and nitrobenzenes. Of these, the aforementioned Japanese Patent Laid-Open No.
As described in page 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, complex salts such as citric acid, tartaric acid and malic acid can be used as bleaching agents. Among these, iron (III) complex salts of aminopolycarboxylic acid such as iron (III) complex salt of ethylenediaminetetraacetate and 1,3-diaminopropanetetraacetate complex salt are particularly preferable. These iron (III) aminopolycarboxylic acid complex salts are particularly useful in a bleaching solution and a 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 bleach accelerators are described in the following specification: U.S. Pat. No. 3,893,858, West German Patent 1,290,812, JP-A-53-95630, Research. Disclosure No. 17129 (197
A compound having a mercapto group or a disulfide bond as described in US Pat. No. 3,706,5.
No. 61; thiourea derivatives described in JP-A-58-1623.
No. 5, iodide salt; West German Patent 2,748,430
No. 45-polyoxyethylene compounds;
Polyamine compounds described in No. 8836; bromide ions 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,
In particular, U.S. Patent No. 3,893,858, West German Patent No. 1,
Compounds described in JP-A-290,812 and JP-A-53-95630 are preferred. No. 4,552,8.
The compound described in No. 34 is 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, besides the bleaching agent, JP-A-3-1
P. 44446 (12), rehalogenating agent, p
H 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 and the like. Among them, succinic acid, maleic acid and glutaric acid are particularly preferred. The pH of the bleaching solution or the bleach-fixing solution is usually from 4.0 to 8.0, but the processing can be carried out at a lower pH in order to speed up the processing.

Examples of the fixing agent used in the fixing solution or the bleach-fixing solution include thiosulfates, thiocyanates, thioether compounds, thioureas, and large amounts of iodides. Use is common, especially ammonium thiosulfate being the most widely used. It is also preferable to use a combination of a thiosulfate with a thiocyanate, a thioether compound, thiourea, or the like. As a preservative of the fixing solution or the bleach-fixing solution, a sulfite, a bisulfite, a carbonyl bisulfite adduct, or a sulfinic acid compound described in EP-A-294769A is preferable. Further, for the purpose of stabilizing the liquid, it is preferable to add a chelating agent such as various aminopolycarboxylic acids or 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 Diaminetetraacetic acid, 1,2
-Propylenediaminetetraacetic acid. Among them, 1-hydroxyethylidene-1,1-diphosphonic acid and ethylenediaminetetraacetic acid are particularly preferred. The fixer and the bleach-fixer have a pKa of 6. for pH adjustment.
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 / l.

The fixing solution or the bleach-fixing solution may further contain various fluorescent whitening agents; defoaming agents; surfactants; polyvinylpyrrolidone; When a replenishment method is employed in the processing, the replenishment amount of the fixing solution or the bleach-fixing solution is 100 to 3000 per m ² of the photographic material.
ml is preferred, but more preferably 300 to 1800 m
l. Replenishment of the bleach-fixing solution may be carried out as a bleach-fixing replenisher, or by using an overflow solution of the bleaching solution and the fixing solution as described in JP-A-61-143755 and Japanese Patent Application No. 2-216389. You may. The total processing time of the desilvering step comprising 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 60.
° C, preferably 35 to 55 ° C.

It is particularly preferred that a processing solution having a bleaching ability is subjected to aeration during processing, since photographic performance is extremely stably maintained. Any means known in the art can be used for aeration, and air can be blown into a processing solution having bleaching ability, or air can be absorbed using an ejector. Further, the processing solution having the bleaching ability can be reused after collecting the overflow solution after use in the processing, correcting the composition by adding components, and then reusing it. Such a method of use is usually referred to as reproduction, but the present invention can also preferably perform such reproduction. For details of reproduction, see Fujifilm Processing Manual, Fujicolor Negative Film, CN-16 processing (revised in August 1990), page 39, issued by Fuji Photo Film Co., Ltd.
The matters described on page 40 are applicable. The automatic developing machine used for the photosensitive material of the present invention is disclosed in JP-A-60-191257 and JP-A-60-191257.
It is preferable to have the photosensitive material conveying means described in JP-A Nos. 191258 and 60-191259. As described in the above-mentioned JP-A-60-191257, such a conveying means can significantly reduce the carry-in of the processing solution from the pre-bath to the post-bath, and is highly effective in preventing the performance of the processing solution from deteriorating. Such an effect is particularly effective for reducing the processing time in each step and reducing the replenishing amount of the processing solution.

A dewatering process is followed by a washing step in general. A stabilizing step may be performed instead of the washing step. In such a stabilization process, Japanese Patent Application Laid-Open No. 57-8543
, 58-14834 and 60-220345 can all be used. Also,
A washing step-stabilizing step may be performed in which a stabilizing bath containing a dye stabilizer and a surfactant is used as a final bath. The washing solution and the stabilizing solution may contain a hard water softener such as inorganic phosphoric acid, polyaminocarboxylic acid, and organic aminophosphonic acid.

The amount of water in the water washing step and the like depends on the characteristics of the photosensitive material (for example, depending on the material used such as a coupler), the use, the liquid temperature, the number of tanks (the number of stages), the replenishment method such as countercurrent, forward flow, etc. It can be set in a wide range depending on conditions. The number of stages is preferably 2 to 4 stages.

The stabilizing solution contains a compound for stabilizing a dye image, for example, benzaldehydes such as formalin and m-hydroxybenzaldehyde, an adduct of formaldehyde bisulfite, hexamethylenetetramine and its derivatives, hexahydrotriazine and its derivatives, N-methylol compounds such as dimethylol urea and N-methylol pyrazole, organic acids and pH buffers are included. The preferable addition amount of these compounds is from 0.001 to 0.02 mol per liter of the stabilizing solution. The lower the concentration of free formaldehyde in the stabilizing solution, the less the formaldehyde gas is scattered.

The washing water and the stabilizing solution may contain various surfactants in order to prevent unevenness of water droplets when the processed photosensitive material is dried. Among them, it is preferable to use a nonionic surfactant, and particularly preferable is an alkylphenol ethylene oxide adduct. Octyl, nonyl, dodecyl, and dinonylphenol are particularly preferred as the alkylphenol, and the number of moles of ethylene oxide added is particularly preferably 8 to 14. It is also preferable to use a silicon surfactant having a high defoaming effect.

The washing water and the stabilizing solution preferably contain various chelating agents. Preferred chelating agents include aminopolycarboxylic acids such as ethylenediaminetetraacetic acid and diethylenetriaminepentaacetic acid, 1-hydroxyethylidene-1,1-diphosphonic acid, N, N, N'-trimethylenephosphonic acid, diethylenetriamine-N, N,
Organic phosphonic acids such as N ', N'-tetramethylenephosphonic acid, and a hydrolyzate of a maleic anhydride polymer described in EP 345,172 A1 can be mentioned.

The water treated and / or stabilized with a reverse osmosis membrane can be used effectively.

The various processing solutions are preferably used at 10 ° C. to 50 ° C. Usually, a temperature of 33 ° C to 38 ° C is standard, but a higher temperature promotes the processing and shortens the processing time, and conversely, lowers the temperature to achieve the improvement of the image quality and the stability of the processing solution. be able to.

Each processing solution can be commonly used for processing two or more kinds of photosensitive materials. For example, by processing the color negative film and the color paper using the same processing liquid, the cost of the processing machine can be reduced and the processing can be simplified.

The present invention can be applied to various color photosensitive materials such as a color negative film for general use or a movie, a color reversal film for slides or a television, a color paper, a color positive film and a color reversal paper. In addition, Tokuhei 2-32615, Jitsuhei 3-39784
It is also suitable for a film unit with a lens described in (1).

The photosensitive material may have at least one photosensitive layer provided on a support. A typical example is a silver halide photographic light-sensitive material having at least one light-sensitive layer comprising a plurality of silver halide emulsion layers having substantially the same color sensitivity but different sensitivities on a support. It is. The photosensitive layer is a unit light-sensitive layer having color sensitivity to any of blue light, green light, and red light. The arrangement is such that a red-sensitive layer, a green-sensitive layer, and a blue-sensitive layer are arranged in this order from the support side. However, depending on the purpose, the order of installation may be reversed, or the order of installation may be such that different photosensitive layers are sandwiched between layers of the same color sensitivity. A non-light-sensitive layer may be provided between the silver halide light-sensitive layers and as the uppermost layer and the lowermost layer. These may contain a coupler, a DIR compound, a color mixing inhibitor and the like described below. As described in DE 1,121,470 or GB 923,045, a plurality of silver halide emulsion layers constituting each unit photosensitive layer are composed of a high-speed emulsion layer and a low-speed emulsion layer.
It is preferable to arrange them so that the photosensitivity becomes lower gradually toward the support. Also, JP-A-57-112751, 62-200350,
As described in JP-A-62-206541 and JP-A-62-206543, a low-sensitivity emulsion layer may be provided on the side remote from the support, and a high-sensitivity emulsion layer may be provided on the side close to the support. As described in JP-B-55-34932, the layers can be arranged in the order of blue-sensitive layer / GH / RH / GL / RL from the side farthest from the support. Further, as described in JP-A-56-25738 and JP-A-62-63936, a blue-sensitive layer / GL / RL is selected from the side farthest from the support.
The sequence may be arranged in the order of / GH / RH.

