JP2006259497A - Processing method for photosensitive material - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a processing method for a silver halide photographic sensitive material by which white background fouling is not caused even if processing time is shortened and which ensures no increase of stain over time even under a light source of high illuminance. <P>SOLUTION: In the processing method for a photosensitive material, a processing solution with which the photosensitive material comes into contact at the last of processing steps contains a compound represented by formula (I) and has an absorbance at 440 nm of 0.05-0.5. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a method for processing a light-sensitive material, and more particularly to a method for processing a silver halide photographic light-sensitive material that does not contaminate a white background even when the processing time is shortened and does not increase the stain over time even under a high illuminance light source.

  In general, a method of forming a dye image by processing a photosensitive material (hereinafter also referred to as photosensitive material, color paper or color negative film) is subjected to color development with a color developer after imagewise exposure, and then photosensitive. Rinse or dye is stabilized through a desilvering process including a bleaching process that oxidizes silver particles contained in the material into silver ions and a fixing process that dissolves and removes silver ions generated by the oxidation from the photosensitive material. For the stabilization process. In the processing of color paper, from the viewpoint of speeding up, the bleaching process and the fixing process are processed in the same bath as the bleach-fixing process.

  By the way, in the development process of photosensitive materials, so-called minilabs that are installed at the photo shop and processed photosensitive materials for quick service to general users and rationalization of collection and delivery between photo shops and large-scale developers. An automatic developing processor referred to as "" is widely used. In these automatic development processors for minilabs, development is performed within the day when a request for development is received, and a photograph is provided to the user. In recent years, a rapid processing service for completing development processing in several tens of minutes from reception has been performed, and the demand for the development of rapid processing technology has increased.

  On the other hand, in recent years, low replenishment processing has been actively carried out to reduce the replenishment amount of processing liquids in order to reduce the cost of development processing agents or to reduce the amount of waste liquids that are expensive to collect and process and to reduce pollution. ing. However, if the processing time is significantly increased and the processing is performed with a low replenishment, a problem occurs in the photographic performance. In particular, if the processing time of the rinsing or stabilizing process is shortened and the amount of replenishment is reduced, there is a problem that sensitizing dyes to be washed away usually remain in the light-sensitive material and stain occurs on the white background. As techniques for solving this, Patent Documents 1 and 2 propose adding a compound having a triazine skeleton to the treatment liquid. As a result of repeated studies by the present inventors, it has been found that the use of these compounds in a stabilization or rinse bath has the highest effect of reducing sensitizing dye contamination. However, when the processed photosensitive material is exposed to a light source with high illuminance for a long time, there has been a problem that yellow stain in a white background portion increases.

In the present situation where rapid processing or low replenishment processing is progressing, these white background contamination and aging stain have not been solved at the same time, and development of an immediate improvement method is required.
JP 2001-174957 A JP 2002-139822 A

  The present invention has been made in view of the above circumstances, and an object of the present invention is to provide a silver halide photograph in which there is no white background contamination even when the processing time is shortened, and there is no increase in the stain over time even under a high illuminance light source. An object of the present invention is to provide a method for processing a photosensitive material.

  The above object of the present invention is achieved by the following configurations.

(Claim 1)
In the method for processing a photosensitive material, the processing solution in contact with the photosensitive material at the end of the processing step contains a compound represented by the following general formula (I), and the absorbance at 440 nm of the processing solution is 0.05 to A processing method of a photosensitive material, characterized in that it is 0.5.

(In the formula, A ₁ and A ₂ each independently represent a hydrogen atom, a halogen atom, an aryl group, a heterocyclic group or an alkyl group, and Y represents a hydrogen atom, a thiol group, a halogen atom, a carboxyl group, a sulfo group, a hydroxylamino group. A group, —NR ₁ R ₂ , —SR ₃ or —OR ₃ ; W ₁ represents a single bond, —O—, —S— or —NR ₄ —, and W ₂ represents —O—, —S—. Or represents —NR ₄ —, wherein R ₁ , R ₂ , R ₃ and R ₄ each represents a hydrogen atom, an alkyl group, an alkenyl group, an aryl group or a heterocyclic group, R ₁ and R ₂ , R ₄ and A ₁ And R ₄ and A ₂ may be bonded to each other to form a ring, provided that the molecule represented by the general formula (I) does not have an azo group or a diaminostilbene structure. .)
(Claim 2)
2. The processing of a photosensitive material according to claim 1, wherein the concentration of the compound represented by the general formula (I) is 5 × 10 ⁻⁵ to 1 × 10 ⁻² mol per liter of the processing solution. Method.

(Claim 3)
3. The method for processing a photosensitive material according to claim 1, wherein the processing solution contains an iron salt.

(Claim 4)
4. The method for processing a photosensitive material according to claim 1, wherein the processing solution has a pH of 4 to 9.

(Claim 5)
5. The photosensitive material according to claim 1, wherein the compound represented by the general formula (I) is a compound represented by the following general formula (II) or (III). Processing method.

Wherein X ₁ , X ₂ , Y ₁ and Y ₂ are each independently —N (R ₁ ) R ₂ , —OR ₃ , —SR ₃ , a heterocyclic group, a hydroxyl group, a hydroxylamino group or a halogen atom. Z ₁ and Z ₂ each represent —NR ₄ —, —O— or —S—, L represents an arylene group, an alkylene group, an alkenylene group or a heterocyclic group, and R ₁ and R ₂ each represent hydrogen. Represents an atom, an alkyl group, an aryl group or a heterocyclic group, R ₃ represents an alkyl group, an aryl group or a heterocyclic group, and R ₄ represents a hydrogen atom, an aryl group, a heterocyclic group or an alkyl group, R ₁ and R ₂ may be bonded to form a nitrogen-containing heterocycle, provided that the molecule represented by the general formula (II) does not have an azo group or a diaminostilbene structure.

(In the formula, L ₁₂ and L ₁₃ may be the same or different and each represents an aryl group or a heterocyclic group; Q represents a hydrogen atom, a thiol group, a carboxyl group, a sulfo group, —NR ₅ R ₆ , —OR; ₇ represents a hydroxylamino group or a halogen atom, and R ₅ , R ₆ and R ₇ each represents a hydrogen atom, an alkyl group, an aryl group or a hetero group, and R ₅ and R ₆ are bonded to each other to form a ring. However, the molecule represented by the above general formula (III) contains at least one group represented by —SO ₃ M, —CO ₂ M or —OH, where M is hydrogen. Represents an atom, an alkali metal, an alkaline earth metal, ammonium or pyridinium, and does not have an azo group or a diaminostilbene structure in the molecule represented by the general formula (III).
(Claim 6)
6. The method for processing a photosensitive material according to claim 5, wherein the compound represented by the general formula (II) is a compound represented by the following general formulas (II-1) to (II-4): .

(In the formula, R _{11 to} R ₁₈ each independently represents a hydrogen atom, an alkyl group, an aryl group, or a heterocyclic group. L ₁ represents a phenylene group or a naphthylene group. Among R _{11 to} R ₁₈ , three or more. R ₁₁ and R ₁₂ , R ₁₃ and R ₁₄ , R ₁₅ and R ₁₆ , R ₁₇ and R ₁₈ may be bonded to each other to form a ring, provided that the general formula (II included in the molecule represented by _{-1), -SO 3 M, -CO} 2 M, based on containing at least one represented by -OH. here, M is an alkali metal ion, an alkaline earth metal ion (In addition, the compound represented by the general formula (II-1) does not contain a group represented by —N═N— or a diaminostilbene structure in the molecule.)

(In the formula, R _{21 to} R ₂₈ each independently represents a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group. L ₂ represents a phenylene group, a naphthylene group, an alkylene group or a heterocyclic group. Ra represents an alkyl group. Represents an aryl group or a heterocyclic group, and Rb represents a hydrogen atom, an alkyl group or an aryl group, R ₂₁ and R ₂₂ , R ₂₃ and R ₂₄ , R ₂₅ and R ₂₆ , R ₂₇ and R ₂₈ are bonded to each other. However, the compound represented by the general formula (II-2) contains at least one group represented by —SO ₃ M, —CO ₂ M, —OH in the molecule. Here, M represents an alkali metal ion, an alkaline earth metal ion or an ammonium ion, and the compound represented by the general formula (II-2) has a —N═N— or diaminostilbene structure in the molecule. Does not contain.)

(In the formula, R _{31 to} R ₃₄ each independently represents a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group. L ₃ represents a phenylene group, a naphthylene group, an alkylene group or a heterocyclic group. A ₃₁ , A ₃₂ each independently represents an alkoxy group, an aryloxy group, a heterocyclic oxy group, an alkylthio group, an arylthio group, a heterocyclic thio group or a hydroxylamino group, R ₃₅ and R ₃₆ each independently represent a hydrogen atom, an alkyl group, R ₃₁ and R ₃₂ , R ₃₃ and R ₃₄ may combine with each other to form a ring, provided that the compound represented by formula (II-3) is a molecule -SO ₃ M, -CO ₂ M, containing at least one group represented by -OH within. here, M represents an alkali metal ion, an alkaline earth metal ion or an ammonium ion. Luo, a compound represented by Formula (II-3) does not contain a group represented by -N = N-in a molecule.)

(Wherein L ₄ represents a phenylene group, a naphthylene group or an alkylene group. X ₁ represents an oxygen atom or a sulfur atom, X ₂ represents an oxygen atom, a sulfur atom or —NH—. A ₄₁ , A ₄₂ , A ₄₃ and A ₄₄ are each independently an alkoxy group, aryloxy group, heterocyclic oxy group, alkylthio group, arylthio group, heterocyclic thio group, hydroxylamino group, or —NR ₄₁ R ₄₂ (R ₄₁ and R ₄₂ are each independently Represents a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group, and R ₄₁ and R ₄₂ may be bonded to each other to form a ring), but represented by the general formula (II-4) _{compounds, -SO 3 M, -CO 2 M} , containing at least one of the groups represented by -OH in the molecule. here, M represents an alkali metal ion, an alkaline earth metal ion or an ammonium ion Further, the compound represented by Formula (II-4), does not contain a group or a diaminostilbene structure represented by -N = N-in a molecule.)

  According to the present invention, it is possible to provide a method for processing a silver halide photographic light-sensitive material which does not cause white background contamination even when the processing time is shortened and does not increase the aging stain even under a high illuminance light source.

  As a result of diligent research, the present inventor has found that in the processing method of a photosensitive material, the processing liquid in contact with the photosensitive material at the end of the processing step contains the compound represented by the general formula (I), and the processing liquid Silver halide photography with a light-sensitive material processing method having a light absorbance at 440 nm of 0.05 to 0.5, with no white background contamination even when the processing time is shortened and no increase in stain over time even under a high illuminance light source It has been found that a method for processing a photosensitive material can be obtained.

  The present invention will be described in detail below.

  In the present invention, the processing solution in contact with the photosensitive material at the end of the processing step contains the compound represented by the general formula (I), and the absorbance at 440 nm of the processing solution is 0.05 to 0.5. It is a feature.

  The processing method for processing a light-sensitive material according to the present invention preferably comprises at least a color development step, a bleach-fixing step, and a stabilization step (or a rinse step). In the present invention, the light-sensitive material is a processing step. The treatment liquid that comes into contact with the liquid lastly is preferably a stabilization liquid used in the stabilization step. When the stabilization process has a plurality of stabilization treatment tanks, it refers to the stabilization liquid of the final stabilization treatment tank.

[Compound represented by formula (I)]
In the processing method (hereinafter also simply referred to as processing method) of the photosensitive material of the present invention, the processing solution that comes into contact with the photosensitive material at the end of the processing step contains the compound represented by the general formula (I).

In the general formula (I), A ₁ and A ₂ each independently represent a hydrogen atom, a halogen atom, an aryl group, a heterocyclic group or an alkyl group, and Y represents a hydrogen atom, a thiol group, a halogen atom, a carboxyl group, a sulfo group. Group, a hydroxylamino group, —NR ₁ R ₂ , —SR ₃ or —OR ₃ , W ₁ represents a single bond, —O—, —S— or —NR ₄ —, and W ₂ represents —O—. , -S- or -NR ₄ - represents a. R ₁ , R ₂ , R ₃ and R ₄ each represent a hydrogen atom, an alkyl group, an alkenyl group, an aryl group or a heterocyclic group. R ₁ and R ₂ , R ₄ and A ₁ , and R ₄ and A ₂ may be bonded to each other to form a ring. However, the molecule represented by the general formula (I) does not have an azo group or a diaminostilbene structure.

  The compound represented by formula (I) according to the present invention will be described in more detail.

A ₁ and A ₂ each independently represent a hydrogen atom, a halogen atom, an aryl group, a heterocyclic group or an alkyl group, and the aryl group, heterocyclic group or alkyl group includes those having a substituent.

When A ₁ and A ₂ are each an aryl group, the carbon number thereof is preferably 6 to 20, more preferably 6 to 15, particularly preferably 6 to 10, and examples thereof include a phenyl group, a 4-methoxyphenyl group, 4-toluyl group, naphthyl group, 3-carboxyphenyl group, 4-carboxyphenyl group, 2-sulfophenyl group, 4-sulfophenyl group, 2-methyl-4-sulfophenyl group, 2,5-disulfophenyl group 4-sulfo-1-naphthyl group, 6,8-disulfo-2-naphthyl group, and 5,7-disulfo-2-naphthyl group.

When A ₁ and A ₂ are each a heterocyclic group, the carbon number thereof is preferably 2 to 20, more preferably 2 to 10 carbon atoms, particularly preferably 3 to 8 carbon atoms, most preferably 5 carbon atoms. Or a monovalent group obtained by removing one hydrogen atom from a 6-membered aromatic or non-aromatic heterocyclic compound, for example, 2-furyl group, 2-thienyl group, 2-pyrimidinyl group, 2-benzothiazolyl Groups.

When A ₁ and A ₂ are each an alkyl group, the number of carbon atoms is preferably 1-20, more preferably 1-8, particularly preferably 1-4, and examples thereof include a methyl group, an ethyl group, and isopropyl. Group, 2-methoxyethyl group, sulfomethyl group, 2-sulfoethyl group, 1,2-dicarboxyethyl, 2-hydroxyethyl group, 3-hydroxypropyl group, 2-hydroxypropyl group, 2,3-dihydroxypropyl group, Examples include 3,4-dihydroxybutyl group, 2- (2-hydroxyethoxy) ethyl group, and 2- [2- (2-hydroxyethoxy) ethoxy] ethyl group.

R _{1 to} R ₄ represent a hydrogen atom, an aryl group, an alkenyl group, a heterocyclic group or an alkyl group, and these groups include those having a substituent.

When R ₁ to R ₄ is an alkyl or alkenyl group preferably has 1 to 20 carbon atoms, more preferably 1-8, particularly preferably 1-4 alkyl groups, for example, a methyl group, an ethyl group, i-propyl group, n-propyl group, n-octyl group, vinyl group, sulfomethyl group, 2-hydroxyethyl group, 3-hydroxypropyl group, 2-hydroxypropyl group, 2-sulfoethyl group, 2-methoxyethyl group, 2- (2-hydroxyethoxy) ethyl group, 2- [2- (2-hydroxyethoxy) ethoxy] ethyl group, 2- (2- [2- (2-hydroxyethoxy) ethoxy] ethoxy) ethyl group, 2, 3-dihydroxypropyl group, 3,4-dihydroxybutyl group, 2,3,4,5,6-pentahydroxyhexyl group, 1,2-dicarboxyethyl group It is below.

The aryl group represented by R _{1 to} R ₄ is preferably an aryl group having 6 to 20 carbon atoms, more preferably an aryl group having 6 to 10, particularly preferably 6 to 8, and examples thereof include a phenyl group and a naphthyl group. , 3-carboxyphenyl group, 4-carboxyphenyl group, 3,5-dicarboxyphenyl group, 4-methoxyphenyl group, 2-sulfophenyl group, 4-sulfophenyl group.

The heterocyclic group represented by R _{1 to} R ₄ preferably has 2 to 20 carbon atoms, more preferably 2 to 10 carbon atoms, particularly preferably 3 to 8 carbon atoms, and most preferably A monovalent group obtained by removing one hydrogen atom from a 5- or 6-membered aromatic or non-aromatic heterocyclic compound, such as a 2-furyl group, a 2-thienyl group, a 2-pyrimidinyl group, 2- A benzothiazolyl group may be mentioned.

R _{1 to} R ₄ are preferably a hydrogen atom, a methyl group, an ethyl group, an n-propyl group, a sulfomethyl group, a 2-hydroxyethyl group, a 3-hydroxypropyl group, a 2-hydroxypropyl group, a 2-sulfoethyl group, 2 -Methoxyethyl group, 2- (2-hydroxyethoxy) ethyl group, 2- [2- (2-hydroxyethoxy) ethoxy] ethyl group, 2,3-dihydroxypropyl group, 3,4-dihydroxybutyl group, phenyl group , 3-carboxyphenyl group, 4-carboxyphenyl group, 3,5-dicarboxyphenyl group, 4-methoxyphenyl group, 2-sulfophenyl group, 4-sulfophenyl group, more preferably hydrogen atom, methyl group , Ethyl group, sulfomethyl group, 2-hydroxyethyl group, 2-sulfoethyl group, 2- (2-hydroxyeth E) ethyl group, 2,3-dihydroxypropyl group, phenyl group, 3-carboxyphenyl group, 4-carboxyphenyl group, 2-sulfophenyl group, 4-sulfophenyl group, particularly preferably a hydrogen atom or a methyl group , Sulfomethyl group, 2-hydroxyethyl group, 2-sulfoethyl group, 2- (2-hydroxyethoxy) ethyl group, 2,3-dihydroxypropyl group, phenyl group, 4-sulfophenyl group.

Y represents a hydrogen atom, a thiol group, a halogen atom, a carboxyl group, a sulfo group, a hydroxylamino group, —NR ₁ R ₂ , —SR ₃ or —OR ₃ , and R ₁ , R ₂ and R ₃ are each a hydrogen atom, It represents an alkyl group, an aryl group or a heterocyclic group, and R ₁ , R ₂ and R ₃ each include those having a substituent, and preferred examples are the same as those for the respective groups represented by R ₄ .

The ring formed by combining R ₁ and R ₂ , R ₄ and A ₁ and R ₄ and A ₂ with each other is preferably a 5-membered ring or a 6-membered ring, such as a pyrrolidine ring, piperidine ring, Examples include piperazine ring and morpholine ring.

  The compound represented by the general formula (I) preferably has a water-soluble group in the molecule, and examples of the water-soluble group include a sulfo group, a carboxyl group, a hydroxyl group, a carbamoyl group, and a sulfamoyl group. A sulfo group, a carboxyl group and a hydroxyl group are particularly preferred. In the case of having a carboxyl group or a sulfo group, these may be free forms or salts, and the salt in the case of a salt is preferably an alkali metal, alkaline earth metal, ammonium or pyridinium, of which alkali metal or alkaline earth metal is more preferred. Na and K are preferred and particularly preferred. Examples of the ammonium group include ammonium, triethylammonium, and tetrabutylammonium, among which ammonium is preferable.

When W ₁ and W ₂ are both —O—, or when one is —O— and the other is —NR ₄ —, A ₁ and A ₂ are each an alkyl group, an aryl group or a heterocyclic group. And at least one is more preferably an aryl group or a heterocyclic group.

When both W ₁ and W ₂ are —NR ₄ —, it is preferable that the number of aryl groups is 2 or less among R ₁ , R ₂ , R ₃ , and two R ₄ , A ₁ , A ₂ .

  Among the compounds represented by the general formula (I) according to the present invention, particularly preferable compounds are the compounds represented by the general formula (II) or the general formula (III).

[Compound represented by formula (II)]
In the general formula (II), X ₁ , X ₂ , Y ₁ and Y ₂ are each independently —N (R ₁ ) R ₂ , —OR ₃ , —SR ₃ , heterocyclic group, hydroxyl group, hydroxylamino Represents a group or a halogen atom, Z ₁ and Z ₂ each represent —NR ₄ —, —O— or —S—, L represents an arylene group, an alkylene group, an alkenylene group or a heterocyclic group, and R ₁ and R ₂ represents a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group, R ₃ represents an alkyl group, an aryl group or a heterocyclic group, and R ₄ represents a hydrogen atom, an aryl group, a heterocyclic group or an alkyl group. . R ₁ and R ₂ may combine to form a nitrogen-containing heterocycle. However, the molecule represented by the general formula (II) does not have an azo group or a diaminostilbene structure.

  The compound represented by formula (II) will be described in more detail.

The alkyl group represented by R ₁ , R ₂ , R ₃ or R ₄ includes those having a substituent, preferably those having 1 to 20 carbon atoms, more preferably 1 to 8, particularly preferably 1 to 4. For example, methyl group, ethyl group, i-propyl group, n-propyl group, n-octyl group, sulfomethyl group, 2-hydroxyethyl group, 3-hydroxypropyl group, 2-hydroxypropyl group, 2 -Sulfoethyl group, 2-methoxyethyl group, 2- (2-hydroxyethoxy) ethyl group, 2- [2- (2-hydroxyethoxy) ethoxy] ethyl group, 2- (2- [2- (2-hydroxyethoxy) ) Ethoxy] ethoxy) ethyl group, 2,3-dihydroxypropyl group, 3,4-dihydroxybutyl group, 2,3,4,5,6-pentahydroxyhexyl group.

The aryl group represented by R ₁ , R ₂ , R ₃ or R ₄ includes those having a substituent, preferably those having 6 to 20 carbon atoms, more preferably 6 to 10 and particularly preferably 6 to 8. For example, phenyl group, naphthyl group, 3-carboxyphenyl group, 4-carboxyphenyl group, 3,5-dicarboxyphenyl group, 4-methoxyphenyl group, 2-sulfophenyl group, 4-sulfophenyl group 2,4-disulfophenyl group.

The heterocyclic group represented by R ₁ , R ₂ , R ₃ or R ₄ includes those having a substituent, preferably those having 2 to 20 carbon atoms, more preferably those having 2 to 10 carbon atoms, particularly preferably carbon. A compound in which one hydrogen atom is removed from a 5- or 6-membered aromatic or non-aromatic heterocyclic compound of 3 to 8, for example, a 2-furyl group, a 2-thienyl group, a 2-pyrimidinyl group, A 2-benzothiazolyl group may be mentioned.

R ₁ and R ₂ are preferably a hydrogen atom, an alkyl group and an aryl group, more preferably a hydrogen atom, a methyl group, an ethyl group, an n-propyl group, a sulfomethyl group, a 2-hydroxyethyl group, and a 3-hydroxypropyl group. Group, 2-hydroxypropyl group, 2-sulfoethyl group, 2-methoxyethyl group, 2- (2-hydroxyethoxy) ethyl group, 2- [2- (2-hydroxyethoxy) ethoxy] ethyl group, 2,3- Dihydroxypropyl group, 3,4-dihydroxybutyl group, phenyl group, 3-carboxyphenyl group, 4-carboxyphenyl group, 3,5-dicarboxyphenyl group, 4-methoxyphenyl group, 2-sulfophenyl group, 4- A sulfophenyl group, more preferably a hydrogen atom, a methyl group, an ethyl group, a sulfomethyl group, 2-hydroxy Ethyl group, 2-sulfoethyl group, 2- (2-hydroxyethoxy) ethyl group, 2,3-dihydroxypropyl group, phenyl group, 3-carboxyphenyl group, 4-carboxyphenyl group, 2-sulfophenyl group, 4- A sulfophenyl group, more preferably a hydrogen atom, methyl group, sulfomethyl group, 2-hydroxyethyl group, 2-sulfoethyl group, 2- (2-hydroxyethoxy) ethyl group, 2,3-dihydroxypropyl group, phenyl group; 4-sulfophenyl group.

The nitrogen-containing heterocycle formed by combining R ₁ and R ₂ is preferably a 5-membered ring or a 6-membered ring. Examples of the ring include pyrrolidine ring, piperidine ring, piperazine ring and morpholine ring.

The alkyl group represented by R ₄ includes those having a substituent, preferably an alkyl group having 1 to 6 carbon atoms, and examples thereof include a methyl group, an ethyl group, an i-propyl group, and an n-propyl group.

When X ₁ , X ₂ , Y ₁ or Y ₂ is a heterocyclic group, including those having a substituent, preferably bonded to a nitrogen atom from a 5- or 6-membered aromatic or non-aromatic nitrogen-containing heterocyclic compound A monovalent 5-membered or 6-membered ring group from which one hydrogen atom has been removed. Examples of the ring include a pyrrolidine ring, a piperidine ring, a piperazine ring, and a morpholine ring.

When X ₁ , X ₂ , Y ₁ and Y ₂ are all —N (R ₁ ) R ₂ , it is preferable that the number of aryl groups is 4 or less among the four R ₁ and the four R ₂ .

  The arylene group represented by L includes those having a substituent, preferably a phenylene group or a naphthylene group, preferably those having 6 to 20 carbon atoms, more preferably 6 to 15 and particularly preferably 6 to 11 phenylene groups or A naphthylene group, for example, 1,4-phenylene, 1,3-phenylene, 1,2-phenylene, 1,5-naphthylene, 1,8-naphthylene, 4-carboxy-1,2-phenylene, 5-carboxy -1,3-phenylene, 3-sulfo-1,4-phenylene, 5-sulfo-1,3-phenylene, 2,5-dimethoxy 1,4-phenylene, 2,6-dichloro-1,4-phenylene It is done. Among these, 1,4-phenylene, 1,3-phenylene, 1,2-phenylene, 1,5-naphthylene, 5-carboxy-1,3-phenylene, and 5-sulfo-1,3-phenylene are preferable. More preferred are 1,4-phenylene and 1,3-phenylene. The heterocyclic group represented by L includes those having a substituent, preferably 2 to 20 carbon atoms, more preferably 2 to 10 carbon atoms, still more preferably 2 to 8 carbon atoms. 1,2,4-triazole) -diyl group, 3,5-isothiazole diyl group, 2,6-pyridinediyl group, 2,6-pyrazinediyl group, 2,6-pyrimidinediyl group, 3,6-pyridazinediyl Group, and 1,4-phthalazinediyl group.

  The alkylene group and alkenylene group represented by L include those having a substituent, and those having 1 to 10 carbon atoms are preferred, and 2 to 5 are more preferred. For example, ethylene, triethylene, propylene, vinylene, propylene, etc. are mentioned.

[Compound represented by formula (III)]
Next, the compound represented by formula (III) according to the present invention will be described.

In the general formula (III), L ₁₂ and L ₁₃ may be the same or different and each represents an aryl group or a heterocyclic group, and Q represents a hydrogen atom, a thiol group, a carboxyl group, a sulfo group, —NR ₅ R ₆ , —OR ₇ , a hydroxylamino group or a halogen atom, and R ₅ , R ₆ and R ₇ each represent a hydrogen atom, an alkyl group, an aryl group or a hetero group. R ₅ and R ₆ may combine with each other to form a ring. However, the molecule represented by the above general formula (III) contains at least one group represented by —SO ₃ M, —CO ₂ M or —OH, where M is a hydrogen atom, an alkali Represents metal, alkaline earth metal, ammonium or pyridinium. The molecule represented by the general formula (III) does not have an azo group or a diaminostilbene structure.

  Hereinafter, the compound represented by formula (III) according to the present invention will be described in detail.

The aryl group represented by L ₁₂ and L ₁₃ includes those having a substituent, preferably those having 6 to 20 carbon atoms, more preferably 6 to 15 and particularly preferably 6 to 11 phenylene group or naphthylene. It is a group. The aryl group preferably has at least one substituent. Preferred substituents include —SO ₃ M, —CO ₂ M, —OH, —Cl, —Br, or —NR ₅ R ₆ , —OR. ₇ is mentioned. Here, M represents a hydrogen atom, an alkali metal, an alkaline earth metal, ammonium or pyridinium, and R ₅ , R ₆ and R ₇ each represents a hydrogen atom, an alkyl group, an aryl group or a hetero group. R ₅ and R ₆ may combine with each other to form a ring.

The heterocyclic group represented by L ₁₂ and L ₁₃ includes those having a substituent, preferably those having 2 to 20 carbon atoms, more preferably 2 to 10 carbon atoms, particularly preferably 3 to 8 carbon atoms. And most preferably a monovalent group obtained by removing one hydrogen atom from a 5- or 6-membered aromatic or non-aromatic heterocyclic compound, for example, furyl group, thienyl group, pyrimidinyl group, benzothiazolyl Group and benzimidazole group.

Preferable examples of the alkyl group, aryl group and heterocyclic group for R _{5 to} R ₇ are the same as those for R _{1 to} R ₃ in formula (I).

  Specific examples of the compounds represented by the general formulas (I) to (III) according to the present invention are given below, but the present invention is not limited to these.

  In the present invention, among the compounds represented by the general formula (II), more preferable compounds are the compounds represented by the general formulas (II-1) to (II-4).

[Compound represented by formula (II-1)]
First, the compound represented by general formula (II-1) is demonstrated.

In the general formula (II-1), R _{11 to} R ₁₈ each independently represents a hydrogen atom, an alkyl group, an aryl group, or a heterocyclic group. L ₁ represents a phenylene group or a naphthylene group. Three or more of R _{11 to} R ₁₈ are aryl groups. R ₁₁ and R ₁₂ , R ₁₃ and R ₁₄ , R ₁₅ and R ₁₆ , R ₁₇ and R ₁₈ may be bonded to each other to form a ring. However, the molecule represented by the general formula (II-1) contains at least one group represented by —SO ₃ M, —CO ₂ M, and —OH. Here, M represents an alkali metal ion, an alkaline earth metal ion, or an ammonium ion. Furthermore, the compound represented by the general formula (II-1) does not contain a group represented by -N = N- or a diaminostilbene structure in the molecule.