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 having a lower sensitivity than the middle layer. An example is an arrangement in which a silver halide emulsion layer having a low sensitivity is arranged and three layers having different sensitivities are sequentially reduced in sensitivity toward a support. Even when such a three-layer structure having different photosensitivity is used,
As described in JP-A-59-202464, in the same color-sensitive layer, the layers may be arranged in the order of medium-speed emulsion layer / high-speed emulsion layer / low-speed emulsion layer from the side away from the support. Others
High-speed emulsion layers / low-speed emulsion layers / medium-speed emulsion layers, or low-speed emulsion layers / medium-speed emulsion layers / high-speed emulsion layers may be arranged in this order. The arrangement may be changed as described above even in the case of four or more layers. US to improve color reproduction
4,663,271, 4,705,744, 4,707,436, JP-A-62-1
A donor layer (CL) having a multilayer effect having a spectral sensitivity distribution different from that of the main photosensitive layer such as BL, GL, and RL described in the specifications of 60448 and 63-89850, is arranged adjacent to or close to the main photosensitive layer. Is preferred.

In a general photosensitive 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-described color forming layers. It can be constituted by coating on the support in the order described above. However, the order may be different. In other words, from the viewpoint of rapid processing, it is preferable that the photosensitive layer containing the silver halide grains having the largest average grain size be the uppermost layer, or from the viewpoint of storage stability under light irradiation, the lowermost layer should be the magenta coloring photosensitive layer. It may be preferable to do so. The photosensitive layer and the color hue may not have the above correspondence, and at least one infrared-sensitive silver halide emulsion layer may be used.

Preferred silver halides for use in the photographic light-sensitive material are 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 include those having regular crystals such as cubic, octahedral and tetradecahedral, those having irregular crystalline forms such as spheres and plates, twin planes, etc. Or a composite form thereof. The silver halide may be fine grains having a grain size of about 0.2 μm or less or large grains having a projected area diameter of about 10 μm, and may be a polydisperse emulsion or a monodisperse emulsion. Dispersion coefficient 15% or less, 1
Monodispersed particles of 0% or less are preferred. Silver halide photographic emulsions include, for example, Research Disclosure (hereinafter, referred to as “Research Disclosure”).
No. 17643 (December 1978), pp. 22-23,
"I. Emulsion preparation and type
s) ", and No. 18716 (November 1979), p. 648,
No. 307105 (November 1989), pages 863 to 865, and the like.

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).
ngineering), Vol. 14, pp. 248-257 (1970), US 4,43
4,226, GB 2,112,157. The crystal structure may be uniform, the inside and the outside may be composed of different halogen compositions, or may have a layered structure. Silver halides having different compositions may be joined by epitaxial joining, or may be joined to a compound other than silver halide, such as, for example, silver rhodanate or lead oxide. Also, a mixture of particles of various crystal forms may be used. The above emulsion may be either a surface latent image type in which a latent image is mainly formed on the surface, an internal latent image type in which the latent image is formed inside the grains, or a type having a latent image on both the surface and the inside. It is necessary to be.
Among the internal latent image type emulsions, core / shell type internal latent image type emulsions 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 the development process, but is preferably 3 to 40 nm, particularly preferably 5 to 20 nm.

As the silver halide emulsion, usually, those subjected to physical ripening, chemical ripening and spectral sensitization are used. Additives used in such a process are described in RD17643, RD17616 and RDRD 307105, and the relevant portions are summarized in the table below. The amount of silver applied to the photographic material is 6.0 g / m ²
Or less, and most preferably 4.5 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 95 mol% or more of silver chloride as silver halide grains. In particular, silver bromochloride or silver chloride substantially free of silver iodide can be preferably used in order to shorten the development processing time. Here, "contains substantially no silver iodide" means that the silver iodide content is 1 mol% or less, preferably 0.2 mol% or less. On the other hand, 0.01 to 3 mol% of the emulsion surface described in JP-A-3-84545 is used for the purpose of increasing the high illuminance sensitivity, increasing the spectral sensitization sensitivity, or increasing the stability over time of the photosensitive material. 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. However, when an emulsion having the same halogen composition between 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, grains having a so-called uniform structure having the same composition in any part of the silver halide grains, a core inside the silver halide grains and a shell surrounding the core are used. (shell)
[Single or plural layers] grains having a so-called laminated structure having different halogen compositions from each other or a structure having a non-layered portion having a different halogen composition inside or on the surface of the grains. Particles having a structure in which portions having different compositions are joined together) can be appropriately selected and used. It is also effective to further increase the silver chloride content of the silver halide emulsion in order to reduce the replenishment amount of the developing solution. In such a case, a substantially pure silver chloride emulsion having a silver chloride content of 98 to 100 mol% is also preferably used.

Average grain size of silver halide grains contained in the silver halide emulsion (grain size is defined as the diameter of a circle equivalent to the projected area of the grain, and the number average is calculated)
Is preferably 0.1 μm to 2 μm. The particle size distribution is preferably a so-called monodisperse coefficient of variation (a standard deviation of the particle size distribution divided by the average particle size) of 20% or less, 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 localized phase of silver halide grains or a substrate thereof may contain a foreign metal ion or a complex ion thereof. Preferred metals are Group VIII and VIII of the periodic table.
It is selected from metal ions or metal complexes belonging to Group IIb, lead ions and thallium ions. Ion selected from iridium, rhodium, iron, etc. or its complex ion for the localized phase, and metal ion selected from osmium, iridium, rhodium, platinum, ruthenium, palladium, cobalt, nickel, iron, etc. for 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. A plurality of these metals may be used. In particular, the iron and iridium compounds are preferably present in the silver bromide localized phase.

The silver halide emulsion is usually subjected to chemical sensitization and spectral sensitization. Chemical sensitization includes chemical sensitization using a chalcogen sensitizer (specifically, sulfur sensitization represented by addition of an unstable sulfur compound, selenium sensitization by a selenium compound, and tellurium sensitization by a tellurium compound). ), Noble metal sensitization typified by gold sensitization, or reduction sensitization, etc. can be used alone or in combination. Compounds used for chemical sensitization are disclosed in
Those described in the lower right column on page 18 to the upper right column on page 22 of JP-A-2-215272 are preferably used.

Various compounds or their precursors may be added to the silver halide emulsion for the purpose of preventing fogging during the production process, storage or photographic processing of the photographic material, or stabilizing photographic performance. Can be. As specific examples of these compounds, those described on pages 39 to 72 of JP-A-62-215272 are preferably used. Further, a 5-arylamino-1,2,3,4-thiatriazole compound (the aryl residue has at least one electron-withdrawing group) described in EP0447647 is also preferably used.

The spectral sensitization is performed for the purpose of imparting spectral sensitivity to a desired light wavelength region to the emulsion of each layer in the photosensitive material. Examples of spectral sensitizing dyes used for spectral sensitization in blue, green, and red regions include, for example, Heterocyclic co
mpounds-Cyanine dyes and related compounds (John W
iley & Sons [New York, London], 1964). Specific examples of the compounds and the spectral sensitization method are disclosed in the above-mentioned JP-A-62-2.
No. 15,272, from page 22, upper right column to page 38, are preferably used. In particular, as the red-sensitive spectral sensitizing dye for silver halide emulsion grains having a high silver chloride content, spectral sensitizing dyes described in JP-A-3-123340 are useful in terms of stability, adsorption strength, and exposure temperature. It is very preferable from the viewpoint of dependence and the like.

For efficient spectral sensitization in the infrared region, JP-A-3-15049, page 12, upper left column to page 21, lower left column, 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 4, page 12, EP 0,420,012
Lines to 10 pages, 33 lines, European Patent EP 0,443,466
And sensitizing dyes described in U.S. Pat. No. 4,975,362 are preferably used.

In the light-sensitive material, a hydrophilic colloid layer is added to a hydrophilic colloid layer for the purpose of preventing irradiation or halation or improving safelight safety and the like.
Dyes which can be decolorized by treatment (among others, 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 color separation and safelight safety when used in an increased amount. As dyes that can be used without deteriorating color separation, water-soluble dyes described in Japanese Patent Application Nos. 03-310143, 03-310189, and 03-310139 are preferable.

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

When exposing the photosensitive material for printing to a printer, it is preferable to use a band stop filter described in US Pat. No. 4,880,726. As a result, light color mixing is removed, and color reproducibility is significantly improved. The exposed light-sensitive material can be subjected to conventional color development processing, but it is preferable to perform bleach-fix processing after color development for the purpose of rapid processing. Particularly when the high silver chloride emulsion is used, the pH of the bleach-fixing solution is preferably about 6.5 or less, more preferably about 6 or less, for the purpose of accelerating desilvering.

The photographic additives that can be used are also described in the RD, and the relevant places are shown in the following table. Type of additive RD17643 RD18716 RD307105 Chemical sensitizer page 23, page 648, right column, page 866 2. Sensitivity enhancer page 648, right column 3. Spectral sensitizer, pages 23 to 24, page 648, right column 866 to 868 Super sensitizer, page 649, right column 4. Brightener 24 page 647, right column page 868 5 Light absorbers, pages 25 to 26, page 649, right column, page 873 Filters, page 650, left column Dyes, ultraviolet absorbers 6. Binders, page 26, page 651, left column 873 to 874 7. Plasticizers, page 27, page 650, right Column 876 Lubricant 8. Coating aid, pages 26 to 27 Page 650 Right column 875 to 876 Surfactant 9. Static 27 page 650 650 Right column 876 to 877 Inhibitor 10. Mast agent 878 to 879

Although various dye-forming couplers can be used in the light-sensitive material, the following couplers are particularly preferred. Yellow coupler: a coupler represented by formulas (I) and (II) of EP 502,424A; a coupler represented by formulas (1) and (2) of EP 513,496A (especially Y-28 on page 18); Claim 1 of -134523
A coupler represented by the general formula (I) of US Pat. No. 5,066,576, column 1, lines 45 to 55;
Couplers represented by general formula (I) in paragraph 0008 of JP-A-4-274425; couplers described in claim 1 on page 40 of EP 498,381A1 (especially D-35 on page 18); formulas on page 4 of EP 447,969A1 (Y)
(Particularly Y-1 (page 17), Y-54 (page 41));
Couplers represented by formulas (II) to (IV) in columns 7, 36 to 58 of US Pat. Acylacetanilide type couplers,
Pivaloyl acetanilide type coupler having a halogen atom or an alkoxy group at the ortho position of the anilide ring, EP0447969A, JP-A-5-107701
, An acyl group described in JP-A-5-113624 and the like.
Acylacetanilide-type couplers which are cycloalkanecarbonyl groups substituted at the position, European Patent EP-0448252
No. A, and a malondianilide type coupler described in EP-0524540A and the like.