  The compound represented by the general formula (II-1) will be described in detail.

R _{11 to} R ₁₈ each independently represent a hydrogen atom, an alkyl group, an aryl group, or a heterocyclic group, including those each having a substituent. The alkyl group represented by R _{11 to} R ₁₈ preferably has 1 to 20 carbon atoms, more preferably 1 to 8, particularly preferably 1 to 4, and examples thereof include a methyl group, an ethyl group, i- Propyl group, n-propyl group, n-octyl group, sulfomethyl group, 2-hydroxyethyl group, 3-hydroxypropyl group, 2-hydroxypropyl group, 2-sulfoethyl group, 2-methoxyethyl group, 2- (2- Hydroxyethoxy) ethyl group, 2- [2- (2-hydroxyethoxy) ethoxy] ethyl group, 2- (2- [2- (2-hydroxyethoxy) ethoxy] ethoxy) ethyl group, 2,3-dihydroxypropyl group 3,4-dihydroxybutyl group and 2,3,4,5,6-pentahydroxyhexyl group.

The aryl group represented by R _{11 to} R ₁₈ preferably has 6 to 20 carbon atoms, more preferably 6 to 10 and particularly preferably 6 to 8 and includes, for example, a phenyl group, a naphthyl group, 3 -Carboxyphenyl group, 4-carboxyphenyl group, 3,5-dicarboxyphenyl group, 4-methoxyphenyl group, 2-sulfophenyl group, 4-sulfophenyl group are mentioned.

The heterocyclic group represented by R ₁₁ to R _18, 2 to 20 carbon atoms, more preferably 2 to 10 carbon atoms, particularly preferably an aromatic or non-5 or 6-membered having 3 to 8 carbon atoms A monovalent group obtained by removing one hydrogen atom from an aromatic heterocyclic compound, and examples thereof include a 2-furyl group, a 2-thienyl group, a 2-pyrimidinyl group, and a 2-benzothiazolyl group.

R _{11 to} R ₁₈ are preferably a hydrogen atom, an alkyl group, and an aryl group, and more preferably a hydrogen atom, a methyl group, an ethyl group, an n-propyl group, a sulfomethyl group, a 2-hydroxyethyl group, and a 3-hydroxypropyl group. Group, 2-hydroxypropyl group, 2-sulfoethyl group, 2-methoxyethyl group, 2- (2-hydroxyethoxy) ethyl group, 2- [2- (2-hydroxyethoxy) ethoxy] ethyl group, 2,3- Dihydroxypropyl group, 3,4-dihydroxybutyl group, phenyl group, 3-carboxyphenyl group, 4-carboxyphenyl group, 3,5-dicarboxyphenyl group, 4-methoxyphenyl group, 2-sulfophenyl group, 4- A sulfophenyl group, more preferably a hydrogen atom, a methyl group, an ethyl group, a sulfomethyl group, 2-hydroxy Ethyl group, 2-sulfoethyl group, 2- (2-hydroxyethoxy) ethyl group, 2,3-dihydroxypropyl group, phenyl group, 3-carboxyphenyl group, 4-carboxyphenyl group, 2-sulfophenyl group, 4- And is more preferably a hydrogen atom, methyl group, sulfomethyl group, 2-hydroxyethyl group, 2-sulfoethyl group, 2- (2-hydroxyethoxy) ethyl group, 2,3-dihydroxypropyl group, phenyl Group, 4-sulfophenyl group.

Three or more of R _{11 to} R ₁₈ are aryl groups.

L ₁ represents a phenylene group or a naphthylene group. The phenylene group or naphthylene group represented by L ₁ preferably has 6 to 20 carbon atoms, more preferably 6 to 15 and particularly preferably 6 to 11 substituted or unsubstituted phenylene group or naphthylene group. 1,4-phenylene, 1,3-phenylene, 1,2-phenylene, 1,5-naphthylene, 1,8-naphthylene, 4-carboxy-1,2-phenylene, 5-carboxy-1,3-phenylene, Examples include 3-sulfo-1,4-phenylene, 5-sulfo-1,3-phenylene, 2,5-dimethoxy 1,4-phenylene, and 2,6-dichloro-1,4-phenylene.

L ₁ is preferably 1,4-phenylene, 1,3-phenylene, 1,2-phenylene, 1,5-naphthylene, 5-carboxy-1,3-phenylene, 5-sulfo-1,3-phenylene. More preferred are 1,4-phenylene and 1,3-phenylene.

R ₁₁ and R ₁₂ , R ₁₃ and R ₁₄ , R ₁₅ and R ₁₆ , R ₁₇ and R ₁₈ may be bonded to each other to form a ring. The ring formed by combining R ₁₁ and R ₁₂ , R ₁₃ and R ₁₄ , R ₁₅ and R ₁₆ , and R ₁₇ and R ₁₈ , including those having a substituent, is a 5-membered or 6-membered ring. Preferably there is. Examples of the ring include a pyrrolidine ring, a piperidine ring, a piperazine ring, and a morpholine ring.

The compound represented by the general formula (II-1) according to the present invention contains at least one group represented by —SO ₃ M, —CO ₂ M, and —OH in the molecule. Here, M represents an alkali metal ion, an alkaline earth metal ion, or an ammonium group. Of the alkali metals and alkaline earth metals represented by M, Na and K are particularly preferable. Examples of the ammonium group include an ammonium group, a triethylammonium group, a tetrabutylammonium group, and a pyridinium group. Most preferred as M is Na and K.

  Furthermore, the compound represented by the general formula (II-1) according to the present invention does not contain —N═N— or a diaminostilbene structure in the molecule.

  Although the specific example of a compound represented by general formula (II-1) based on this invention below is given, this invention is not limited to these.

[Compound represented by formula (II-2)]
Next, the compound represented by formula (II-2) according to the present invention will be described.

In the general formula (II-2), R _{21 to} R ₂₈ each independently represent a hydrogen atom, an alkyl group, an aryl group, or a heterocyclic group. L ₂ represents a phenylene group, a naphthylene group, an alkylene group or a heterocyclic group.

  Ra represents an alkyl group, an aryl group or a heterocyclic group, and Rb represents a hydrogen atom, an alkyl group or an aryl group.

R ₂₁ and R ₂₂ , R ₂₃ and R ₂₄ , R ₂₅ and R ₂₆ , R ₂₇ and R ₂₈ may be bonded to each other to form a ring. However, the compound represented by the general formula (II-2) contains at least one group represented by —SO ₃ M, —CO ₂ M, and —OH in the molecule. Here, M represents an alkali metal ion, an alkaline earth metal ion, or an ammonium ion. Furthermore, the compound represented by the general formula (II-2) does not contain —N═N— or a diaminostilbene structure in the molecule.

  The compound represented by formula (II-2) according to the present invention will be described in more detail.

R _{21 to} R ₂₈ each represent a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group, and include those having a substituent. Specific examples and preferred groups of the alkyl group, aryl group and heterocyclic group represented by R _{21 to} R ₂₈ include the same groups as R _{11 to} R ₁₈ in formula (II-1).

L ₂ represents a phenylene group, a naphthylene group, an alkylene group or a heterocyclic group, and includes those having a substituent. Specific examples and preferred examples of the phenylene group and naphthylene group represented by L ₂ include those similar to the phenylene group and naphthylene group represented by L ₁ in formula (II-1).

The alkylene group represented by L ₂ may be a methylene group at both ends, and may have an oxy group, sulfide group, imino group, sulfonyl group or the like in the main chain.

The heterocycle represented by L ₂ is a linking group having two bonds extending from any substitutable position on the aromatic ring and non-aromatic ring containing a hetero atom. Specific examples of the heterocyclic ring that can be a divalent linking group represented by L ₂ include furan, thiophene, pyrrole, pyridine, pyrimidine, pyridazine, pyrazine, quinoline, isoquinoline, pyrazole, imidazole, triazole, oxazole, isoxazole, Examples include thiazole, benzoxazole, benzimidazole, benzothiazole, indazole, pyrrolidine, piperidine, morpholine, tetrahydropyran, dioxane and the like.

  Ra represents an alkyl group, an aryl group or a heterocyclic group, and includes those having a substituent. Rb represents a hydrogen atom, an alkyl group or an aryl group, and includes those having a substituent.

Specific examples of the alkyl group, aryl group, and heterocyclic group represented by Ra and Rb are the same as the alkyl group, aryl group, and heterocyclic group represented by R _{11 to} R ₁₈ in formula (II-1). Can be mentioned.

R ₂₁ and R ₂₂ , R ₂₃ and R ₂₄ , R ₂₅ and R ₂₆ , R ₂₇ and R ₂₈ may be bonded to each other to form a ring, and include those having a substituent. Examples of the ring formed by combining R ₂₁ and R ₂₂ , R ₂₃ and R ₂₄ , R ₂₅ and R ₂₆ , R ₂₇ and R ₂₈ are R ₁₁ and R ₁₂ , R _{13 in the} general formula (II-1). And R ₁₄ , R ₁₅ and R ₁₆ , and R ₁₇ and R ₁₈ may be the same as the ring formed by bonding to each other.

The compound represented by the general formula (II-2) contains at least one group represented by —SO ₃ M, —CO ₂ M, and —OH in the molecule. Here, M is synonymous with M in General Formula (II-1). Furthermore, the compound represented by the general formula (II-2) does not contain a group represented by —N═N— or a diaminostilbene structure in the molecule.

  Although the specific example of a compound represented by general formula (II-2) based on this invention below is given, this invention is not limited to these.

[Compound represented by formula (II-3)]
Next, the compound represented by formula (II-3) according to the present invention will be described.

In the general formula (II-3), R _{31 to} R ₃₄ each independently represents a hydrogen atom, an alkyl group, an aryl group, or a heterocyclic group. L ₃ represents a phenylene group, a naphthylene group, an alkylene group or a heterocyclic group. A ₃₁ and A ₃₂ each independently represents an alkoxy group, an aryloxy group, a heterocyclic oxy group, an alkylthio group, an arylthio group, a heterocyclic thio group or a hydroxylamino group. R ₃₅ and R ₃₆ each independently represents a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group.

R ₃₁ and R ₃₂ , R ₃₃ and R ₃₄ may be bonded to each other to form a ring. However, the compound represented by the general formula (II-3) contains at least one group represented by —SO ₃ M, —CO ₂ M, and —OH in the molecule. Here, M represents an alkali metal ion, an alkaline earth metal ion, or an ammonium ion. Furthermore, the compound represented by the general formula (II-3) does not contain a group represented by -N = N- or a diaminostilbene structure in the molecule.

  The compound represented by the general formula (II-3) will be described in detail.

In General Formula (II-3), R _{31 to} R ₃₄ each independently represent a hydrogen atom, an alkyl group, an aryl group, or a heterocyclic group, including those having a substituent. L ₃ represents a phenylene group, a naphthylene group, an alkylene group, or a heterocyclic group, and includes those having a substituent. Specific examples and preferred examples of R _{31 to} R ₃₄ can be the same as R _{11 to} R ₁₈ in formula (II-1).

A ₃₁ and A ₃₂ each independently represents an alkoxy group, an aryloxy group, a heterocyclic oxy group, an alkylthio group, an arylthio group, a heterocyclic thio group, or a hydroxyamino group.

Examples of the alkyl group constituting the alkoxy group represented by A ₃₁ and A ₃₂ include the same alkyl groups represented by R _{11 to} R ₁₈ in formula (II-1).

Examples of the aryl group constituting the aryloxy group represented by A ₃₁ and A ₃₂ include the same aryl groups represented by R _{11 to} R ₁₈ in the general formula (II-1).

Examples of the heterocyclic group constituting the heterocyclic oxy group represented by A ₃₁ or A ₃₂ include the same heterocyclic groups as those represented by R _{11 to} R ₁₈ in formula (II-1).

The alkylthio group, arylthio group, and alkyl group, aryl group and heterocyclic group constituting the heterocyclic thio group represented by A ₃₁ and A ₃₂ are represented by R _{11 to} R ₁₈ in the general formula (II-1). Examples thereof include the same alkyl groups, aryl groups, and heterocyclic groups as described above.

The alkyl group, aryl group, and heterocyclic group represented by R ₃₅ and R ₃₆ have the same meaning as Ra and Rb in formula (II-2).

However, General Formula (II-3) contains at least one group represented by —SO ₃ M, —CO ₂ M, and —OH in the molecule. Here, M is synonymous with M in General Formula (II-1).

  Furthermore, the compound represented by the general formula (II-3) does not contain a group represented by -N = N- or a diaminostilbene structure in the molecule.

  Although the specific example of a compound represented by general formula (II-3) based on this invention below is given, this invention is not limited to these.

[Compound represented by formula (II-4)]
Next, the compound represented by formula (II-4) according to the present invention will be described.

In the general formula (II-4), L ₄ represents a phenylene group, a naphthylene group, or an alkylene group.

X ₁ represents an oxygen atom or a sulfur atom, and X ₂ represents an oxygen atom, a sulfur atom or —NH—. A ₄₁ , A ₄₂ , A ₄₃ and A ₄₄ are each independently an alkoxy group, an aryloxy group, a heterocyclic oxy group, an alkylthio group, an arylthio group, a heterocyclic thio group, a hydroxylamino group, or —NR ₄₁ R ₄₂ (R ₄₁ And R ₄₂ each independently represents a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group, and R ₄₁ and R ₄₂ may be bonded to each other to form a ring).

The compound represented by the general formula (II-4) contains at least one group represented by —SO ₃ M, —CO ₂ M, and —OH in the molecule. Here, M represents an alkali metal ion, an alkaline earth metal ion, or an ammonium ion. Furthermore, the compound represented by the general formula (II-4) does not contain a group represented by -N = N- or a diaminostilbene structure in the molecule.

  Next, the compound represented by formula (II-4) according to the present invention will be further described.

L ₄ in the general formula (II-4) represents a phenylene group, a naphthylene group, or an alkylene group, and includes those having a substituent. As the phenylene group, naphthylene group, and alkylene group, the same groups as those described above for L ₂ in formula (II-2) can be given.

The alkoxy group, aryloxy group, heterocyclic oxy group, alkylthio group, arylthio group, and heterocyclic thio group in A _{41 to} A ₄₄ include those having a substituent, and A ₃₁ , A in the general formula (II-3) Similar to ₃₂ . When A _{41 to} A ₄₄ represent —NR ₄₁ R ₄₂ , R ₄₁ , R ₄₂ and the ring formed by combining R ₄₁ and R ₄₂ include those having a substituent, and are represented by the general formula (II-1) The same thing as R < ₁₁ > -R < ₁₈ > in can be mentioned.

In General Formula (II-4), X ₁ represents an oxygen atom or a sulfur atom, and X ₂ represents an oxygen atom, a sulfur atom, or —NH—.

However, the compound represented by the general formula (II-4) contains at least one group represented by —SO ₃ M, —CO ₂ M, and —OH in the molecule. Here, M is synonymous with M in General Formula (II-1).