Magenta coupler; JP-A-3-39737 (L-57 (1
L-68 (lower right of page 12), L-77 (lower right of page 13); EP 456,
257 (A-4 -63 (p. 134), (A-4) -73, -75 (p. 139); E
M-4, -6 (p. 26), M-7 (p. 27) of P 486, 965; Japanese Patent Application No. 4-234120
Paragraph 0024 of M-45; Japanese Patent Application No. 4-36917, Paragraph 0036 of M-1; Japanese Patent Application Laid-Open No. 4-326261, Paragraph 0237 of M-22.
No. WO92 / 18902 and WO92 / 1890
An arylthio-eliminated 5-pyrazolone magenta coupler as described in No. 3. Pyrazoloazole type couplers include pyrazoloazole couplers containing a sulfonamide group in the molecule as described in JP-A-61-65246, and alkoxyphenyl sulfones as described in JP-A-61-147254. Pyrazoloazole couplers having an amide ballast group and pyrazoloazole couplers having an alkoxy group or an aryloxy group at the 6-position as described in EP 226,849A and EP 294,785A.

Cyan coupler: CX-1, described in JP-A-4-04843
3,4,5,11,12,14,15 (pages 14-16); JP-A-4-43345, C-7,1
0 (page 35), 34, 35 (page 37), (I-1), (I-17) (pages 42 to 43); the general formula (Ia) or (Ia) of claim 1 of Japanese Patent Application No. 4-236333. A coupler represented by Ib). Polymer coupler: P-1, P-5 (p. 11) of JP-A-2-44345.
Phenol couplers, naphthol couplers, diphenylimidazole cyan couplers described in JP-A-2-33144, 3-hydroxypyridine cyan couplers described in EP 0 333 185 A2, and JP-A 64-32260. Cyclic active methylene cyan couplers described, EP 0 562
No. 26A1, a pyrrolopyrazole type cyan coupler described in EP-A-0 484 909, a pyrroloimidazole type cyan coupler described in EP 0484909, and EP 0488.
Pyrrolotriazole type cyan couplers described in JP-A-248 and EP0491197A1.

Examples of couplers in which the coloring dye has an appropriate diffusibility include US Pat. No. 4,366,237, GB 2,125,570, EP 96,873B,
Those described in DE 3,234,533 are preferred. Couplers for correcting unnecessary absorption of color-forming dyes are yellow colored cyan couplers 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
), EX-1 (page 249), EX-7 (page 251), magenta colored cyan coupler CC-9 (column 8) described in US 4,833,069,
CC-13 (column 10), US 4,837,136 (2) (column 8), WO92
Colorless masking couplers of formula (A) of claim 1 of US Pat. Examples of the compound (including a coupler) which releases a photographically useful compound residue by reacting with an oxidized developing agent include the following. Development inhibitor releasing compound: EP 378,2
Compounds represented by formulas (I), (II), (III) and (IV) described on page 11 of 36A1 (especially T-101 (page 30), T-104 (page 31), T-113 (36 page),
T-131 (p. 45), T-144 (p. 51), T-158 (p. 58)), EP436, 938A2
Compounds of the formula (I) described on page 7 (particularly D-49 (5
1)), a compound represented by formula (1) of Japanese Patent Application No. 4-134523 (particularly, paragraph (0027) of paragraph 0027), a compound represented by formulas (I), (II), Compounds represented by (III) (especially on page 29)
I- (1)); Bleaching accelerator releasing compounds: compounds represented by the formulas (I) and (I ′) on page 5 of EP 310,125A2 (especially (60) and (6) on page 61)
1)) and a compound represented by formula (I) of claim 1 of Japanese Patent Application No. 4-325564 (particularly, paragraph (0022) (7)); a ligand releasing compound: represented by LIG-X described in claim 1 of US Pat. No. 4,555,478. Compounds (especially compounds on lines 21-41 of column 12); leuco dye releasing compounds: compounds 1-6 of columns 3-8 of US 4,749,641; fluorescent dye releasing compounds: represented by COUP-DYE of claim 1 of US 4,774,181. Compounds (especially columns 7 to 10)
Compounds of formulas (1) to (11); Development accelerator or fogging agent release compounds: compounds represented by formulas (1), (2) and (3) in column 3 of US Pat. No. 4,656,123 (especially (I-22) in column 25) and EP 450,6
ExZK-2, p. 75, lines 36-38 of 37A2; a compound which releases a group which becomes a dye only when it is cleaved: a compound represented by formula (I) in claim 1 of US Pat. No. 4,857,447 (especially, Y- 1 to
Y-19).

As the additives other than the coupler, the following are preferable. Dispersion medium of oil-soluble organic compound: P-3,5, 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 4,199,3
63. Latex according to 63; oxidized developing agent scavenger: a compound represented by the formula (I) in columns 54 to 62 of column 2, US 4,978,606 (especially I-, (1), (2), (6), ) (Column 4 ~
5), US Pat. No. 4,923,787, columns 5 to 10 of formula (particularly compound 1 (column 3); stain inhibitor: EP 298321A 4
Formulas (I) to (III) on page 30-33, especially I-47, 72, III-1, 27 (24
-48 pages); Anti-fading agent: A-6, 7, 20, 21, 23, 24, EP 298321A
25,26,30,37,40,42,48,63,90,92,94,164 (pp.69-118),
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 amount of color enhancer or color mixture inhibitor used:
EP 411324A, pages 1 to 24, I-1 to II-15, especially I-46; Formalin Scavenger: EP 477932A, pages 24 to 29, SCV-1 to
28, especially SCV-8; hardener: H-1,4 on page 17 of JP-A-1-214845,
6,8,14, US 4,618,573, columns 13 to 23 of formulas (VII) to (XI
Compound (H-1 to 54) represented by I), JP-A-2-214852-8
Compounds (H-1 to 76) represented by the formula (6) at the lower right of the page, especially H-1
4, compounds described in claim 1 of US Pat. No. 3,325,287; development inhibitor precursors: P-24,37,39 of JP-A-62-168139 (6 to
Compounds described in claim 1 of US 5,019,492, especially 28, 29 of column 7; Preservatives, fungicides: I-1 to III-43 of columns 3 to 15 of US 4,923,790, especially II-1, 9,10,18, III-25;
Stabilizers, antifoggants: US 4,923,793 columns 6 to 16
I-1 to (14), especially I-1,60, (2), (13), compounds 1 to 65 in columns 25 to 32 of US 4,952,483, especially 36: Chemical sensitizer: triphenylphosphine selenide, especially Compound 50 of Kaihei 5-40324; Dye: JP-A-3-156450, pages 15-18, a-1 to b-20,
In particular, a-1, 12, 18, 18, 27, 35, 36, b-5, V-1 to 23 on pages 27 to 29, especially FI-1, F-II on pages 33 to 55 of V-1, EP 445627A. -43, especially
FI-11, F-II-8, III-1 to 36 on pages 17 to 28 of EP 457153A,
In particular, III-1,3, a microcrystalline dispersion of Dye-1 to 124 of 8-26 of WO 88/04794, compounds 1 to 22 of EP 319999A, pages 6 to 11, especially compound 1, a compound of formula (1) of EP 519306A Compounds D-1 to 87 represented by (3) to (3) (pages 3 to 28), compounds 1 to 22 represented by the formula (I) of US Pat. No. 4,268,622 (columns 3 to 10), US Pat.
Compounds (1) to (31) represented by the formula (I)
9); UV absorber: Compounds (18b) to (18r), 101 to 427 (pages 6 to 9) represented by formula (1) of JP-A-46-3335, represented by formula (I) of EP 520938A Compounds (3) to (66) (pages 10 to 44) and compound HBT-1 to 10 (page 14) represented by formula (III), EP 52
Compounds (1) to (31) represented by the formula (1) of 1823A (columns 2 to 9).

The support used for the photographic material for printing may be any support such as glass, paper and plastic film on which a photographic emulsion layer can be coated, and the most preferred is a reflective support. The term "reflective support" used in the present invention refers to a support that enhances reflectivity to sharpen a dye image formed in a silver halide emulsion layer. Such a reflective support includes a support. One coated with a hydrophobic resin dispersedly containing a light-reflective substance such as titanium oxide, zinc oxide, calcium carbonate, calcium sulfate, etc., or one using a hydrophobic resin itself dispersedly containing a light-reflective substance as a support Is included. For example, polyethylene coated paper,
Polyethylene terephthalate-coated paper, polypropylene-based synthetic paper, transparent support provided with a reflective layer or combined with a reflective substance, such as a glass plate, polyethylene terephthalate, polyester film such as cellulose triacetate or cellulose nitrate, polyamide film, polycarbonate Film, polystyrene film, vinyl chloride resin and the like. As the reflective support used in the present invention, a paper support coated on both sides with a water-resistant resin layer,
Preferably, at least one of the water-resistant resin layers contains white pigment fine particles.

The water-resistant resin of the reflective support is a resin having a water absorption (% by weight) of 0.5, preferably 0.1 or less, for example, polyolefin such as polyethylene, polypropylene and polyethylene polymer, vinyl polymer and the like. Copolymers (polystyrene, polyacrylate and copolymers thereof), polyesters (polyethylene terephthalate, polyethylene isophthalate, etc.) and copolymers thereof. Particularly preferred are polyethylene and polyester. As the polyethylene, high-density polyethylene, low-density polyethylene, linear low-density polyethylene, and a blend of these polyethylenes can be used. The melt flow rate (hereinafter abbreviated as MFR) of these polyethylene resins before processing is preferably in the range of 1.2 g / 10 min to 12 g / 10 min as measured under the condition 4 in Table 1 of JIS K7210. The MFR of the polyolefin resin before processing refers to the MFR of the resin before kneading the bluing agent and the white pigment.
Indicates FR.

A suitable support for the light-sensitive material is 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 on page 879 of the same 307105.

In a photographic light-sensitive material, the total thickness of all the hydrophilic colloid layers on the side having the emulsion layer is preferably 23 μm or less, more preferably 20 μm or less, and 13 to 17 μm.
Is particularly preferred. Further, the film swelling speed T _1/2 is preferably 5 to 15 seconds. T _1/2 is the time required for the film thickness to reach 1/2 when the saturated film thickness is 90% of the maximum swollen film thickness reached when the color developing solution is processed at 30 ° C. for 3 minutes and 15 seconds. Is defined.
T _1/2 can be adjusted by adding a hardening agent to gelatin as a binder or by changing the aging conditions after coating. The swelling ratio is 150-350%
Is preferred. The swelling ratio can be calculated from the maximum swelling film thickness under the conditions described above by the formula: (maximum swelling film thickness-film thickness) / film thickness. The photosensitive material can 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. The back layer preferably contains the above-described light absorber, filter dye, ultraviolet absorber, antistatic agent, hardener, binder, plasticizer, lubricant, coating aid, and surfactant. The swelling ratio of the back layer is preferably from 150 to 500%.

The following materials can be preferably used as the light-sensitive material used in the present invention. A photosensitive material having a magnetic recording layer. The recording layer is composed of magnetic particles (preferably, Co-coated ferromagnetic iron oxide or the like) dispersed in a binder. It is preferably provided on the entire surface. The magnetic particles may be treated with a coupling agent as described in JP-A-6-161032. As a binder,
The polymers described in JP-A-4-219569 and the like can be preferably used. The recording layer may be provided anywhere, but is preferably provided on the side opposite to the emulsion layer with respect to the support (back layer). A layer containing a slip agent is provided on the upper layer of the recording layer,
The outermost layer on the side of the photosensitive emulsion layer with respect to the support preferably contains a matting agent. Further, the photosensitive material preferably contains an antistatic agent in order to impart antistatic properties even after the development processing, and the antistatic agent is preferably a conductive metal oxide or an ionic polymer. . The antistatic agent is preferably used so that the electrical resistance is 10 ¹² Ω · cm or less under the conditions of 25 degrees and 10% RH. Regarding photosensitive materials having a magnetic recording layer, U.S. Patents 5,336,589, 5,250,404, 5,229,259, and 5,215,8
74, EP 466130 A. As the support used for the light-sensitive material, a polyester support having improved curl and a reduced thickness is preferable. The thickness is preferably from 50 to 105 μm, and the material is preferably a polyethylene aromatic dicarboxylate-based polyester (preferably, a material mainly composed of benzenedicarboxylic acid, naphthalenedicarboxylic acid and ethylene glycol).
Those having a glass transition temperature of 50 to 200 degrees are preferred.
As the surface treatment of the support, ultraviolet irradiation treatment, corona discharge treatment, glow discharge treatment, and flame treatment are preferable. Further, it is preferable to heat-treat the support at a temperature ranging from 40 ° C. to the glass transition temperature of the support for 0.1 to 1500 hours before or after the undercoat layer is applied to the support and before coating of the emulsion layer. In addition to the support, photosensitive materials, development processing, cartridges, and the like are described in Published Technical Report, Publication No. 94-6023 (published by the Invention Association, 1994).

[0104]

EXAMPLES Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited thereto.

Example 1 An exemplified compound (D-16) of the present invention was synthesized based on the following formula.

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Synthesis of Compound (2) 500 g of m-toluidine and iodine in a three-necked flask.
After adding 0 g, acetone 1332 ml was added dropwise thereto over 8 hours and 30 minutes while heating and stirring at an external temperature of 200 ° C. Low boiling components such as water generated from the reaction system were distilled off by setting a cooling device in the branch pipe. After completion of the dropwise addition, the obtained reaction mixture was distilled to obtain 701 g of the desired compound (2) (80% yield).
I got Boiling point: 165 to 170 ° C / 18 to 20 mmHg ・ Synthesis of compound (3) 290 g of compound (2) and 900 ml of N, N-dimethylacetamide are placed in a three-necked flask, and 162 ml of acetic anhydride is added at an external temperature of 50 ° C for 20 minutes. It dripped over. Then outside temperature 15
After heating and stirring at 0 ° C. for 2 hours, the mixture was allowed to cool to room temperature, poured into ice water, and extracted with 1.5 liter of ethyl acetate. The obtained ethyl acetate layer was combined with 100 ml of saturated saline and water 1
After washing four times with a mixture of liters, the mixture was dried over anhydrous sodium sulfate. The ethyl acetate layer thus obtained was concentrated by a rotary evaporator, and the obtained residue was purified by silica gel column chromatography to obtain 267 g (yield: 75%) of the desired compound (3). -Synthesis of compound (4) 276 g of compound (2) and 900 ml of methylene chloride were placed in a three-necked flask, and 235 g of N-bromosuccinimide was added thereto over 1 hour while stirring under ice cooling.
At this time, the internal temperature rose to a maximum of 12 ° C. After completion of the addition, the mixture was further stirred under ice cooling for 30 minutes, and then the ice bath was removed, followed by stirring for 1 hour. One liter of water was added thereto for extraction, and the obtained methylene chloride layer was washed three times with a mixed solution of 100 ml of saturated saline and 500 ml of water. The methylene chloride layer thus obtained was dried over anhydrous sodium sulfate and then concentrated on a rotary evaporator, and the obtained residue was mixed with 250 ml of acetonitrile.
Was added and dissolved. The mixture was allowed to stand at room temperature overnight, and the precipitated crystals were collected by filtration to obtain 265 g of the desired compound (4) (yield: 72%). -Synthesis of compound (5) 555 g of tetraethylene glycol was placed in a three-necked flask.
500 ml of tetrahydrofuran was added, and 44.1 g of potassium-t-butoxide was added thereto while stirring at room temperature, followed by stirring for 30 minutes. At this time, the temperature rose to a maximum of 40 ° C. Next, 110 g of compound (4) was added dropwise thereto over 30 minutes under ice cooling, and the ice bath was removed, followed by stirring at room temperature for 8 hours. The solvent was distilled off under reduced pressure using an aspirator, and 1 liter of ethyl acetate and 1 liter of water were added for extraction. The obtained ethyl acetate layer was mixed with a mixed solution of 100 ml of saturated saline and 900 ml of water. And washed 4 times. The ethyl acetate layer thus obtained was dried over anhydrous sodium sulfate, concentrated by a rotary evaporator, and the obtained residue was purified by silica gel column chromatography to obtain 90 g of the target compound (5) (yield: 60).
%). -Synthesis of compound (6) 84.2 g of compound (5), 4 g of Pd-C (10%), and 180 ml of ethanol were placed in an autoclave, and hydrogen pressure was adjusted to 10
The pressure was adjusted to 0 atm, and the mixture was stirred at 50 ° C for 8 hours. The filtrate obtained by suction filtration was concentrated with a rotary evaporator to obtain 85 g of the desired compound (6) as a residue. This was used in the next step without purification. -Synthesis of compound (7) 42.3 g of the compound (6) obtained above, 16.6 ml of concentrated hydrochloric acid and 120 ml of ethanol were placed in a three-necked flask, and 5.6 ml of sulfuric acid was added thereto while stirring under heating and reflux conditions. The mixture was added dropwise, and the mixture was stirred under heating and reflux for 1 hour.
6 ml was added dropwise, and the mixture was stirred under reflux with heating for 5 hours. After distilling off low-boiling components mainly composed of ethanol using an aspirator at an internal temperature of 50 ° C. or lower, the mixture was poured into ice and neutralized with sodium hydrogen carbonate. Ethyl acetate 50 here
0 ml and 200 ml of water were added for extraction, and the obtained ethyl acetate layer was washed three times with a mixed solution of 500 ml of saturated saline and 300 ml of water, dried over anhydrous sodium sulfate, and concentrated by a rotary evaporator. 35 g of the desired compound (7) was obtained as a residue. This was used in the next step without purification. -Synthesis of compound (8) 35 g of the compound (7) obtained above in a three-necked flask, 8.2 g of sodium iodide, 23.2 g of sodium hydrogen carbonate,
Add 80 ml of N, N-dimethylacetamide,
While stirring at 30 ° C. while heating, 10.4 g of 3-chloropropanol was added dropwise thereto over 10 minutes. After completion of the dropwise addition, the mixture was heated and stirred for 3 hours, and then cooled to room temperature. 400 ml of ethyl acetate and 400 ml of water were added thereto, followed by stirring and extraction. The obtained ethyl acetate layer was washed with water 3
Washed four times with a mixture of 00 ml and 100 ml of saturated saline,
It was dried over anhydrous sodium sulfate. The residue was concentrated on a rotary evaporator, and the residue was purified by silica gel column chromatography to obtain the desired compound (8).
32.9 g was obtained (82% yield). -Synthesis of compound (9) 2,5-dichloroaniline 20.1 in a three-necked flask
g and 115 ml of water, and 39.7 ml of sulfuric acid was added thereto while stirring under ice cooling. Further, a solution prepared by dissolving 9.5 g of sodium nitrite in 25 ml of water was added dropwise thereto over 10 minutes while maintaining the internal temperature at 8 ° C. or lower, and stirring was continued for 30 minutes after completion of the dropwise addition. Compound (8) 32 in another three-necked flask
g, 71.2 g of sodium acetate, 49.4 ml of acetic acid, and 90 ml of methanol, and the solution of the diazonium salt prepared above was added while stirring under ice-cooling while maintaining the internal temperature at 16 ° C. or lower. The reaction was followed by TLC on the way, and when the compound (8) disappeared in the reaction system, the addition of the diazonium salt solution was terminated. After continuing the stirring for 30 minutes after the completion of the addition, methanol was distilled off under reduced pressure, the reaction mixture was poured on ice, and neutralized by adding a sodium hydroxide solution.
One liter of ethyl acetate and 500 ml of water were added for extraction. The obtained ethyl acetate layer was washed four times with a mixture of 400 ml of water and 100 ml of saturated saline, and dried over anhydrous sodium sulfate. This was concentrated by a rotary evaporator, and the obtained residue was purified by silica gel column chromatography to obtain 33.4 g of the desired compound (9) (yield: 75%). -Synthesis of exemplary compound (D-16) Compound (9) 26.0 g, palladium-carbon (10%)
1.3 g and methanol (150 ml) were placed in an autoclave and stirred at a hydrogen pressure of 100 atm at room temperature for 5 hours. Naphthalene-1,5-disulfonic acid is added to the obtained reaction mixture.
A solution prepared by dissolving 15.1 g of tetrahydrate in 35 ml of methanol was added thereto, followed by filtration. The obtained filtrate was concentrated on a rotary evaporator, and then 200 ml of ethyl acetate and 200 ml of water were added.
The resulting aqueous layer was further washed three times with 200 ml of ethyl acetate. The aqueous layer thus obtained was concentrated using a rotary evaporator, and then the solvent was distilled off using a vacuum pump to remove the target compound (D-1).
6) 28.0 g were obtained (90% yield).