  Furthermore, the compound represented by the general formula (II-4) does not contain a group represented by -N = N- or a diaminostilbene structure in the molecule.

  Although the specific example of a compound represented by general formula (II-4) based on this invention below is given, this invention is not limited to these.

  Compounds represented by the general formula (I) exemplified above (hereinafter referred to as general formula (I) including general formulas (II) and (III) and general formulas (II-1) to (II-4)) Can be added in the form of any salt such as sodium salt and ammonium salt.

  When the compound represented by the general formula (I) according to the present invention has a plurality of asymmetric carbons in the molecule, there are a plurality of stereoisomers with respect to the same structure. These stereoisomers are shown, and only one of a plurality of stereoisomers can be used, or several of them can be used as a mixture.

  Further, in the present invention, only one type of the compound represented by the general formula (I) according to the present invention may be used, but two or more types may be mixed and used as necessary, such as improvement of solubility. preferable.

The amount of the compound represented by the general formula (I) according to the present invention added to the treatment liquid (preferably a stabilizing liquid or a rinsing liquid) that comes into contact with the last is determined per liter of the used liquid from the viewpoint of the effect of the present invention. 5 × 10 ⁻⁵ to 1 × 10 ⁻² mol is preferable.

  Further, the compound represented by the general formula (I) can be used in combination with a triazinyl stilbene compound. For example, JP-A-6-329936, JP-A-7-140625, JP-A-10-104809, JP-A-10-104809, The triazinyl stilbene compound described in each publication of Japanese Patent No. 2000-39690 can also be used in combination. Commercially available compounds are disclosed in, for example, “Dyeing Note” 19th Edition (Color Dyeing) P.A. 165-168.

  The compound represented by formula (I) can be synthesized with reference to, for example, Koji Matsui, Journal of Synthetic Organic Chemistry, Vol. 17, 528 (1959) and Japanese Patent No. 2618748. That is, a method in which cyanuric chloride is first reacted with a phenylenediamine derivative or a naphthalenediamine derivative, and then amines are sequentially reacted is preferable. Alternatively, it is also preferable to react the phenylenediamine derivative or naphthalenediamine derivative in the second stage or at the end. Examples of the solvent used in this reaction include water and organic solvents such as alcohols, ketones, ethers and amides, but water and water-soluble organic solvents are preferable, and a mixed solvent thereof may be used. Of these, a mixed solvent system of water and acetone is most preferable. Bases used are organic bases such as triethylamine, pyridine, 1,8-diazabicyclo [5,4,0] -7-undecene, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, carbonate. An inorganic base such as potassium hydrogen can be used. Of these, inorganic bases are preferable, and sodium hydroxide, potassium hydroxide, sodium carbonate, and potassium carbonate are particularly preferable. The reaction temperature can be in the range of -20 to 150 ° C, and preferably in the range of -10 to 100 ° C. More specifically, the first stage is preferably -10 to 10 ° C, the second stage is preferably 0 to 40 ° C, and the third stage is preferably 40 to 100 ° C.

  The stabilizing solution according to the present invention includes a chelating agent (for example, ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, 1-hydroxyethylidene-1,1-diphosphonic acid, etc.) as a sequestering agent for metal ions in water, a buffer (for example, Potassium carbonate, borates, acetates, phosphates, etc.), antifungal agents, optical brighteners (eg, triazinyl stilbene compounds), antioxidants (eg, ascorbate, etc.), water-soluble metals Components that are usually contained in a stabilizing solution such as a salt (for example, zinc salt, magnesium salt, etc.) can be appropriately used.

  In addition, sulfites, bisulfites or metabisulfites can also be included. Any organic or inorganic substance may be used as long as it releases sulfite ions, but inorganic salts are preferred. Preferred specific compounds include sodium sulfite, potassium sulfite, ammonium sulfite, ammonium bisulfite, potassium bisulfite, sodium bisulfite, sodium metabisulfite, potassium metabisulfite, ammonium metabisulfite and the like. Further, a sulfinic acid compound, a compound having a pyrrolidone structure, and a surfactant can be added.

[Compound represented by formula (IV)]
In the stabilizing solution according to the present invention, it is preferable to use a compound represented by the following general formula (IV) together with the compound represented by the general formula (I) according to the present invention.

In the formula, X ₁ , X ₂ , Y ₁ and Y ₂ are each a hydroxyl group, halogen atom, sulfo group, morpholino group, alkoxy group, aryloxy group, alkyl group, aryl group, amino group, alkylamino group or arylamino group Represents. M represents a hydrogen atom, sodium, potassium, ammonium or lithium.

  By adopting the above configuration, the effect of solidified substances generated in the stabilization tank is reduced, the white background is improved, and the maximum concentration is reduced due to the adhering to the color paper caused by the stabilizing liquid and stored at high temperature. The effect to alleviate the influence on the yellow stain at the time is maximized.

  Hereinafter, the triazylstilbene fluorescent whitening agent represented by the general formula (IV) according to the present invention will be described.

In the general formula (IV), X ₁ , X ₂ , Y ₁ and Y ₂ are each a hydroxyl group, a halogen atom such as chlorine or bromine, a morpholino group, an alkoxy group (for example, methoxy, ethoxy, methoxyethoxy etc.), an aryloxy group (Eg phenoxy, p-sulfophenoxy, etc.), alkyl group (eg methyl, ethyl etc.), aryl group (eg phenyl, methoxyphenyl etc.), amino group, alkylamino group (eg methylamino, ethylamino, propylamino, dimethyl) Amino, cyclohexylamino, β-hydroxyethylamino, di (β-hydroxyethyl) amino, β-sulfoethylamino, N- (β-sulfoethyl) -N-methylamino, N- (β-hydroxyethyl) -N- Methylamino, etc.), arylamino groups (eg anilino, o-, m-, p -Sulfoanilino, o-, m-, p-chloroanilino, o-, m-, p-toluidino, o-, m-, p-carboxyanilino, o-, m-, p-hydroxyanilino, sulfonaphthylamino , O-, mp-aminoanilino, o-, m-, p-anidino and the like). M represents a hydrogen atom, sodium, potassium, ammonium or lithium.

  Specific examples of the compound represented by formula (IV) are shown below, but the present invention is not limited to these exemplified compounds.

  The triazyl stilbene type fluorescent whitening agent represented by the general formula (IV) is, for example, an ordinary method described in “Fluorescent whitening agent” (published in August, 1976) edited by Chemical Industry Association. Can be synthesized.

  The addition amount of the triazyl stilbene-based optical brightener represented by the general formula (IV) to the stabilizing liquid composition is preferably 0.2 to 6.0 g per liter, particularly preferably 0.4 to 3. 0 g.

  The various compounds added to the stabilizing solution described above can be added in any salt form, but in the stabilizing solution according to the present invention, the ratio of the ammonium salt to the total cation is less than 50 mol%. More preferably, it is less than 25%, and it is particularly preferable that the stabilizing solution does not contain any ammonium salt.

[Absorbance of processing solution with which photosensitive material comes into contact at the end of processing step]
The present invention is characterized in that the absorbance at 440 nm of the processing solution with which the photosensitive material comes into contact at the end of the processing step is 0.05 to 0.5. Hereinafter, a method for adjusting the absorbance within the range of the present invention will be described.

  In general, the photosensitive material is developed by an automatic developing machine. FIG. 1 is a configuration diagram of a general automatic developing machine 8 used for color paper processing. A color developing tank 110, a bleach-fixing tank 120, a stabilizing tank (1) 130A, and a stabilizing tank (2) 130B. The stabilization processing tank (3) 130C holds a color developer, a bleach-fixing solution, and a stabilizing solution, respectively. The photosensitive material is dipped sequentially in these processing solutions, and then dried through the drying chamber 160 to obtain a finished cut paper P1. Each processing solution is supplemented with a replenisher for each processing tank for the purpose of supplementing the components consumed by the photosensitive material and diluting unnecessary components eluted from the photosensitive material. In the stabilization process, the stabilization replenisher is supplied to the final process tank (stabilization process tank (3) 130C), and the overflow liquid is sequentially supplied to the previous stabilization process tank. By introducing the overflow of the stabilization processing tank (1) 130A) to the waste liquid tank, an effort is made to efficiently wash away unnecessary components in the photosensitive material with a small replenishment amount (referred to as cascade flow).

  In general, aminopolycarboxylic acid ferric salt is added as a bleaching main agent to the bleach-fixing solution described later, and it exhibits a dark brown color. Since the bleach-fixing component that has penetrated into the photosensitive material is washed away sequentially in the stabilization process, it is colored by the bleach-fixing solution component eluted from the photosensitive material. The degree of coloring becomes smaller as the downstream stabilizing liquid is reduced. In the present invention, it is preferable that the stabilizing solution contains an iron salt. However, since the iron salt in the bleach-fixing solution component is brought into the stabilizing solution in this manner, the iron salt is added to the replenishing solution of the stabilizing solution. There is no need to keep it.

  Further, sensitizing dyes and dyes are added to the light-sensitive material, and some of them are eluted in the stabilization process. As a result, even in the final treatment liquid of the stabilization treatment step, the absorption is not less than 440 nm. A specific method for controlling the absorbance of the final treatment solution will be described below, but the present invention is not limited to this.

  First, the absorbance can be controlled by selecting the type and amount of coloring components used in the bleaching solution or bleach-fixing solution. As a main coloring component, aminopolycarboxylic acid ferric salt is mentioned as a bleaching main agent. Since the molar extinction coefficient at 440 nm of the iron complex salt differs depending on the type of aminopolycarboxylic acid that is a ligand, by appropriately selecting the type and addition amount of the ferric salt of aminopolycarboxylic acid, the final treatment solution at 440 nm The absorbance can be controlled within the range of the present invention. However, since it is necessary to maintain the desilvering performance that is the original function of the bleaching solution or the bleach-fixing solution, the type and amount of the bleaching agent are restricted. The aminopolycarboxylic acid ferric salt preferably used in the present invention is a ferric salt of a compound represented by the general formulas [AI] to [A-VI] described in JP-A-6-35151. In addition, diethylenetriaminepentaacetic acid ferric salt is also a preferred compound. Of these, particularly preferred are ethylenediaminetetraacetic acid ferric salt, 1,3-propylenediaminetetraacetic acid ferric salt, diethylenamine amine pentaacetic acid ferric salt, and ethylenediamine disuccinic acid ferric salt. .

  It is also a preferred method to select the type and amount of the sensitizing dye or dye added to the light-sensitive material. The absorbance at 440 nm of the final treatment liquid is controlled within the range of the present invention by designing considering that it has a different molar extinction coefficient depending on the type of sensitizing dye or dye and the solubility in each treatment liquid is different. It becomes possible.

  A method of controlling the absorbance at 440 nm of the final processing solution by using an automatic developing machine member or configuration is also preferable. Pre-processing by controlling the material, hardness, nip pressure, etc. of the transport roller (also called the crossing roller) installed outside the liquid between the processing tanks to transport the photosensitive material to the next processing tank The amount of processing solution brought from the tank by the photosensitive material can be controlled within a desired range. Further, the amount of the bleach-fixing solution component and the elution component from the photosensitive material brought to the final processing tank varies depending on the number of tanks in the stabilization process (including the rinsing process). As the number of stabilization processing tanks, 2 to 10 tanks are preferable, and 3 or 4 tanks are particularly preferable.

  It is also a preferred method to control the replenishment amount of the stabilizing replenisher (or rinse replenisher). In general, each processing solution is replenished at a constant rate with respect to the processing amount (area) of the photosensitive material. If the bleaching / fixing component brought into the photosensitive material or the elution of the coloring component from the photosensitive material is almost constant, setting the replenishment amount of the stabilizing solution to a large value will dilute the component, and conversely if the replenishment amount is set to a small amount, Since the components are concentrated, it is easy to control the 440 nn absorbance of the final treatment bath by the replenishment amount.

  Furthermore, it is also preferable to control the absorbance of the final treatment liquid by adding a specific compound to the stabilization (or rinse) treatment liquid. As a method for increasing the absorbance at 440 nm, a yellow dye may be added. Commercially available water-soluble pigments and dyes may be used, but sensitizing pigments and dyes added to the light-sensitive material are preferably used. Conversely, the method of reducing the absorbance at 440 nm should be selected depending on the coloring factor. When the main coloring substance is a bleaching agent (especially aminopolycarboxylic acid ferric salt) brought from the bleaching solution or the bleach-fixing solution, a ligand (chelate) that forms an iron complex salt having a lower molar extinction coefficient It is preferable to add an agent. When the iron complex undergoes chelate exchange, the absorbance at 440 nm can be lowered. A compound (chelating agent) represented by the following general formula [K-IX] is preferably used because it has a high complex stability constant with iron and forms an iron complex close to colorlessness. Further, in order to promote chelate exchange, a metal having a higher complex stability constant with the ligand of the bleaching agent than iron can be added.

In the formula, R _{1 to} R ₃ represent a hydrogen atom, —OH, —PO ₃ M ₂ , a lower alkyl group, and include those having a substituent. Examples of the substituent include —OH, —COOM, —SO ₃ M, and —PO ₃ M ₂ . B _{1 to} B ₃ represent a hydrogen atom, —OH, —COOM ₁ , —PO ₃ M ₂ , —N (R ′) ₂ , R ′ represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, —PO ₃ M ₂ represents, M represents a hydrogen atom or an alkali metal, and n and m represent an integer of 0 or 1.

  Preferred specific examples of the compound represented by the general formula [K-IX] are given.

  In the case where the main coloring component is a sensitizing dye or dye eluted from the light-sensitive material, it is preferable to add an oxidizing agent or a reducing agent that promotes the decomposition thereof.

  Also, the molar extinction coefficient of the bleaching agent brought in by the photosensitive material and the elution amount of the coloring component from the photosensitive material change depending on the pH of the final processing solution, which is one preferred control method. In the present invention, the pH of the treatment liquid in contact with the end of the treatment step is preferably 4-9.

  Further, it is one of preferable methods to reduce absorption near 440 nm by adding a fluorescent brightening agent. The fluorescent brightening agent used in this case is not limited as long as it has light emission in the vicinity of 440 nm, but the bis (triazinylamino) stilbene fluorescent brightening agent exhibits the effect of the present invention more remarkably.

  The processing temperature in the stabilization processing step can be variously set depending on the type and characteristics of the photosensitive material to be processed, but is generally preferably 15 to 45 ° C, more preferably 20 to 40 ° C. Although the time can be set arbitrarily, a shorter time is desirable from the viewpoint of reducing the processing time. It is preferably 5 seconds to 1 minute 45 seconds, more preferably 10 seconds to 1 minute.

A smaller replenishment amount is preferable from the viewpoint of running cost, reduction of discharge amount, handling property, and the like. A specific preferable replenishing amount is preferably 0.5 to 50 times, more preferably 3 to 40 times the amount of the light-sensitive material brought from the previous bath per unit area. Alternatively, the amount is preferably 1 liter or less per 1 m ^{2 of the} photosensitive material, more preferably 500 ml or less. Further, replenishment may be performed continuously or intermittently.