Example 2 Exemplified compound (D-17) of the present invention was synthesized based on the following formula.

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Synthesis of Compound (10) Compound (4) obtained in Example 1 in a three-necked flask 155.
1 g, 205 g of sodium acetate and 80 ml of N, N-dimethylacetamide were added, and the mixture was stirred under heating at an external temperature of 150 ° C. for 2 hours, and then cooled to room temperature. 1.5 L of ethyl acetate and 1 L of water were added thereto, followed by stirring and extraction. The obtained ethyl acetate layer was washed with 800 ml of water and 2
The mixture was washed four times with a mixture of 00 ml and dried over anhydrous sodium sulfate. This was concentrated using a rotary evaporator, and the residue was added with 600 ml of acetonitrile, dissolved and cooled with ice to obtain 127.3 g of the desired compound (10) (yield: 88%). Synthesis of compound (11) 127.3 g of the compound (10) and 700 ml of ethanol were placed in a one-necked flask, and a solution prepared by dissolving 70.4 g of sodium hydroxide in 140 ml of water was added thereto while stirring at room temperature.
After dropping over 0 minutes, the mixture was stirred for 1 hour. During dropping, the internal temperature rose to a maximum of 45 ° C. After distilling off the low-boiling components mainly composed of ethanol using an aspirator at an internal temperature of 50 ° C. or lower, the residue was poured into ice, 142 ml of hydrochloric acid was added thereto, and the mixture was stirred. After adding 40 g of sodium, 800 ml of ethyl acetate and 5 parts of water were added.
After adding 00 ml and stirring, extraction was performed. The obtained ethyl acetate layer was washed four times with a mixed solution of 400 ml of water and 100 ml of saturated saline, dried over anhydrous sodium sulfate, and concentrated by a rotary evaporator to obtain the desired compound (11) as a crude product. Obtained as a product. This was used in the next step without purification. -Synthesis of compound (12) The compound (11) obtained above, 10 g of Pd-C (10%) and 400 ml of ethanol were placed in an autoclave, and hydrogen pressure was adjusted to 10%.
The pressure was adjusted to 0 atm, and the mixture was stirred at 50 ° C for 8 hours. The filtrate obtained by suction filtration was concentrated with a rotary evaporator to obtain the target compound (12) as a residue. This was used in the next step without purification. -Synthesis of compound (13) Compound (12) obtained above in a three-necked flask, concentrated hydrochloric acid 75m
l, 500 ml of ethanol was added thereto, and 50 ml of sulfuric acid was added dropwise while stirring under heating and refluxing conditions, and the mixture was stirred under heating and refluxing for 1 hour, and then 50 ml of sulfuric acid was added dropwise and stirring under heating and reflux was continued for 4 hours. . After distilling off low-boiling components mainly composed of ethanol using an aspirator at an internal temperature of 50 ° C. or lower, the mixture was poured into ice and neutralized with sodium hydrogen carbonate. Ethyl acetate 800ml, water 500ml
Was added and extracted. The obtained ethyl acetate layer was washed four times with a mixed solution of 100 ml of a saturated saline solution and 400 ml of water, dried over anhydrous sodium sulfate and concentrated by a rotary evaporator. Purification by column chromatography gave 65.7 g of the desired compound (13) (72% yield from compound (10)). -Synthesis of compound (15) 65.7 g of the compound (13) obtained above, 178 g of potassium hydroxide, and 500 ml of toluene were placed in a three-necked flask, and 960 g of the compound (14) was added thereto while stirring under heating and reflux. It was added dropwise over 1 hour. Compound (14) is a mixture of tetraethylene glycol mono p-toluenesulfonate and 3,4-
Synthesized from dihydro-2H-pyran. After completion of the dropwise addition, the mixture was continuously heated and stirred for 1 hour, and then a low-boiling component containing toluene as a main component was distilled off at an internal temperature of 120 ° C. or lower using an aspirator, and then cooled to room temperature. This was poured into a mixture of 400 ml of methanol and 1 kg of ice, 1 liter of ethyl acetate was added, 600 ml of hydrochloric acid was added with stirring, and after stirring for 1 hour, 420 g of sodium bicarbonate was further added and stirred, followed by extraction. The obtained ethyl acetate layer was washed four times with a mixed solution of 600 ml of water and 100 ml of saturated saline, and dried with anhydrous sodium sulfate. This was concentrated using a rotary evaporator, and the residue was purified by silica gel column chromatography to obtain 137 g of the desired compound (15) (yield 78%).・ Synthesis of compound (16) 37.0 g of compound (15), 150 ml of methanol and 19 ml of hydrochloric acid were placed in a three-necked flask, and 6.9 g of sodium nitrite was dissolved in 13 ml of water while stirring under ice-cooling. Was added dropwise over 10 minutes. After the completion of the dropwise addition, the ice bath was removed and stirring was continued for 3 hours. The residue obtained by distilling off the low-boiling component mainly composed of methanol at an internal temperature of 25 ° C. or less using an aspirator was poured on ice, 37 g of sodium bicarbonate was added and stirred, 300 ml of ethyl acetate and 1 of water were added.
Extraction was performed by adding 00 ml. The obtained ethyl acetate layer was washed with a mixed solution consisting of 200 ml of water and 50 ml of a saturated saline solution.
After washing twice and drying over anhydrous sodium sulfate, the mixture was concentrated using a rotary evaporator. The obtained residue was purified by silica gel column chromatography to obtain 26.6 g of the desired compound (16) (68% yield). -Synthesis of exemplary compound (D-17) 26.6 g of compound (16), palladium-carbon (10%)
2.0 g and methanol (150 ml) were placed in an autoclave and stirred at room temperature under a hydrogen pressure of 100 atm for 5 hours. Naphthalene-1,5-disulfonic acid is added to the obtained reaction mixture.
A solution prepared by dissolving 16.3 g of tetrahydrate in 35 ml of methanol was added thereto, followed by filtration. The obtained filtrate was concentrated by a rotary evaporator, and the solvent was distilled off by a vacuum pump to remove the target compound (D). -17) 38.2 g was obtained (98% yield).

Example 3 The exemplified compound (D-20) of the present invention was synthesized based on the following formula.

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Synthesis of Compound (18) Compound (7) obtained in Example 1 in a three-necked flask 114.
5 g, 168 g of potassium hydroxide and 500 ml of toluene were added, and the compound (17) 3 was added thereto while stirring under heating and reflux.
45.7 g was added dropwise over 1 hour. Compound (17) was synthesized from ethylene chlorohydrin and 3,4-dihydro-2H-pyran. After completion of the dropwise addition, the mixture was continuously heated and stirred for 1 hour, and then a low-boiling component containing toluene as a main component was distilled off at an internal temperature of 120 ° C. or lower using an aspirator, and then cooled to room temperature. 400 ml of methanol and 1 piece of ice
1 liter of ethyl acetate was added to the mixture, and 515 ml of hydrochloric acid was added with stirring. After stirring for 1 hour, 300 g of sodium hydrogencarbonate was further added and stirred, followed by extraction. The obtained ethyl acetate layer was washed four times with a mixed solution of 600 ml of water and 100 ml of saturated saline, and dried with anhydrous sodium sulfate. The residue was concentrated by a rotary evaporator and the residue was purified by silica gel column chromatography to obtain 104.7 g of the desired compound (18) (yield: 82%). -Synthesis of compound (19) 38.3 g of compound (18), 150 ml of methanol and 26 ml of hydrochloric acid were placed in a three-necked flask, and 9.3 g of sodium nitrite was dissolved in 18 ml of water while stirring under ice-cooling. Was added dropwise over 10 minutes. After completion of the dropwise addition, the ice bath was removed, and stirring was continued for 5 hours. The residue obtained by distilling off the low-boiling component mainly composed of methanol at an internal temperature of 25 ° C. or lower using an aspirator was poured on ice, 50 g of sodium bicarbonate was added and the mixture was stirred.
Extraction was performed by adding 00 ml. The obtained ethyl acetate layer was washed with a mixed solution consisting of 200 ml of water and 50 ml of a saturated saline solution.
After washing twice and drying over anhydrous sodium sulfate, the mixture was concentrated with a rotary evaporator. The obtained residue was purified by silica gel column chromatography to obtain 32.8 g of the desired compound (19) (yield 81%). -Synthesis of exemplary compound (D-20) 26.7 g of compound (19), palladium-carbon (10%)
2.0 g and methanol (150 ml) were placed in an autoclave and stirred at room temperature under a hydrogen pressure of 100 atm for 5 hours. Naphthalene-1,5-disulfonic acid is added to the obtained reaction mixture.
A solution obtained by dissolving 18.0 g of tetrahydrate in 40 ml of methanol was added thereto, followed by filtration. The obtained filtrate was concentrated by a rotary evaporator, and the solvent was distilled off by a vacuum pump to remove the target compound (D). -20) 36.3 g (94% yield).