  In the present invention, the stabilizing process using the stabilizing liquid is preferably composed of 2 to 10 tanks as described above, particularly composed of 3 tanks or 4 tanks, and a multistage countercurrent system. It is preferable to use it.

  In the multistage counter-current system, in the stabilization tank divided into a plurality, along the photosensitive material conveyance path, the stabilizing solution overflows into each multistage divisional stabilization tank from the downstream to the upstream in the conveyance direction of the photosensitive material. This is a method in which flow and stabilization processing is performed.

  In the method for processing a light-sensitive material of the present invention, preferably, the exposed light-sensitive material is subjected to a bleaching step (bleaching solution), a fixing step (fixing solution), or a processing in the color developing step (color developing solution). It is dried after being subjected to a bleach-fixing step (bleach-fixing solution), a stabilizing step (stabilizing solution) or a rinsing step (rinsing solution). Further, development processing can be continuously performed while replenishing a replenishing color developer, a replenishing bleaching solution, a replenishing fixing solution, a replenishing bleach-fixing solution, a replenishing stabilizing solution, or the like. The color developer, bleaching solution, bleach-fixing solution, and fixing solution used in the present invention will be described below.

[Color developer]
Preferred examples of the color developing agent used in the color developing solution according to the present invention are known aromatic primary amine color developing agents, particularly p-phenylenediamine derivatives. Representative examples are shown below, but are not limited thereto. It is not something.

1) N, N-diethyl-p-phenylenediamine 2) 4-amino-3-methyl-N, N-diethylaniline 3) 4-amino-N- (β-hydroxyethyl) -N-methylaniline 4) 4 -Amino-N-ethyl-N- (β-hydroxyethyl) aniline 5) 4-amino-3-methyl-N-ethyl-N- (β-hydroxyethyl) aniline 6) 4-amino-3-methyl-N -Ethyl-N- (3-hydroxypropyl) aniline 7) 4-Amino-3-methyl-N-ethyl-N- (4-hydroxybutyl) aniline 8) 4-Amino-3-methyl-N-ethyl-N -(Β-Methanesulfonamidoethyl) aniline 9) 4-Amino-N, N-diethyl-3- (β-hydroxyethyl) aniline 10) 4-Amino-3-methyl-N-ethyl-N- (β- Me Xylethyl) aniline 11) 4-Amino-3-methyl-N- (β-ethoxyethyl) -N-ethylaniline 12) 4-Amino-3-methyl-N- (3-carbamoylpropyl) -Nn-propyl -Aniline 13) 4-amino-N- (4-carbamoylbutyl) -Nn-propyl-3-methylaniline 14) N- (4-amino-3-methylphenyl) -3-hydroxypyrrolidine 15) N- (4-Amino-3-methylphenyl) -3- (hydroquinmethyl) pyrrolidine 16) N- (4-amino-3-methylphenyl) -3-pyrrolidinecarboxamide Among the p-phenylenediamine derivatives, particularly preferred Exemplified compounds 5), 6), 7), 8) and 12), among which Exemplified compounds 5) and 8) are preferred. These p-phenylenediamine derivatives are in the form of salts such as sulfates, hydrochlorides, sulfites, naphthalenedisulfonates, p-toluenesulfonates, or free base types (also referred to as free forms). The concentration of the aromatic primary amine developing agent in the working solution is preferably 2 to 200 mmol, more preferably 6 to 100 mmol, and particularly preferably 10 to 40 mmol per liter of the developing solution.

  The color developer used in the present invention preferably contains a preservative to reduce the disappearance of the color developing agent due to oxidation. Representative preservatives include hydroxylamine derivatives. Examples of the hydroxylamine derivatives that can be used in the present invention include hydroxylamine salts such as hydroxylamine sulfate and hydroxylamine hydrochloride, as well as JP-A-1-97953, 1-186939, 1-186940, Although the hydroxylamine derivative described in 1-187557 etc. can be used, the hydroxylamine derivative represented with the following general formula [A] is especially preferable.

  In the above general formula [A], L represents an alkylene group which may be substituted, and A represents a carboxyl group, a sulfo group, a phosphono group, a phosphine group, a hydroxyl group, an amino group which may be alkyl-substituted, or an alkyl-substituted group. Represents an ammonio group which may be substituted, a carbamoyl group which may be substituted with alkyl, a sulfamoyl group which may be substituted with alkyl, an alkylsulfonyl group, a hydrogen atom, an alkoxyl group, or —O— (B—O) n—R ′; , R ′ each represents a hydrogen atom or an optionally substituted alkyl group. B represents an alkylene group which may be substituted, and n represents an integer of 1 to 4.

  In the above general formula [A], L is preferably a linear or branched alkylene group having 1 to 10 carbon atoms, more preferably 1 to 5 carbon atoms. Specifically, groups such as methylene, ethylene, trimethylene and propylene are preferred examples. Examples of the substituent include a carboxyl group, a sulfo group, a phosphono group, a phosphine group, a hydroxyl group, and an ammonio group that may be alkyl-substituted, and preferred examples include a carboxyl group, a sulfo group, a phosphine group, and a hydroxyl group. A represents a carboxyl group, a sulfo group, a phosphono group, a phosphine group, a hydroxyl group, or an amino group, an ammonio group, a carbamoyl group, or a sulfamoyl group, each of which may be alkyl-substituted. Preferred examples include a carbamoyl group which may be substituted with a group or an alkyl group. As examples of -LA, carboxymethyl group, carboxyethyl group, carboxypropyl group, sulfoethyl group, sulfopropyl group, sulfobutyl group, phosphonomethyl group, phosphonoethyl group, and hydroxyethyl group can be mentioned as preferred examples. The group, carboxyethyl group, sulfoethyl group, sulfopropyl group, phosphonomethyl group, phosphonoethyl group can be mentioned as particularly preferred examples. R is preferably a hydrogen atom or a linear or branched alkyl group having 1 to 10 carbon atoms, particularly preferably having 1 to 5 carbon atoms. Examples of the substituent include a carboxyl group, a sulfo group, a phosphono group, a phosphinic acid group, a hydroxyl group, or an amino group, an ammonio group, a carbamoyl group, a sulfamoyl group, an alkoxyl group, -O- (B -O) n-R 'and the like. B and R ′ are synonymous with those described in the description of A. There may be two or more substituents. Preferred examples of R include a hydrogen atom, a carboxymethyl group, a carboxyethyl group, a carboxypropyl group, a sulfoethyl group, a sulfopropyl group, a sulfobutyl group, a phosphonomethyl group, a phosphonoethyl group, and a hydroxyethyl group. The group, carboxyethyl group, sulfoethyl group, sulfopropyl group, phosphonomethyl group, phosphonoethyl group can be mentioned as particularly preferred examples. L and R may be linked to form a ring.

  Although the typical compound example is shown below among the compounds represented by general formula [A], this invention is not limited to these compounds.

  Further, it is also preferable to use sulfite as a preservative, and the concentration thereof is preferably 0.005 to 1.0 mol / L in the color developer for color negative film, and in the color developer for color paper, 0 to 0.1 mol / L is preferable. Examples of sulfites that can be used in the present invention include sodium sulfite and potassium sulfite.

  In the color developer, in addition to the above-described preservatives, use of the preservatives shown below is not limited. Hydroxamic acids, hydrazides, phenols, α-hydroxy ketones, α-amino ketones, sugars, monoamines, diamines, polyamines, quaternary ammonium salts, nitroxy radicals, alcohols, oximes, diamide compounds And condensed ring amines. These are disclosed in JP-A 63-4235, 63-30845, 63-21647, 63-44655, 63-53551, 63-43140, 63-56654, 63- 58346, 63-43138, 63-146041, 63-44657, 63-44656, US Pat. Nos. 3,615,503, 2,494,903, JP-A-52. -1433020, Japanese Patent Publication No. 4830696 and the like.

  In addition, various metals described in JP-A-57-44148 and JP-A-57-53749, salicylic acids described in JP-A-59-180588, triethanolamine, and triisopananolamine The alkanolamines described in US Pat. No. 54-3532, aromatic polyhydroxy compounds described in US Pat. No. 3,746,544 and the like may be contained as necessary.

  The color developer used in the present invention is preferably from 9.0 to 13.5, more preferably from 9.5 to 12.0, and an alkali agent, a buffering agent and, if necessary, to maintain the pH value. Can contain an acid.

  From the viewpoint of maintaining the pH when the color developing solution is prepared, the following buffering agent is preferably used. Examples of the buffer include carbonate, phosphate, borate, tetraborate, hydroxybenzoate, glycyl salt, N, N-dimethylglycine salt, leucine salt, norleucine salt, guanine salt, 3,4- Dihydroxyphenylalanine salt, alanine salt, aminobutyrate, 2-amino-2-methyl-1,3-propandiol salt, valine salt, proline salt, trishydroquinaminomethane salt, lysine salt, and the like can be used. Carbonate, phosphate, tetraborate, and hydroxybenzoate are particularly excellent in buffering ability in a high pH range of pH 10.0 or higher, and even when added to a color developer, they adversely affect photographic performance (capriformation). Etc.) and a preferable buffer from the viewpoint of being inexpensive.

  Exemplary compounds of the buffer include sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, trisodium phosphate, tripotassium phosphate, disodium phosphate, dipotassium phosphate, sodium borate, potassium borate , Sodium tetraborate (borax), potassium tetraborate, sodium o-hydroxybenzoate (sodium salicylate), potassium o-hydroxybenzoate, sodium 5-sulfo-2-hydroxybenzoate (sodium 5-sulfosalicylate) , Potassium 5-sulfo-2-hydroxybenzoate (potassium 5-sulfosalicylate) and the like. However, the present invention is not limited to these compounds.

  These buffers are preferably used in an amount of 0.01 to 2 mol, more preferably 0.1 to 0.5 mol, per liter of color developer.

  As the other components, for example, calcium and magnesium precipitation inhibitors and various chelating agents which are also stability improvers can be added to the color developer used in the present invention. For example, nitrilotriacetic acid, diethylenetriaminepentaacetic acid, ethylenediaminetetraacetic acid, N, N, N-trimethylenephosphonic acid, ethylenediamine-N, N, N ′, N′-tetramethylenesulfonic acid, transsirohexasidiaminetetraacetic acid, 1,2-diaminopropan tetraacetic acid, glycol ether diamine tetraacetic acid, ethylenediamine orthohydroxyphenylacetic acid, ethylenediamine disuccinic acid (SS form), N- (2-carboxylateethyl) -L-aspartic acid, β-alanine diacetic acid, 2-phosphonobutane-1,2,4-tricarboxylic acid, 1-hydroxyethylidene-1,1-diphosphonic acid, N, N′-bis (2-hydroxybenzyl) ethylenediamine-N, N′-diacetic acid, 1,2 -Dihydroxybenzene-4,6-disulfonic acid and the like It is. Two or more of these chelating agents may be used in combination as necessary. Further, the amount of these chelating agents may be an amount sufficient to sequester metal ions during color developer processing. For example, 0. 1 per liter. Add 1 to 10 g.

  If necessary, an arbitrary development accelerator can be added to the color developer used in the present invention. Examples of the development accelerator include JP-B-37-16088, JP-A-37-5987, JP-A-38-7826, JP-A-44-12380, JP-A-45-9019, and U.S. Pat. No. 3,813,247. Or thioether compounds represented in the specification, p-phenylenediamine compounds represented in JP-A-52-49829 and JP-A-50-15554, JP-A-50-137726, JP-B-44-30074 Quaternary ammonium salts represented in JP-A-56-156826 and JP-A-52-43429, U.S. Pat. Nos. 2,494,903, 3,128,182, 4,230, 796, 3,253,919, Japanese Patent Publication No. 41-11431, U.S. Pat. Nos. 2,482,546, 2,596,926, and 3,582,34. No. 3,128,183, Japanese Patent Publication No. 41-11431, Japanese Patent Publication No. 42-23883 In addition, polyalkylene oxides represented in each publication or specification such as U.S. Pat. No. 3,532,501, other 1-phenyl-3-virazolitones or imidazoles can be added as necessary. Their concentration is preferably 0.001 to 0.2 mol, more preferably 0.01 to 0.05 mol, per liter of the color developer.

  In addition to halogen ions, an optional antifoggant can be added to the color developer as necessary. Examples of organic antifoggants include benzotriazole, 6-nitrobenzimidazole, 5-nitroisoindazole, 5-methylbenzotriazole, 5-nitrobenzotriazole, 5-chloro-benzotriazole, 2-thiazolyl-benzimidazole, 2 -Nitrogen-containing heterocyclic compounds such as thiazolylmethyl-benzimidazole, indazole, hydroxyazaindolizine, and adenine are typical examples.

  In addition, a fluorescent whitening agent can be used in the color developer used in the present invention, if necessary. As the optical brightener, a bis (triazinylamino) stilbene sulfonic acid compound is preferred. As the bis (triazinylamino) stilbene sulfonic acid compound, a known or commercially available diaminostilbene-based auto-enhancing agent can be used. As the known bis (triazinylamino) stilbene sulfonic acid compound, for example, compounds described in JP-A-6-329936, JP-A-7-140625, JP-A-10-140849 and the like are preferable. Commercially available compounds are described, for example, in “Dyeing Note”, 9th edition (Colored Dyeing), pages 165 to 168, and among the compounds described therein, Blankophor BSU liq. And Hakkol BRK.

  Other bis (triazinylamino) stilbene sulfonic acid compounds include compounds I-1 to I-48 and paragraphs [0038] to [0049] described in paragraphs [0038] to [0049] of JP-A No. 2001-281823. The compounds II-1 to II-16 described in paragraph Nos. [0050] to [0052] of JP-A-281823 can also be mentioned. The addition amount of the above-described optical brightener is preferably 0.1 mmol to 0.1 mol per liter of color developer.

The color developer for color negative film preferably contains 0.2 × 10 ^{−2 to} 1.5 × 10 ⁻¹ mol / liter of bromine ions, more preferably 0.5 × 10 ^{−2 to} 5 × 5. Although it is 0.0 × 10 ⁻² mol / liter, bromine ions are usually released as a by-product of development to the color development processing developer, so that it may not be necessary to add to the replenisher. Further, iodine ions are preferably contained in an amount of 0.2 × 10 ^{−3 to} 1.5 × 10 ⁻¹ mol / liter, more preferably 0.5 × 10 ^{−3 to} 5.0 × 10 ⁻³ mol / liter. However, iodine ions are usually released to the developer as a by-product of development, and conversely, they may be absorbed and consumed by undeveloped silver halide. In order to maintain the iodine ion concentration, it may not be necessary to add to the replenisher, or it may be added to the replenisher. Further, when bromine ions are contained in the color developing solution for color paper, it is preferably 1.0 × 10 ⁻³ mol / liter or less. The color developing solution for color paper preferably contains chlorine ions of 3.5 × 10 ^{−2 to} 1.5 × 10 ⁻¹ mol / liter, but chlorine ions are usually used as a by-product in development. Since it is released into the developer, it may not be necessary to add it to the replenisher.

In the present invention, the color development processing temperature that can be applied in the processing method is preferably 30 to 55 ° C., more preferably 35 to 55 ° C. when the photosensitive material to be developed is color paper. Preferably it is 38-45 degreeC. The color development processing time is preferably from 5 to 90 seconds, more preferably from 15 to 60 seconds. The replenishment amount is preferably small, but 15 to 600 ml per 1 m ^{2 of} the light-sensitive material is suitable, preferably 15 to 120 ml, particularly preferably 30 to 60 ml. On the other hand, in the case of color negative color development processing, the development temperature is preferably 20 to 55 ° C, more preferably 30 to 55 ° C, and further preferably 38 to 45 ° C. The color development processing time is preferably 20 seconds to 6 minutes, more preferably 30 to 200 seconds. A smaller replenishing amount is preferred, but 100 to 800 ml per 1 m ^{2 of} the light-sensitive material is suitable, preferably 200 to 500 ml, particularly preferably 250 to 400 ml. In the present invention, the color development time refers to the time from when the photosensitive material enters the color developer to the next processing step (for example, bleach-fixing solution). When processed by an automatic developing machine or the like, the time during which the photosensitive material is immersed in the color developer (so-called submerged time) and the photosensitive material leave the color developer, and the solution is prepared for the next processing step. The total of both the time for transporting outside (so-called crossover time) is called color development time. The crossover time is preferably 10 seconds or less, more preferably 5 seconds or less.

[Bleaching solution, Bleach fixing solution]
In the present invention, any bleaching agent may be used as the bleaching agent used in the bleaching solution or the bleach-fixing solution. Particularly, iron (III) organic complex salts (for example, ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, nitrilotriacetic acid Aminopolycarboxylic acids such as cyclohexanediaminetetraacetic acid and ethylenediaminedisuccinic acid, complex salts such as aminopolyphosphonic acid, phosphonocarboxylic acid and organic phosphonic acid) or organic acids such as citric acid, tartaric acid and malic acid; persulfates Hydrogen peroxide and the like are preferable.

  Of these, ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, 1,3-diaminopropanetetraacetic acid, ethylenediaminedisuccinic acid, and iron (III) complex salt of methyliminodiacetic acid are preferred because of their high bleaching power. These ferric ion complex salts may be used in the form of complex salts or ferric salts such as ferric sulfate, ferric chloride, ferric nitrate, ferric ammonium sulfate, ferric phosphate. And a chelating agent such as aminopolycarboxylic acid, aminopolyphosphonic acid and phosphonocarboxylic acid may be used to form a ferric ion complex salt in the solution. Moreover, you may use a chelating agent in excess rather than forming a ferric ion complex salt. Among the iron complexes, aminopolycarboxylic acid iron complexes are preferable, and the addition amount is preferably 0.01 to 1.0 mol / liter, more preferably 0.05 to 0.50 mol / liter.

  In the bleaching solution or the bleach-fixing solution, various compounds can be used as a bleaching accelerator. For example, a compound having a mercapto group or a disulfide bond described in Research Disclosure No. 17129 (July 1978), a thiourea compound, or a halide such as iodine or bromine ion is preferable in terms of excellent bleaching power.

  In addition, the bleaching solution or the bleach-fixing solution may contain a rehalogenating agent such as bromide (for example, potassium bromide), chloride (for example, potassium chloride) or iodide (for example, ammonium iodide). One or more inorganic acids with pH buffering capacity such as borax, sodium metaborate, acetic acid, sodium acetate, sodium carbonate, potassium carbonate, citric acid, sodium citrate, tartaric acid, succinic acid, maleic acid, glycolic acid Organic acids and alkali metal or ammonium salts thereof, or corrosion inhibitors such as ammonium nitrate and guanidine can be added.

  Fixing agents used in the fixing solution or the bleach-fixing solution are known fixing agents, that is, thiosulfates such as sodium thiosulfate and ammonium thiosulfate; thiocyanates such as sodium thiocyanate and ammonium thiocyanate; ethylene bisthioglycolic acid Water-soluble silver halide solubilizers such as thioether compounds such as 3,6-dithia-1,8-octanediol and thioureas can be used alone or in combination of two or more. In the present invention, it is preferable to use thiosulfuric acid, particularly ammonium thiosulfate. The amount of the fixing agent per liter is preferably from 0.1 to 5.0 mol, more preferably from 0.3 to 2.0 mol. The pH range of the bleach-fixing solution or the fixing solution is preferably from 3 to 10, more preferably from 5 to 9.

  In addition, the bleaching solution, the fixing solution, and the bleach-fixing solution may contain various other kinds of fluorescent whitening agents, antifoaming agents or surfactants, and organic solvents such as polyvinylpyrrolidone and methanol.

  Bleaching solutions, fixing solutions, and bleach-fixing solutions are sulphites as preservatives, such as sodium sulfite, potassium sulfite, ammonium sulfite, potassium bisulfite, sodium bisulfite, sodium metabisulfite, potassium metabisulfite, metabisulfite. Addition of ammonium sulfate or the like is common, but in addition, ascorbic acid, a carbonyl bisulfite adduct, a carbonyl compound, or the like may be added.

  Furthermore, you may add a buffering agent, a fluorescent whitening agent, a chelating agent, an antifoamer, an antifungal agent, etc. as needed.

The time required for the bleach-fixing step that can be applied to the processing method of the present invention is preferably 90 seconds or less, more preferably 45 seconds or less. The time required for the bleach-fixing step here refers to the time from when the photosensitive material is immersed in the first tank until it leaves the final tank when the process has a plurality of tanks. It refers to the time until the photosensitive material is immersed in the subsequent rinsing or stabilizing solution, and includes the crossover time therebetween. The crossover time is preferably 10 seconds or less, more preferably 5 seconds or less. Also. The temperature of the bleach-fixing solution is preferably 20 to 70 ° C, and desirably 25 to 50 ° C. Further, the replenishment rate of the bleach-fixing solution is preferably 200 ml / m ² or less, more preferably 20-100 / m ^2.

The replenishment rate of the bleaching treatment solution is preferably 200 ml / m ² or less, more preferably 50~200ml / m ^2. The total processing time of the bleaching step is preferably 15 to 90 seconds. The time required for the bleaching step here refers to the time from when the photosensitive material is immersed in the first tank until it leaves the final tank when the process has a plurality of tanks. It refers to the time until the photosensitive material is immersed in the rinse or stabilizing solution, and includes the crossover time between them. The crossover time is preferably 10 seconds or less, more preferably 5 seconds or less. Moreover, it is preferable that processing temperature is 25-50 degreeC. The replenishment rate of the fixing treatment solution is preferably 600 ml / m ² or less, more preferably 20~500ml / m ^2. The total processing time of the fixing process is preferably 15 to 90 seconds. The time required for the fixing process here refers to the time from when the photosensitive material is immersed in the first tank until it exits the final tank when the process has a plurality of tanks. It refers to the time until the photosensitive material is immersed in the rinse or stabilizing solution, and includes the crossover time between them. The crossover time is preferably 10 seconds or less, more preferably 5 seconds or less. Moreover, it is preferable that processing temperature is 25-50 degreeC.

[Photosensitive material]
Photosensitive materials applicable to the method for processing a photosensitive material of the present invention include a wide variety of photographic elements having a silver halide photosensitive layer on a support, such as color negative films, color reversal films, color papers, and color movie films. Etc.

  The light-sensitive material according to the present invention mainly comprises a yellow dye-forming coupler-containing blue-sensitive silver halide emulsion layer, a magenta dye-forming coupler-containing green light-sensitive silver halide emulsion layer, and a cyan dye-forming coupler. It has a photographic composition layer comprising at least one each of a red-sensitive silver halide emulsion layer and a non-photosensitive hydrophilic colloid layer. The silver halide emulsion layer containing the yellow dye-forming coupler is used as a yellow coloring layer, the silver halide emulsion layer containing the magenta dye-forming coupler is used as a magenta coloring layer, and the silver halide containing the cyan dye-forming coupler. The emulsion layer functions as a cyan coloring layer. The silver halide emulsions contained in the yellow coloring layer, the magenta coloring layer and the cyan coloring layer, respectively, are sensitive to light in different wavelength regions (for example, light in the blue region, green region and red region). It is preferable to have it. In addition to the yellow coloring layer, the magenta coloring layer, and the cyan coloring layer, the photosensitive material may have an antihalation layer, an intermediate layer, and a colored layer as a non-photosensitive hydrophilic colloid layer to be described later if desired.

  Hereinafter, a configuration example of color paper which is a kind of photosensitive material will be described.

  The composition of the silver halide emulsion used in the light-sensitive material according to the present invention may be any halogen composition such as silver chloride, silver bromide, silver chlorobromide, silver iodobromide, silver chloroiodobromide, silver chloroiodide. In particular, silver chlorobromide or silver chloroiodide containing 95 mol% or more of silver chloride is preferable because the effect of the present invention is remarkable. Further, from the viewpoint of rapid processability and process stability, a silver halide emulsion containing 97 mol% or more, more preferably 98 to 99.9 mol% of silver chloride is preferable.

  In the light-sensitive material according to the present invention, a silver halide emulsion having a portion containing silver bromide at a high concentration is also preferably used from the viewpoint of reducing softening of the characteristic curve in a high concentration region in short exposure at high illuminance. be able to. In this case, the portion containing silver bromide at a high concentration may be an epitaxy junction with silver halide grains or a so-called core-shell emulsion, or may be only partially formed without forming a complete layer. There may only be regions of different composition. Further, the composition may change continuously or discontinuously. The portion where silver bromide is present at a high concentration is particularly preferably the surface of silver halide grains or the apex of crystal grains.

  In the light-sensitive material according to the present invention, it is preferable to use silver halide grains containing heavy metal ions from the viewpoint of reducing softening in high-illuminance and short-time scanning exposure. Examples of heavy metal ions that can be used for such purposes include Group 8-10 metals such as iron, iridium, platinum, palladium, nickel, rhodium, osmium, ruthenium, cobalt, cadmium, zinc, mercury, etc. Examples include Group 12 transition metals and ions of lead, rhenium, molybdenum, tungsten, gallium, and chromium. Of these, metal ions of iron, iridium, platinum, ruthenium, gallium and osmium are preferable. These metal ions can be added to the silver halide emulsion in the form of a salt or a complex salt.

  When the heavy metal ion forms a complex, the ligand or ion includes, for example, cyanide ion, thiocyanate ion, cyanate ion, chloride ion, bromide ion, iodide ion, nitrate ion, carbonyl And ammonia. Of these, cyanide ion, thiocyanate ion, isothiocyanate ion, chloride ion, bromide ion and the like are preferable.

  In order for silver halide grains to contain the above heavy metal ions, each heavy metal compound is subjected to physical ripening before formation of silver halide grains, during formation of silver halide grains, after formation of silver halide grains, etc. What is necessary is just to add at the arbitrary time in a process. Moreover, in addition, the solution of a heavy metal compound can be continuously performed over the whole or a part of particle formation process.

The amount of the heavy metal ion added to the silver halide emulsion is preferably 1 × 10 ⁻⁹ to 1 × 10 ⁻² mol per mol of silver halide, and preferably 1 × 10 ^{−8 to} 5 × 10 ⁻⁵ mol. More preferred.

  In the light-sensitive material according to the present invention, any silver halide grains can be used. One preferable example is a cube having a (100) plane as a crystal surface. Also, U.S. Pat. Nos. 4,183,756, 4,225,666, JP-A-55-26589, JP-B-55-42737, The Journal of Photographic Science (J. Photogr. Sci.) 21, 39 (1973) and the like, particles having a shape such as octahedron, tetrahedron, dodecahedron, etc. can be produced and used. Furthermore, particles having twin planes may be used.

  In the light-sensitive material according to the present invention, the silver halide grains are preferably grains having a single shape, but it is particularly preferred to add two or more monodispersed silver halide emulsions in the same layer.

  The grain size of the silver halide grains according to the present invention is not particularly limited, but is preferably 0.1 to 1.2 μm, more preferably 0.1 μm, considering rapid processability, sensitivity, and other photographic performance. It is in the range of 2 to 1.0 μm. This particle size can be measured using the projected area or diameter approximation of the particle. If the particles are substantially uniform in shape, the particle size distribution can be expressed as a diameter or a projected area.

  The particle size distribution of the silver halide grains used in the light-sensitive material according to the present invention is preferably monodispersed silver halide grains having a coefficient of variation of 0.22 or less, more preferably 0.15 or less, and particularly preferably fluctuations. Two or more monodispersed emulsions having a coefficient of 0.15 or less are added to the same layer. The variation coefficient here is a coefficient representing the breadth of the particle size distribution, and is defined by the following equation.

Coefficient of variation = S / R
(Here, S represents the standard deviation of the particle size distribution, and R represents the average particle size.)
The particle diameter here means the diameter in the case of spherical silver halide grains, and the diameter when the projected image is converted into a circular image of the same area in the case of grains having a shape other than a cube or a sphere. .

  As a silver halide emulsion preparation apparatus and preparation method, various methods known in the art can be used. The silver halide emulsion used in the light-sensitive material according to the present invention may be obtained by any method of acidic method, neutral method and ammonia method. The silver halide grains may be grown at once, or may be grown after preparing seed grains. The method of preparing the seed particles and the method of growing the particles may be the same or different.

  In addition, the form of reacting the soluble silver salt and the soluble halide salt may be any of a forward mixing method, a back mixing method, a simultaneous mixing method, or a combination thereof, but is obtained by the simultaneous mixing method. Is preferred. Furthermore, the pAg controlled double jet method described in JP-A No. 54-48521 and the like can be used as one type of the simultaneous mixing method.

  Further, an apparatus for supplying a water-soluble silver salt and a water-soluble halide salt aqueous solution from an adding apparatus disposed in a reaction mother liquor described in JP-A-57-92523 and JP-A-57-92524, German Patent No. 2 , 921,164, etc., an apparatus for continuously adding an aqueous solution of a water-soluble silver salt and a water-soluble halide salt, and a reaction mother liquor outside the reactor described in JP-B-56-501776, etc. An apparatus or the like that forms grains while keeping the distance between silver halide grains constant by taking out and concentrating by ultrafiltration may be used. Further, if necessary, a silver halide solvent such as thioether may be used. Further, a compound having a mercapto group, a nitrogen-containing heterocyclic compound, or a compound such as a sensitizing dye may be added at the time of forming silver halide grains or after the completion of grain formation.

The silver halide emulsion used in the light-sensitive material according to the present invention can be used in combination of a sensitization method using a gold compound and a sensitization method using a chalcogen sensitizer. As the chalcogen sensitizer applied to the silver halide emulsion, for example, a sulfur sensitizer, a selenium sensitizer, a tellurium sensitizer and the like can be used, and among them, a sulfur sensitizer is preferable. Examples of the sulfur sensitizer include thiosulfate, allylthiocarbamide thiourea, allyl isothiocyanate, cystine, p-toluenethiosulfonate, rhodanine, inorganic sulfur and the like. The addition amount of the sulfur sensitizer is preferably changed depending on the type of the silver halide emulsion to be applied, the magnitude of the expected effect, etc., but is generally 5 × 10 ^{−10 to} 5 × 10 10 per mol of silver halide. The range of ⁻⁵ mol, preferably 5 × 10 ^{−8 to} 3 × 10 ⁻⁵ mol is preferable.