Example 4 Preparation of Multilayer Color Photosensitive Material Each layer having the following composition was applied to prepare Sample 101 as a multilayer color photographic material. (Composition of photosensitive layer) The main materials used for each layer are classified as follows: ExC: cyan coupler UV: ultraviolet absorber ExM: magenta coupler HBS: high boiling point organic solvent ExY: yellow coupler H: gelatin Curing agent ExS: Sensitizing dye The number corresponding to each component indicates the coating amount in g / m ² , and for silver halide, it indicates the coating amount in terms of silver. However, as for the sensitizing dye, the coating amount is shown in mol unit with respect to 1 mol of silver halide in the same layer.

(Sample 101) First Layer (Antihalation Layer) Black Colloidal Silver Silver 0.18 Gelatin 1.60 ExM-1 0.11 ExF-1 3.4 × 10 ^-3 ExF-2 (Solid Disperse Dye) 0.03 ExF-3 (Solid Disperse Dye) ) 0.04 HBS-1 0.16

Second layer (intermediate layer) ExC-2 0.055 UV-1 0.011 UV-2 0.030 UV-3 0.053 HBS-1 0.05 HBS-2 0.02 Polyethyl acrylate latex 8.1 × 10 ^-2 gelatin 1.75

Third layer (low-sensitivity red-sensitive emulsion layer) Silver iodobromide emulsion A silver 0.46 ExS-1 5.0 × 10 ^-4 ExS-2 1.8 × 10 ^-5 ExS-3 5.0 × 10 ^-4 ExC-1 0.16 ExC-3 0.045 ExC-5 0.0050 ExC-7 0.001 ExC-8 0.010 Cpd-2 0.005 HBS-1 0.090 Gelatin 0.87

Fourth layer (medium-sensitivity red-sensitive emulsion layer) Silver iodobromide emulsion D Silver 0.70 ExS-1 3.0 × 10 ^-4 ExS-2 1.2 × 10 ^-5 ExS-3 4.0 × 10 ^-4 ExC-1 0.22 ExC-2 0.055 ExC-5 0.007 ExC-8 0.009 Cpd-2 0.036 HBS-1 0.11 Gelatin 0.70

Fifth layer (high-sensitivity red-sensitive emulsion layer) Silver iodobromide emulsion E 1.62 ExS-1 2.0 × 10 ^-4 ExS-2 1.0 × 10 ^-5 ExS-3 3.0 × 10 ^-4 ExC-1 0.133 ExC-3 0.040 ExC-6 0.040 ExC-8 0.014 Cpd-2 0.050 HBS-1 0.22 HBS-2 0.10 Gelatin 0.85

Sixth layer (intermediate layer) Cpd-1 0.07 HBS-1 0.04 Polyethyl acrylate latex 0.19 Gelatin 2.30

Seventh layer (low-sensitivity green-sensitive emulsion layer) Silver iodobromide emulsion A silver 0.24 silver iodobromide emulsion B silver 0.10 silver iodobromide emulsion C silver 0.14 ExS-4 4.0 × 10 ^-5 ExS-5 1.8 × 10 ^-4 ExS-6 6.5 × 10 ^-4 ExM-1 0.005 ExM-2 0.30 ExM-3 0.09 ExY-1 0.015 HBS-1 0.26 HBS-3 0.006 Gelatin 0.80

Eighth Layer (Medium Speed Green Sensitive Emulsion Layer) Silver Iodobromide Emulsion D Silver 0.94 ExS-4 2.0 × 10 ^-5 ExS-5 1.4 × 10 ^-4 ExS-6 5.4 × 10 ^-4 ExM-2 0.16 ExM-3 0.045 ExY-1 0.008 ExY-5 0.030 HBS-1 0.14 HBS-3 8.0 × 10 ^-3 Gelatin 0.90

Ninth layer (high-sensitivity green-sensitive emulsion layer) Silver iodobromide emulsion E 1.29 ExS-4 3.7 × 10 ^-5 ExS-5 8.1 × 10 ^-5 ExS-6 3.2 × 10 ^-4 ExC-4 0.011 ExM-1 0.016 ExM-4 0.046 ExM-5 0.023 Cpd-3 0.050 HBS-1 0.20 HBS-2 0.08 Polyethyl acrylate latex 0.26 Gelatin 0.82

10th layer (yellow filter layer) Yellow colloidal silver silver 0.010 Cpd-1 0.10 ExF-5 (solid disperse dye) 0.06 ExF-6 (solid disperse dye) 0.06 ExF-7 (oil-soluble dye) 0.005 HBS-1 0.055 gelatin 0.70

Eleventh layer (low-sensitivity blue-sensitive emulsion layer) Silver iodobromide emulsion A silver 0.25 silver iodobromide emulsion C silver 0.25 silver iodobromide emulsion D silver 0.10 ExS-7 8.0 × 10 ^-4 ExY-1 0.010 ExY-2 0.70 ExY-3 0.055 ExY-4 0.006 ExY-6 0.075 ExC-7 0.040 HBS-1 0.25 Gelatin 1.60

12th layer (high-sensitivity blue-sensitive emulsion layer) Silver iodobromide emulsion F silver 1.30 ExS-7 3.0 × 10 ^-4 ExY-2 0.15 ExY-3 0.06 HBS-1 0.070 Gelatin 1.13

13th layer (first protective layer) UV-2 0.08 UV-3 0.11 UV-4 0.26 HBS-1 0.09 Gelatin 1.20

Fourteenth layer (second protective layer) Silver iodobromide emulsion Silver 0.10 H-1 0.30 B-1 (1.7 μm in diameter) 5.0 × 10 ^-2 B-2 (1.7 μm in diameter) 0.10 B-3 0.10 S-1 0.20 Gelatin 1.75

Further, in order to improve the storability, processability, pressure resistance, fungicide / antibacterial property, antistatic property and coatability of each layer, W-1 to W-3, B-4 to B -6,
F-1 to F-17 and iron salts, lead salts, gold salts, platinum salts,
Contains iridium, palladium and rhodium salts.

Table 1 ──────────────────────────────────── Average AgI Average Particle Size Related to Particle Size Diameter / thickness ratio Particle structure / shape Content (%) μm Variation coefficient (%) Ratio of 2 or more%乳 剤 Emulsion A 2.1 0.55 25 81 Uniform structure tabular emulsion Emulsion B 9.1 0.63 26 84 Triple structure tabular emulsion E 3.1 0.60 24 98 Triple structure tabular emulsion E 4.2 0.80 19 92 Triple structure tabular Emulsion E 3.2 1.10 17 96 Triple structure tabular emulsion E 10.8 1.75 27 60 Double structure tabular emulsion G 1 0.07 15 0 Uniform structure cube ──────────────────── ────────────────

In Table 1, (1) Emulsions A to F were prepared according to the examples of JP-A-2-91938.
Reduction sensitization was performed using thiourea dioxide and thiosulfonic acid during the preparation of the particles. (2) Emulsions A to F were prepared according to the examples in JP-A-3-237450.
Gold sensitization, sulfur sensitization and selenium sensitization were performed in the presence of the spectral sensitizing dye and sodium thiocyanate described in each photosensitive layer. (3) For preparing tabular grains, low molecular weight gelatin is used according to the examples of JP-A-1-158426. (4) Dislocation lines described in JP-A-3-237450 are observed in the tabular grains using a high-pressure electron microscope.

Preparation of Dispersion of Organic Solid Disperse Dye ExF-2 shown below was dispersed by the following method. That is, water 2
1.7 ml and 3 ml of a 5% aqueous solution of sodium p-octylphenoxyethoxy ethanesulfonate and 0.5 g of a 5% aqueous solution of 0.5 g of p-octylphenoxypolyoxyethylene ether (polymerization degree 10) were placed in a 700 ml pot mill, and the dye ExF- 2 and 5.0 ml of zirconium oxide beads (diameter 1 mm) were added, and the contents were dispersed for 2 hours. For this dispersion, a BO type vibration boat mill manufactured by Chuo Koki was used. After dispersion, take out the contents, 12.5%
8 g of an aqueous gelatin solution was added, and the beads were removed by filtration.
A gelatin dispersion of the dye was obtained. The average particle size of the fine dye particles was 0.44 μm.

In the same manner, solid dispersions of ExF-3, ExF-4 and ExF-6 were obtained. The average particle size of the fine dye particles is 0.24 μm, 0.45 μm, and 0.52 μm, respectively.
m. ExF-5 is published in European Patent Application (EP)
The particles were dispersed by a microprecipitation dispersion method described in Example 1 of Japanese Patent No. 0,549,489A. The average particle size was 0.06 μm.