As the gold sensitizer, for example, various gold complexes such as chloroauric acid and gold sulfide can be added. Examples of the ligand compound used include dimethyl rhodanine, thiocyanic acid, mercaptotetrazole, mercaptotriazole and the like. The amount of gold compound used is not uniform depending on the type of silver halide emulsion, the type of compound used, ripening conditions, etc., but usually 1 × 10 ⁻⁴ to 1 × 10 ⁻⁸ mol per mol of silver halide. It is preferable that More preferably, it is 1 * 10 < ^-5 > -1 * 10 <^-8> mol. As chemical sensitization of the silver halide emulsion according to the present invention, reduction sensitization may be used.

The silver halide emulsion used in the light-sensitive material according to the present invention is publicly known for the purpose of preventing fogging that occurs during the preparation process of the light-sensitive material, reducing performance fluctuations during storage, and preventing fogging that occurs during development. Antifoggants and stabilizers can be used. Examples of preferable compounds that can be used for such purposes include compounds represented by the general formula (II) described in JP-A-2-14636, page 7, lower column, and more preferable. Specific compounds include compounds (IIa-1) to (IIa-8) and (IIb-1) to (IIb-7) described on page 8 of the same publication, and 1- (3-methoxyphenyl). Examples include compounds such as -5-mercaptotetrazole and 1- (4-ethoxyphenyl) -5-mercaptotetrazole. Depending on the purpose, these compounds are added in steps such as a silver halide emulsion grain preparation step, a chemical sensitization step, a chemical sensitization step, and a coating solution preparation step. When chemical sensitization is performed in the presence of these compounds, it is preferably used in an amount of about 1 × 10 ^{−5 to} 5 × 10 ⁻⁴ mol per mol of silver halide. When added at the end of chemical sensitization, the amount is preferably about 1 × 10 ⁻⁶ to 1 × 10 ⁻² mol per mol of silver halide, more preferably 1 × 10 ^{−5 to} 5 × 10 ⁻³ mol. . In the coating solution preparation step, when added to the silver halide emulsion layer, the amount is preferably about 1 × 10 ⁻⁶ to 1 × 10 ⁻¹ mol per mol of silver halide, and 1 × 10 ⁻⁵ to 1 ×. 10 ⁻² mol is more preferred. Further, when added to a constituent layer other than the silver halide emulsion layer, the amount in the coating film is preferably about 1 × 10 ⁻⁹ to 1 × 10 ⁻³ mol per 1 m ² .

  In the light-sensitive material according to the present invention, dyes having absorption in various wavelength ranges can be used for the purpose of preventing irradiation and preventing halation. For this purpose, any known compound can be used. In particular, as dyes having absorption in the visible region, the dyes AI-1 to 11 described in JP-A-3-251840, page 308, and special dyes can be used. The dyes described in the specification of Kaihei 6-3770 and the dyes described in JP-A-11-119379 are preferably used. The infrared absorbing dye is described in the lower left column on page 2 of JP-A-1-280750. The compounds represented by the general formulas (I), (II) and (III) have preferable spectral characteristics, and are preferable without affecting the photographic characteristics of the silver halide photographic emulsion and without causing contamination by residual colors.

  It is preferable to add a fluorescent brightening agent to the light-sensitive material according to the present invention from the viewpoint of improving the white background. Preferred examples of the compound include compounds represented by the general formula II described in JP-A-2-232652.

  The light-sensitive material according to the present invention has a layer containing a silver halide emulsion spectrally sensitized in a specific region of a wavelength region of 400 to 900 nm in combination with a yellow coupler, a magenta coupler, and a cyan coupler. The silver halide emulsion contains one or a combination of two or more sensitizing dyes.

  Any known compound can be used as the spectral sensitizing dye for spectral sensitization of the silver halide emulsion used in the light-sensitive material according to the present invention. No. 251840, page 28, BS-1 to 8 can be preferably used alone or in combination. As the green photosensitive sensitizing dye, GS-1 to 5 described on page 28 of the same publication are preferably used. As the red photosensitive sensitizing dye, RS-1 to 8 described in page 29 of the same publication are preferably used. In addition, when image exposure is performed with infrared light using a semiconductor laser or the like, it is necessary to use an infrared photosensitive sensitizing dye. As the infrared photosensitive sensitizing dye, JP-A-4-285950 can be used. The pigments of IRS-1 to 11 described in JP-A No. 6-8 are preferably used. Further, these infrared, red, green, and blue photosensitive sensitizing dyes are supersensitizers SS-1 to SS-9 described in JP-A-4-285950, pages 8 to 9 and JP-A-5-66515. It is preferable to use a combination of compounds S-1 to S-17 described in JP-A No. 15-17. These sensitizing dyes may be added at any time from the formation of silver halide grains to the end of chemical sensitization.

  As a method for adding a sensitizing dye, it may be added as a solution by dissolving it in water-miscible organic solvent such as methanol, ethanol, fluorinated alcohol, acetone, dimethylformamide or water, or as a solid dispersion. Also good.

  As the coupler used in the light-sensitive material according to the present invention, any compound capable of forming a coupling product having a spectral absorption maximum wavelength in a wavelength region longer than 340 nm by a coupling reaction with an oxidized form of a color developing agent is used. However, typical examples include a yellow dye-forming coupler having a spectral absorption maximum wavelength in a wavelength range of 350 to 500 nm, a magenta dye-forming coupler having a spectral absorption maximum wavelength in a wavelength range of 500 to 600 nm, and a wavelength range of 600 Representative are cyan dye-forming couplers having a spectral absorption maximum wavelength at ˜750 nm.

  As a cyan coupler that can be preferably used in the light-sensitive material according to the present invention, a pyrrolotriazole-based coupler is preferably used, and a coupler represented by the general formula (I) or (II) in JP-A-5-313324 and a special coupler. The couplers represented by general formula (I) in Kaihei 6-347960 and the exemplified couplers described in these patents are particularly preferred. Phenol-based and naphthol-based cyan couplers are also preferable. For example, cyan couplers represented by the general formula (ADF) described in JP-A-10-333297 are preferable. Examples of cyan couplers other than those described above include pyrroloazole type cyan couplers described in European Patent Nos. 488,248 and 491,197 A1, and 2,5 described in US Pat. No. 5,888,716. -Diacylaminophenol coupler, pyrazoloazole type cyan coupler having an electron-withdrawing group and a hydrogen-bonding group at the 6-position described in US Pat. Nos. 4,873,183 and 4,916,051 In particular, pyrazoloazole type cyan couplers having a carbamoyl group at the 6-position described in JP-A-8-171185, JP-A-8-31360, and JP-A-8-339060 are also preferable.

  In addition to the diphenylimidazole cyan coupler described in JP-A-2-33144, 3-hydroxypyridine cyan couplers described in European Patent No. 333,185A2 (particularly couplers listed as specific examples ( 42) 4-equivalent couplers having a chlorine-eliminating group to give 2 equivalents, couplers (6) and (9) are particularly preferred) and cyclic active methylene cyanides described in JP-A No. 64-32260. Couplers (among others, coupler examples 3, 8, and 34 listed as specific examples are particularly preferred), pyrrolopyrazole type cyan couplers described in EP 456,226A1, and EP 484,909. A pyrroloimidazole type cyan coupler can also be used.

  Of these cyan couplers, pyrroloazole cyan couplers represented by the general formula (I) described in JP-A No. 11-282138 are particularly preferred, and those in paragraphs [0012] to [0059] of the patent are preferred. The description, including the exemplified cyan couplers (1) to (47), is applied to the present application as it is, and is preferably incorporated as part of the specification of the present application.

  In the present invention, as the magenta coupler used in the magenta image forming layer, for example, a 5-pyrazolone-based magenta coupler or a pyrazoloazole-based magenta coupler is used, and among them, in terms of hue, image stability, color developability, etc. A pyrazolotriazole coupler in which a secondary or tertiary alkyl group as described in JP-A-61-65245 is directly connected to the 2, 3 or 6-position of a pyrazolotriazole ring, described in JP-A-61-65246 Pyrazoloazole couplers containing a sulfonamide group in the molecule, pyrazoloazole couplers having an alkoxyphenylsulfonamide ballast group as described in JP-A-61-147254, and European Patent No. 226,849A Al in the 6th position as described in the specification and 294,785A. Use of pyrazoloazole couplers having an alkoxy group or an aryloxy group. In particular, as the magenta coupler, a pyrazoloazole coupler represented by the general formula (M-I) described in JP-A-8-122984 is preferable, and paragraph numbers [0009] to [0026] of the patent are incorporated in the present application as they are. Applied and incorporated as part of the specification of this application. In addition, pyrazoloazole couplers having sterically hindered groups at both the 3-position and the 6-position described in European Patent Nos. 854,384 and 884,640 are also preferably used.

  Examples of yellow couplers that can be preferably used in the light-sensitive material according to the present invention include acylacetamide-type yellow couplers having a 3- to 5-membered cyclic structure in the acyl group described in European Patent No. 447,969A1, Malondianilide type yellow coupler having a cyclic structure described in Japanese Patent No. 482,552A1, European Patent Nos. 953,870A1, 953,871A1, 953,872A1, No. 953,873A1, 953,874A1, 953,875A1, etc., pyrrole-2 or 3-yl or indole-2 or 3-ylcarbonylacetic acid anilide couplers Having a dioxane structure described in US Pat. No. 5,118,599 Sill acetamide type yellow couplers are preferably used. Among them, the use of an acylacetamide type yellow coupler in which the acyl group is a 1-alkylcyclopropane-1-carbonyl group and a malondianilide type yellow coupler in which one of the anilides constitutes an indoline ring is particularly preferred. These couplers can be used alone or in combination.

  When using an oil-in-water emulsion dispersion method as a method of adding a coupler or other organic compound used in the light-sensitive material according to the present invention, it is usually necessary for a water-insoluble high-boiling organic solvent having a boiling point of 150 ° C. or higher. Accordingly, it is dissolved by using a low boiling point and / or water-soluble organic solvent in combination, and emulsified and dispersed in a hydrophilic binder such as an aqueous gelatin solution using a surfactant. As the dispersing means, a stirrer, a homogenizer, a colloid mill, a flow jet mixer, an ultrasonic disperser, or the like can be used. A step of removing the low-boiling organic solvent after the dispersion or simultaneously with the dispersion may be added. Examples of the high-boiling organic solvent that can be used to dissolve and disperse the coupler include phthalates such as dioctyl phthalate, diisodecyl phthalate, and dibutyl phthalate, and phosphate esters such as tricresyl phosphate and trioctyl phthalate. Are preferably used. Further, the dielectric constant of the high boiling point organic solvent is preferably 3.5 to 7.0. Two or more high-boiling organic solvents can be used in combination.

  Further, instead of using a high-boiling organic solvent or in combination with a high-boiling organic solvent, a water-insoluble and organic solvent-soluble polymer compound is dissolved in a low-boiling and / or water-soluble organic solvent as necessary. Alternatively, a method of emulsifying and dispersing by various dispersing means using a surfactant in a hydrophilic binder such as an aqueous gelatin solution may be employed. Examples of the water-insoluble and organic solvent-soluble polymer used at this time include poly (Nt-butylacrylamide).

  Compounds containing a hydrophobic group having 8 to 30 carbon atoms and a sulfonic acid group or a salt thereof as one of the surfactants used for dispersing the photographic additive and adjusting the surface tension during coating. Is mentioned. Specific examples include A-1 to A-11 described in JP-A No. 64-26854. A surfactant in which a fluorine atom is substituted for an alkyl group can also be used.

  Each of the above couplers is preferably used in combination with an anti-fading agent in order to prevent fading of the formed dye image due to light, heat, humidity and the like. Particularly preferred compounds include phenyl ether compounds represented by the general formulas I and II described in JP-A-2-66541, page 3, and phenol compounds represented by the general formula IIIB described in JP-A-3-174150. An amine compound represented by the general formula A described in JP-A No. 64-90445 and a metal complex represented by the general formulas XII, XIII, XIV, and XV described in JP-A No. 62-182741 are particularly preferable for magenta dyes. . Further, compounds represented by general formula I 'described in JP-A-1-196049 and compounds represented by general formula II described in JP-A-5-11417 are particularly preferred for yellow and cyan dyes.

  For the purpose of shifting the absorption wavelength of the coloring dye, compound (d-11) described in page 9, lower left column of JP-A-4-114154, compound (A'-1) described in page 10, lower left column of the same publication ) And the like can be used. In addition, the fluorescent dye releasing compound described in US Pat. No. 4,774,187 can also be used.

  In the light-sensitive material according to the present invention, a compound that reacts with the oxidized developer is added to the layer between the light-sensitive layer to prevent color turbidity, or added to the silver halide emulsion layer to cause fogging, etc. It is preferable to improve. The compound for this purpose is preferably a hydroquinone derivative, more preferably a dialkyl hydroquinone such as 2,5-di-t-octyl hydroquinone. Particularly preferred compounds are compounds represented by the general formula II described in JP-A-4-13356, and the compounds II-1 to II-14 described on pages 13 to 14 and the compound 1 described on page 17 are the same. Can be mentioned.

  In the light-sensitive material according to the present invention, it is preferable to add an ultraviolet absorber to prevent static fogging or to improve the light resistance of the dye image. Preferred ultraviolet absorbers include benzotriazoles, and particularly preferred compounds include compounds represented by general formula III-3 described in JP-A-1-250944 and general compounds described in JP-A-64-66646. Compounds represented by formula III, UV-1L to UV-27L described in JP-A-63-187240, compounds represented by general formula I described in JP-A-4-1633, described in JP-A-5-165144 And compounds represented by the general formulas (I) and (II).

  In the light-sensitive material according to the present invention, it is advantageous to use gelatin as a binder, but if necessary, gelatin derivatives, graft polymers of gelatin and other polymers, proteins other than gelatin, sugar derivatives, cellulose derivatives, simple substances. Hydrophilic colloids such as synthetic hydrophilic polymer materials such as mono- or copolymers can also be used.

  As the binder hardener, it is preferable to use a vinyl sulfone type hardener or a chlorotriazine type hardener alone or in combination, for example, as described in JP-A Nos. 61-249054 and 61-245153. It is preferable to use the compound of. In order to prevent the growth of mold and bacteria that adversely affect photographic performance and image storage stability, it is preferable to add a preservative and an antifungal agent as described in JP-A-3-157646 in the colloid layer. In order to improve the surface physical properties of the photosensitive material before or after processing, it is preferable to add a slipping agent or matting agent described in JP-A-6-118543 and JP-A-2-73250 to the protective layer.