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(Processing step) Process Processing time Processing temperature Replenishment amount * Tank capacity Color development 3 minutes 40.0 ° C 200 ml 2.0 liters Bleaching 30 seconds 45.0 ° C 130 ml 0.7 liters Fixing (1) 30 seconds 45.0 ° C 100 ml 0.7 liters Settling (2) 30 seconds 45.0 ° C 70 ml 0.7 liter Rinse (1) 15 seconds 45.0 ° C-0.4 liter Rinse (2) 15 seconds 45.0 ° C 400 ml 0.4 liter Stability 15 seconds 45.0 ° C 400 ml 0.4 liter Drying 20 sec 80 ° C. * the replenishing amount is the light-sensitive material 1 m ² per (washing (3 tank countercurrent multistage cascade from 2) to the fixing (2)) (fixing (2) from to the fixing (1) is 2 tank countercurrent multistage cascade )

The composition of the processing liquid is shown below. (Color developer) Tank solution (g) Replenisher (g) Diethylenediaminetetraacetic acid 4.0 4.0 Sodium 4,5-dihydroxybenzene-1,3-disulfonate 0.5 0.5 Sodium sulfite 3.9 6.5 Potassium carbonate 37.5 39.0 Potassium bromide 2.7- Potassium iodide 1.3 mg-N-methylhydroxylamine hydrochloride 4.5 5.5 2-Methyl-4- [N-ethyl-N- (β-hydroxyethyl) amino] aniline sulfate (p-5) 5.0 9.0 1.0 liter 1.0 liter pH (prepared with potassium hydroxide and sulfuric acid) 10.05 10.25

(Bleaching solution) Tank solution (mol) Replenisher (mol) 1,3-diaminopropanetetraacetic acid ferric chloride ammonium monohydrate 0.33 0.50 ferric nitrate nonahydrate 0.30 4.5 ammonium bromide 0.80 1.20 Ammonium nitrate 0.20 0.30 Acetic acid 0.67 1.0 Add water 1.0 liter 1.0 liter pH (prepared with aqueous ammonia) 4.5 4.0

(Fixing solution) Common to tank solution and replenisher (g) Ammonium sulfite 28 Ammonium thiosulfate aqueous solution (700 g / L) 280 mL Imidazole 15 Ethylenediaminetetraacetic acid 15 Add water and add 1.0 L pH [prepared with ammonia water and acetic acid] 5.8

(Washing water) Common to tank liquid and replenisher tap water is H-type strongly acidic cation exchange resin (Amberlite IR-120B manufactured by Rohm and Haas) and OH type anion exchange resin (Amberlite IR-400). The mixture is passed through a mixed-bed column packed with water to treat the calcium and magnesium ion concentrations to 3 mg / l or less, and then treated by adding 20 mg / l of sodium diisocyanurate and 0.15 g / l of sodium sulfate. Water was used. The pH of this solution was in the range of 6.5 to 7.5.

(Stabilizing solution) Common to tank solution and replenishing solution 1,2-benzoisothiazolin-3-one 0.1 polyoxyethylene-p-monononyl 0.2 phenyl ether (average degree of polymerization: 10) , Adjusted with hydrochloric acid) 8.50

Sample 101 was subjected to imagewise exposure, and was subjected to continuous processing until the replenishment amount of the bleach-fixing solution became three times the tank amount in the above-mentioned processing steps. The running treatment liquid thus obtained is referred to as treatment 201. Next, the same color developer except that the color developing agent P-5 sulfate in the color developing solution was changed to an equimolar amount of the comparative color developing agent shown in Table 2 and the color developing agent of the present invention. Is prepared and the same continuous processing is performed to obtain each running processing solution (processing 202).
To 211). The promptness of the treatment was evaluated as follows. First, after subjecting the sample 101 to wedge exposure, the color developing process is changed from 1 minute to 3 minutes in steps of 10 seconds, and the process is performed using each of the running processing solutions (processing 202 to 211) [running process step (a). )], And the optical densities of the yellow, magenta, and cyan images of the obtained samples were measured. Next, after subjecting the sample 101 to the same wedge exposure, the sample 101 was subjected to a process in a comparative development process (b) shown below, and the optical densities of the yellow, magenta, and cyan images were measured in the same manner. The density curve of the magenta image obtained in the comparative development processing step (b) was compared with each of the above-described processing at intervals of 10 seconds, and the color development time required to obtain a magenta density equal to or higher than that was obtained.

The graininess is represented by an RMS value, and the aperture is determined by φ4.
It is determined by the usual method using a sample having a thickness of 8 μm.
Table 1 shows the relative values of the sample of No. 1 as 100. As the RMS value, measurement at a magenta density of fog + 0.4 was adopted for each sample.

Comparative color developing agent

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Comparative development processing step (b) (Processing method) Process Processing time Processing temperature Color development 3 minutes and 15 seconds 38 ° C Bleaching 1 minute and 00 seconds 38 ° Bleaching and fixing 3 minutes and 15 seconds 38 ° C Rinse with water (1) 40 seconds 35 ° C water wash (2) 1 minute 00 seconds 35 ° C Stable 40 seconds 38 ° C Drying 1 minute 15 seconds 55 ° C

Next, the composition of the processing solution will be described. (Color developing solution) (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 [P-5] 4.5 Add water and add 1.0 liter pH ( Adjusted with potassium hydroxide and sulfuric acid) 10.05

(Bleaching solution) (Unit g) Ferric ammonium ethylenediaminetetraacetate dihydrate 120.0 Disodium ethylenediaminetetraacetate 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%) of 15.0 ml water was added to 1.0 l pH (ammonia (Adjust with water and nitric acid) 6.3

(Bleach-fixing solution) (unit g) Ferric ammonium ethylenediaminetetraacetate dihydrate 50.0 Disodium ethylenediaminetetraacetate 5.0 Sodium sulfite 12.0 Aqueous ammonium thiosulfate solution (700 g / liter) 240.0 Milliliter ammonia water (27%) 6.0 milliliters add water 1.0 liter pH (adjusted with ammonia water and acetic acid) 7.2

(Rinse water) Tap water was replaced with H-type strongly acidic cation exchange resin (Amberlite IR-Rohm and Haas).
120B) and water through a mixed-bed column filled with an OH-type anion exchange resin (Amberlite IR-400) to treat the calcium and magnesium ion concentrations to 3 mg / l or less, followed by isocyanuric dichloride 20 mg / liter of sodium and 0.15 g / liter of sodium sulfate were added. The pH of this solution was in the range of 6.5 to 7.5.

(Stabilizing Solution) (Unit g) Sodium p-toluenesulfinate 0.03 Polyoxyethylene-p-monononylphenyl ether (average degree of polymerization 10) 0.2 Disodium ethylenediaminetetraacetate 0.05 1, 2,4-triazole 1.3 1,4-bis (1,2,4-triazol-1-ylmethyl) piperazine 0.75 1.0 liter with water added pH 8.5

Table 2 処理 Processing number Color developing agent Constant magenta density granular Remarks Color development time to obtain ────────────────────────────────── 201 P-5 2min 50 Second 100 Comparative Example 202 Comparative Compound-1 2:00 sec 107 203 Comparative Compound-2 2min10sec 104 ２０４204 Comparative Compound-3 2min10sec 103 ２０５205 Comparative Compound-4 2,000sec 105 ２０６206 Compare Compound-5 2,000 seconds 103 {207 D-2 2:00 seconds 96 of the present invention 208 D-13 2 minutes 10 seconds 93} 209 D-14 2:00 seconds 95 95 210 D-16 2 minutes 10 seconds 93 211 D-25 2min 10sec 97 〃 ──────────── ─────────────────────

From Table 2, it can be seen that the color developing agents of the present invention or the comparative compounds 1 to 5 can obtain a magenta image density in a much shorter development processing time than P-5 (processing No. 201). Recognize. It can be seen that Comparative Compounds 1 to 5 have excellent quickness, but the granularity is worse than P-5.

In the color developing agent of the present invention, the graininess is P-5.
Could be improved. That is, by using the developing agent of the present invention, the processing speed was improved and the granularity was improved at the same time.

Example 5 After the sample 101 in Example 4 was exposed, development processing was performed by the following processing method using the exemplified compound (D-13) of the present invention as a color developing agent in a color developing solution. However, the desired gradation can be obtained while the color development time is as short as 60 seconds, and the graininess is favorable. Also,
Instead of the exemplary compound (D-13), the exemplary compound (D-1)
5), exemplary compound (D-20), exemplary compound (D-2)
9), similar results could be obtained using Exemplified Compound (D-1).

Development process and processing solution composition Processing time Temperature Time Color development 45 ° C. 60 seconds Bleaching and fixing 45 ° C. 60 seconds Rinse with water (1) 40 ° C. 15 seconds Rinse with water (2) 40 ° C. 15 seconds Rinse with water (3) 40 ° C. 15 seconds Stable 40 ° C 15 seconds Drying 80 ° C 30 seconds

Liquid composition (color developing solution) Tank solution (g) Diethylenetriaminepentaacetic acid 4.0 1-hydroxyethylidene-1,1-diphosphonic acid 3.0 Sodium sulfite 4.0 Potassium carbonate 50.0 Potassium bromide 4.0 Potassium iodide 1.3 mg Hydroxylamine sulfate 4.0 Color developing agent (D-13 / naphthalene-1,5-disulfonate) 22.2 Add water and 1.0 liter pH (prepared with potassium hydroxide and sulfuric acid) 10.05 (Bleaching and fixing solution) (Unit mol) Formula A 0.17 Ferric nitrate nonahydrate 0.15 Ammonium thiosulfate 1.25 Ammonium sulfite 0.10 Metacarboxybenzenesulfinic acid 0.05 Add water 1.0 liter pH (prepared with acetic acid and ammonia) 5.8 (Wash water) Tap water Strongly acidic cation exchange resin (Amberlite IR-120B manufactured by Rohm and Haas)
And OH type anion exchange resin (Amberlite IR-
400) to treat the calcium and magnesium ion concentrations to 3 mg / L or less, followed by 20 mg of sodium diisocyanurate dichloride.
/ L and water treated by adding 0.15 g / L of sodium sulfate were used. The pH of this solution is 6.5-
It was in the range of 7.5. (Stabilizing solution) Tank solution (g) 1,2-benzisothiazolin-3-one 0.1 polyoxyethylene-p-monononylphenyl ether (average degree of polymerization 10) 0.2 Add water and add 1.0 liter pH [Ammonia water, hydrochloric acid Adjustment) 8.50

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Embodiment 6 After exposing the sample 101 in the embodiment 4, the process number 211 was used.
The same processing was carried out using D-5 and D-21 as color developing agents in a color developing solution, and the image fastness of a sample provided with a magenta density of 2.0 was examined. Was good.

Example 7 The sample 301 of Example 3 described in JP-A-5-188550 was prepared by using the color developing agent (D) of the present invention in an equimolar amount of the color developing agent in the color developing solution described in the same publication. -2), (D-
13), (D-24) and (D-31) were prepared, except that the same processing solution was prepared, exposed and developed, so that the development time could be reduced, the fog density was low, and the magenta density and The difference between the yellow density and the cyan density was small, and the graininess was favorable.

[0179]

When the compound of the present invention is used as a color developing agent for a silver halide photographic light-sensitive material, an image having rapid processing suitability and good graininess can be obtained.

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Synthesis of Compound (2) 500 g of m-toluidine and iodine in a three-necked flask.
Then, while heating and stirring at 200 ° C. at an external temperature, 1332 ml of acetone was added dropwise thereto over 8 hours and 30 minutes.
Low boiling components such as water generated from the reaction system were distilled off by setting a cooling device in the branch pipe. After completion of the dropwise addition, the obtained reaction mixture was distilled to obtain 701 g of the desired compound (2) (yield: 80%).
%). Boiling point: 165 to 170 ° C / 18 to 20 mmHg ・ Synthesis of compound (3) 290 g of compound (3) and 900 ml of N, N-dimethylacetamide are placed in a three-necked flask, and 162 ml of acetic anhydride is added at an external temperature of 50 ° C for 20 minutes. It dripped over. Thereafter, the mixture was heated and stirred at an external temperature of 150 ° C. for 2 hours, allowed to cool to room temperature, poured into ice water, and extracted with 1.5 liter of ethyl acetate. The obtained ethyl acetate layer was washed with a saturated saline solution (100 m).
After washing four times with a mixed solution consisting of l and 1 liter of water,
It was dried over anhydrous sodium sulfate. The ethyl acetate layer thus obtained was concentrated by a rotary evaporator, and the obtained residue was purified by silica gel column chromatography to obtain 267 g of the desired compound (3) (yield: 75%).
I got・ Synthesis of compound (4) 276 g of compound (3) and 900 ml of methylene chloride were placed in a three-necked flask, and stirred under ice-cooling.
235 g of bromosuccinimide were added over 1 hour. At this time, the internal temperature rose to a maximum of 12 ° C. After completion of the addition, the mixture was further stirred under ice cooling for 30 minutes, and then the ice bath was removed, followed by stirring for 1 hour. One liter of water was added thereto for extraction, and the obtained methylene chloride layer was extracted with 100 ml of saturated saline and 500 m of water.
Washed three times with 1 of the mixed solution. The methylene chloride layer thus obtained was dried over anhydrous sodium sulfate and then concentrated on a rotary evaporator. 250 ml of acetonitrile was added to the obtained residue to dissolve the residue. 265 g of the desired compound (4)
(72% yield). -Synthesis of compound (5) 555 g of tetraethylene glycol was placed in a three-necked flask.
500 ml of tetrahydrofuran was added, and 44.1 g of potassium-t-butoxide was added thereto while stirring at room temperature, followed by stirring for 30 minutes. At this time, the temperature rose to a maximum of 40 ° C. Next, 110 g of compound (4) was added thereto under ice cooling.
Was added dropwise over 30 minutes, and the ice bath was removed, followed by stirring at room temperature for 8 hours. The solvent was distilled off under reduced pressure using an aspirator, and 1 liter of ethyl acetate and 1 liter of water were added for extraction. The obtained ethyl acetate layer was mixed with a mixed solution of 100 ml of a saturated saline solution and 900 ml of water. And washed 4 times. The ethyl acetate layer thus obtained was dried over anhydrous sodium sulfate and concentrated on a rotary evaporator, and the obtained residue was purified by silica gel column chromatography to obtain 90 g of the desired compound (5)
(60% yield). -Synthesis of compound (6) 84.2 g of compound (5), 4 g of Pd-C (10%), and 180 ml of ethanol were placed in an autoclave, and hydrogen pressure was set to 1
The pressure was adjusted to 00 atm, and the mixture was stirred at 50 ° C for 8 hours. The filtrate obtained by suction filtration was concentrated with a rotary evaporator to obtain 85 g of the desired compound (6) as a residue. This was used in the next step without purification. -Synthesis of compound (7) 42.3 g of the compound (6) obtained above, 16.6 ml of concentrated hydrochloric acid and 120 ml of ethanol were placed in a three-necked flask, and 5.6 ml of sulfuric acid was added thereto while stirring under heating and reflux conditions. After dropwise addition and stirring for 1 hour while heating under reflux, 5.6 ml of sulfuric acid was further added dropwise and stirring under heating and reflux was continued for 5 hours.
After distilling off low-boiling components mainly composed of ethanol using an aspirator at an internal temperature of 50 ° C. or lower, the mixture was poured into ice and neutralized with sodium hydrogen carbonate. To this, 500 ml of ethyl acetate and 200 ml of water were added for extraction, and the obtained ethyl acetate layer was washed with 500 ml of saturated saline and 300 ml of water.
After washing three times with 1 liter of the mixed solution, drying over anhydrous sodium sulfate and concentrating with a rotary evaporator, 35 g of the target compound (7) was obtained as a residue. This was used in the next step without purification. -Synthesis of compound (8) 35 g of the compound (7) obtained above in a three-necked flask, 8.2 g of sodium iodide, 23.2 g of sodium hydrogen carbonate,
80 ml of N, N-dimethylacetamide was added, and 10.4 g of 3-chloropropanol was added dropwise thereto over 10 minutes while stirring at an external temperature of 130 ° C. while heating. After completion of the dropwise addition, the mixture was heated and stirred for 3 hours, and then cooled to room temperature. 400 ml of ethyl acetate and 400 ml of water were added thereto, followed by stirring and extraction. The obtained ethyl acetate layer was washed with a mixed solution of 300 ml of water and 100 ml of saturated saline solution.
Washed twice and dried over anhydrous sodium sulfate. The residue was concentrated by a rotary evaporator, and the residue was purified by silica gel column chromatography to obtain 32.9 g of the desired compound (8) (yield: 82%). -Synthesis of compound (9) 2,5-dichloroaniline 20.1 in a three-necked flask
g, 115 ml of water and 39.7 ml of sulfuric acid were added thereto while stirring under ice cooling. Further, a solution prepared by dissolving 9.5 g of sodium nitrite in 25 ml of water was added dropwise thereto over 10 minutes while maintaining the internal temperature at 8 ° C. or lower.
Stirring was continued for 0 minutes. Compound (8) in another three-necked flask
32 g, sodium acetate 71.2 g, acetic acid 49.4 m
l, 90 ml of methanol was added, and the solution of the diazonium salt prepared above was added while stirring under ice-cooling while maintaining the internal temperature at 16 ° C or lower. Follow the reaction by TLC on the way,
When the compound (8) disappeared in the reaction system, the addition of the diazonium salt solution was terminated. 30 after addition
After continued stirring for a minute, methanol was distilled off under reduced pressure, the reaction mixture was poured into ice, neutralized by adding a sodium hydroxide solution, and extracted by adding 1 liter of ethyl acetate and 500 ml of water. The obtained ethyl acetate layer was washed four times with a mixture of 400 ml of water and 100 ml of saturated saline, and dried over anhydrous sodium sulfate. This was concentrated by a rotary evaporator, and the obtained residue was purified by silica gel column chromatography to obtain the desired compound (9) 3
3.4 g were obtained (yield 75%). -Synthesis of exemplary compound (D-16) Compound (9) 26.0 g, palladium-carbon (10%)
1.3 g and methanol (150 ml) were put in an autoclave and stirred at a hydrogen pressure of 100 atm at room temperature for 5 hours. Naphthalene-1,5-disulfonic acid is added to the obtained reaction mixture.
A solution prepared by dissolving 15.1 g of tetrahydrate in 35 ml of methanol was added thereto, followed by filtration. The obtained filtrate was concentrated on a rotary evaporator, and then 200 ml of ethyl acetate and 200 ml of water were added.
After adding 00 ml and stirring to dissolve and separate, the obtained aqueous layer was further washed three times with 200 ml of ethyl acetate. The aqueous layer thus obtained was concentrated using a rotary evaporator, and then the solvent was distilled off using a vacuum pump to obtain 28.0 g of the desired exemplary compound (D-16) (yield 90%).

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Claims (3)

[Claims] 1. An aniline compound represented by the following general formula (I). General formula (I) In the formula, R ¹ represents an alkyl group, an aryl group or a heterocyclic group, and R ² represents a substituent. R ³ represents a hydrogen atom or a substituent; Z represents an ethylene group or a trimethylene group; and L represents a divalent group or a single bond bonded to a carbon atom on the ethylene chain or trimethylene chain of Z. n represents an integer of 1 to 8, and m represents an integer of 0 to 3. When m is 2 or more, R ² may be the same or different. 2. A color photographic processing composition comprising at least one compound represented by the general formula (I) according to claim 1. 3. A color developing method comprising developing an image-exposed silver halide color photographic light-sensitive material in the presence of at least one of the compounds represented by formula (I) according to claim 1. Image forming method.