  The photosensitive material according to the present invention may have at least one yellow image forming layer, magenta image forming layer, and cyan image forming layer, but a plurality of color image forming layers as necessary. The unit may be formed by.

  In the light-sensitive material according to the present invention, dyes having absorption in various wavelength ranges can be used for the purpose of preventing irradiation and preventing halation. For this purpose, any known compound can be used. In particular, as dyes having absorption in the visible region, dyes AI-1 to 11 described in JP-A-3-251840, page 308 and JP-A-6 A dye described in No. 3770 is preferably used.

  The light-sensitive material according to the present invention has at least one hydrophilic colloid layer colored with a non-diffusible compound on the side closer to the support than the silver halide emulsion layer closest to the support among the silver halide emulsion layers. It is preferable. As the coloring substance, a dye or other organic or inorganic coloring substance can be used.

The light-sensitive material according to the present invention preferably has at least one colored hydrophilic colloid layer on the side closer to the support than the silver halide emulsion layer closest to the support among the silver halide emulsion layers. The layer may contain a white pigment. For example, rutile type titanium dioxide, anatase type titanium dioxide, barium sulfate, barium stearate, silica, alumina, zirconium oxide, kaolin and the like can be used, and titanium dioxide is particularly preferable for various reasons. The white pigment is dispersed in an aqueous binder of hydrophilic colloid such as gelatin so that the treatment liquid can penetrate. The coating amount of the white pigment is preferably in the range of 0.1 to 50 g / m ² , more preferably in the range of 0.2 to 5 g / m ² .

  Between the support and the silver halide emulsion layer closest to the support, in addition to the white pigment-containing layer, an undercoat layer as required, or a non-photosensitive hydrophilic colloid layer such as an intermediate layer at an arbitrary position Can be provided.

  In the light-sensitive material according to the present invention, a whitening property can be further improved by adding a fluorescent brightening agent. The fluorescent whitening agent is not particularly limited as long as it is a compound that can absorb ultraviolet rays and emit visible light fluorescence, but is a diaminostilbene compound having at least one sulfonic acid group in the molecule, These compounds are preferable because they have an effect of promoting the elution of the sensitizing dye to the outside of the photosensitive material. Another preferred form is a solid particulate compound having a fluorescent whitening effect.

  In the light-sensitive material according to the present invention, the silver halide emulsion layer is laminated and coated on a support, but the order from the support may be any order. In addition to this, an intermediate layer, a filter layer, a protective layer, and the like can be disposed as necessary.

  The light-sensitive material according to the present invention preferably contains an oil-soluble dye or pigment, since the white background is improved. Representative examples of oil-soluble dyes include compounds 1-27 described on pages 8-9 of JP-A-2-842.

  In the case of using an oil-in-water emulsion dispersion method to add a stain inhibitor or other organic compound used in the light-sensitive material according to the present invention, usually, a water-insoluble high-boiling organic solvent having a boiling point of 150 ° C. or higher is used. If necessary, it is dissolved in combination with a low boiling point and / or water-soluble organic solvent, and emulsified and dispersed in a hydrophilic binder such as an aqueous gelatin solution using a surfactant. As the dispersing means, a stirrer, a homogenizer, a colloid mill, a flow jet mixer, an ultrasonic disperser, or the like can be used. A step of removing the low-boiling organic solvent after the dispersion or simultaneously with the dispersion may be added. As high-boiling organic solvents that can be used to dissolve and disperse stain inhibitors and the like, phosphate esters such as tricresyl phosphate and trioctyl phosphate, and phosphine oxides such as trioctyl phosphine oxide are preferably used. It is done. The dielectric constant of the high boiling point organic solvent is preferably 3.5 to 7.0. Two or more high-boiling organic solvents can be used in combination.

  As a preferable compound as a surfactant used for dispersion of photographic additives used in the light-sensitive material according to the present invention and adjustment of surface tension during coating, a hydrophobic group having 8 to 30 carbon atoms and sulfone in one molecule. The thing containing an acid group or its salt is mentioned. Specific examples include A-1 to A-11 described in JP-A No. 64-26854. A surfactant in which a fluorine atom is substituted for an alkyl group is also preferably used. These dispersions are usually added to a coating solution containing a silver halide emulsion, but the time until the addition to the coating solution after dispersion and the time after addition to the coating solution should be short, and 10 hours each. Is preferably within 3 hours, and more preferably within 20 minutes.

  As the support used for the photosensitive material according to the present invention, any material may be used, such as paper coated with polyethylene or polyethylene terephthalate, paper support made of natural pulp or synthetic pulp, vinyl chloride sheet, white pigment. Polypropylene, polyethylene terephthalate support, baryta paper or the like which may be contained can be used. Among these, a support having a water-resistant resin coating layer on both sides of the base paper is preferable. As the water resistant resin, polyethylene, polyethylene terephthalate or a copolymer thereof is preferable.

As the support having a water-resistant resin coating layer on the surface of paper, a smooth surface having a mass of 50 to 300 g / m ² is usually used, but for the purpose of obtaining a proof image, a feeling of handling to approximate the printing paper, 130 g / m ² or less of the base paper is preferably used, it is preferably used further 70~120g / m ² base paper.

  The support used in the present invention can be preferably used even if it has random irregularities or is smooth.

  As the white pigment used for the support, inorganic and / or organic white pigments can be used, and inorganic white pigments are preferably used. For example, alkaline earth metal sulfate such as barium sulfate, alkaline earth metal carbonate such as calcium carbonate, silica such as fine silicate, synthetic silicate, calcium silicate, alumina, alumina hydrate, oxidation Examples include titanium, zinc oxide, talc, and clay. The white pigment is preferably barium sulfate or titanium oxide.

  The amount of the white pigment contained in the water-resistant resin layer on the surface of the support is preferably 13% by mass or more, and more preferably 15% by mass for improving sharpness.

  The degree of dispersion of the white pigment in the water-resistant resin layer of the paper support according to the present invention can be measured by the method described in JP-A-2-28640. When measured by this method, the degree of dispersion of the white pigment is preferably 0.20 or less, and more preferably 0.15 or less, as the coefficient of variation described in the above publication.

  The resin layer of the paper support having water-resistant resin layers on both sides used in the present invention may be a single layer or a plurality of layers. When a plurality of layers are used and a white pigment is contained at a high concentration in the contact with the emulsion layer, sharpness is greatly improved.

  Further, it is more preferable that the value of the center plane average roughness (SRa) of the support is 0.15 μm or less, and further 0.12 μm or less, because the effect of good gloss is obtained.

  The photosensitive material according to the present invention is subjected to corona discharge, ultraviolet irradiation, flame treatment, etc. on the support surface as necessary, and then directly or undercoat layer (adhesion of the support surface, antistatic properties, dimensional stability) May be applied via one or more subbing layers to improve the properties, friction resistance, hardness, antihalation properties, frictional properties or other properties.

  When coating a light-sensitive material using a silver halide emulsion, a thickener may be used to improve the coating property. As the coating method, extrusion coating and curtain coating capable of simultaneously coating two or more layers are particularly useful.

  EXAMPLES Hereinafter, although an Example is given and this invention is demonstrated in detail, this invention is not limited to these. Unless otherwise specified, “%” in the examples represents “mass%”.

Example 1
<< Production of photosensitive material >>
Color paper, which is a photosensitive material for reflection viewing, was prepared according to the following method.

High-density polyethylene was laminated on both sides of a paper pulp having a basis weight of 180 g / m ² to prepare a paper support. However, the reflective support A was prepared by laminating a melted polyethylene containing a dispersion of anatase-type titanium oxide (content: 15% by mass) on the side on which each emulsion layer was applied. After this reflective support A was subjected to corona discharge treatment, a gelatin subbing layer was provided, and each constituent layer having the constitution shown in Tables 1 and 2 was further applied to produce a photosensitive material as color paper. However, in Tables 1 and 2, the addition amount of the silver halide emulsion is described in terms of silver.

In the production of the photosensitive material, (H-1) and (H-2) were added as hardeners. As coating aids, surfactants (SU-2) and (SU-3) were added to adjust the surface tension. Further, F-1 was added to each layer so that the total amount was 0.04 g / m ² .

  The details of each additive listed in Tables 1 and 2 are as follows.

SU-1: Sodium tri-i-propylnaphthalenesulfonate SU-2: Disulfosulfonic acid di (2-ethylhexyl) sodium SU-3: Disulfosulfonic acid di (2,2,3,3,4,4,5 , 5, -octafluoropentyl) .sodium DBP: dibutyl phthalate DNP: dinonyl phthalate DOP: dioctyl phthalate DIDP: di-i-decyl phthalate H-1: tetrakis (vinylsulfonylmethyl) methane H-2: 2,4- Dichloro-6-hydroxy-s-triazine sodium HQ-1: 2,5-di-t-octyl hydroquinone HQ-2: 2,5-di-sec-dodecyl hydroquinone HQ-3: 2,5-di-sec -Tetradecyl hydroquinone HQ-4: 2-sec-dodecyl-5-sec-tetradecyl Dorokinon HQ-5: 2,5-di [(1,1-dimethyl-4-hexyloxycarbonyl) butyl] hydroquinone image stabilizer A: p-t-octylphenol image stabilizer B: poly (t-butylacrylamide)

(Preparation of silver halide emulsion)
<Preparation of blue-sensitive silver halide emulsion>
EMP-1, which is a monodispersed cubic emulsion having an average particle size of 0.71 μm, a coefficient of variation of particle size distribution of 0.07, and a silver chloride content of 99.5 mol%, was prepared according to a conventional method. Next, EMP-1B, a monodispersed cubic emulsion having an average particle size of 0.64 μm, a coefficient of variation of particle size distribution of 0.07, and a silver chloride content of 99.5 mol%, was prepared according to a conventional method.

  The following compounds were used for the EMP-1, and chemical sensitization was performed so as to optimize the sensitivity-fogging relationship. Similarly, EMP-1B is chemically sensitized so that the sensitivity-fogging relationship is optimized, and then sensitized EMP-1 and EMP-1B are mixed in a silver ratio of 1: 1. A blue-sensitive silver halide emulsion (Em-B) was prepared.

Sodium thiosulfate 0.8mg / mol AgX
Chloroauric acid 0.5mg / mol AgX
Stabilizer: STAB-1 3 × 10 ⁻⁴ mol / mol AgX
Stabilizer: STAB-2 3 × 10 ⁻⁴ mol / mol AgX
Stabilizer: STAB-3 3 × 10 ⁻⁴ mol / mol AgX
Sensitizing dye: BS-1 4 × 10 ₋₄ mol / mol AgX
Sensitizing dye: BS-2 1 × 10 ⁻⁴ mol / mol AgX
<Preparation of green sensitive silver halide emulsion>
EMP-2, a monodispersed cubic emulsion having an average particle size of 0.40 μm, a coefficient of variation of 0.08, and a silver chloride content of 99.5%, was prepared according to a conventional method. Next, EMP-2B, a monodispersed cubic emulsion having an average particle size of 0.50 μm, a coefficient of variation of 0.08, and a silver chloride content of 99.5%, was prepared according to a conventional method.

  The following compounds were used for the EMP-2, and chemical sensitization was performed so that the sensitivity-fogging relationship was optimized. Similarly for EMP-2B, after chemical sensitization so that the sensitivity-fogging relationship is optimized, sensitized EMP-2 and EMP-2B are mixed at a silver ratio of 1: 1. A green sensitive silver halide emulsion (Em-G) was prepared.

Sodium thiosulfate 1.5mg / mol AgX
Chloroauric acid 1.0mg / mol AgX
Stabilizer: STAB-1 3 × 10 ⁻⁴ mol / mol AgX
Stabilizer: STAB-2 3 × 10 ⁻⁴ mol / mol AgX
Stabilizer: STAB-3 3 × 10 ⁻⁴ mol / mol AgX
Sensitizing dye: GS-1 4 × 10 ⁻⁴ mol / mol AgX
<Preparation of red-sensitive silver halide emulsion>
EMP-3, a monodispersed cubic emulsion having an average particle size of 0.40 μm, a coefficient of variation of 0.08, and a silver chloride content of 99.5%, was prepared according to a conventional method. EMP-3B, a monodispersed cubic emulsion having an average particle size of 0.38 μm, a coefficient of variation of 0.08 and a silver chloride content of 99.5%, was prepared according to a conventional method.

  The following compounds were used for EMP-3, and chemical sensitization was performed so that the sensitivity-fogging relationship was optimized. Similarly for EMP-3B, after chemical sensitization so that the sensitivity-fogging relationship is optimized, sensitized EMP-3 and EMP-3B are mixed in a silver ratio of 1: 1. A red-sensitive silver halide emulsion (Em-R) was prepared.

Sodium thiosulfate 1.8mg / mol AgX
Chloroauric acid 2.0mg / mol AgX
Stabilizer: STAB-1 3 × 10 ⁻⁴ mol / mol AgX
Stabilizer: STAB-2 3 × 10 ⁻⁴ mol / mol AgX
Stabilizer: STAB-3 3 × 10 ⁻⁴ mol / mol AgX
Sensitizing dye: RS-1 1 × 10 ⁻⁴ mol / mol AgX
Sensitizing dye: RS-2 1 × 10 ⁻⁴ mol / mol AgX
Details of the respective compounds used for the preparation of the above silver halide emulsions are as follows.

STAB-1: 1- (3-acetamidophenyl) -5-mercaptotetrazole STAB-2: 1-phenyl-5-mercaptotetrazole STAB-3: 1- (4-ethoxyphenyl) -5-mercaptotetrazole and red photosensitivity To the silver halide emulsion, SS-1 was added at 2.0 × 10 ⁻³ mol per mol of silver halide.

"Evaluation methods"
The produced photosensitive material was subjected to wedge exposure according to a conventional method, and developed under the following processing solution and development processing conditions. Separately from this, the color development and the bleach-fixing treatment were performed under the same conditions, and then a sample washed with running water at 35 to 40 ° C. for 5 minutes was also prepared. The blue reflection density (Dmin) of the lowest density part of both was measured with an X-rite densitometer, and the yellow stain immediately after the treatment was evaluated by the following equation.

(Yellow stain immediately after treatment) = (Dmin of sample subjected to stabilization treatment) − (Dmin of sample subjected to washing treatment)
In addition, the stabilized sample was subjected to forced deterioration storage by irradiating 70,000 lx light for 7 days with ATLAS Ci4000 Xenon Weather Ometer, and the blue reflection density (Dmin) of the lowest density part was measured in the same manner, and after storage The increase in yellow stain was evaluated by the following formula.

(Yellow stain increase after storage) = (Dmin of sample after storage) − (Dmin of sample before storage)
The evaluation results are shown in Table 3.

<< Development processing condition 1 >>
Processing step Processing temperature Processing time Color development 45.0 ° C 22 seconds Bleach fixing 42.5 ° C 22 seconds Stabilization (1) 40.0 ° C 15 seconds Stabilization (2) 40.0 ° C 15 seconds Stabilization (3) 40 0 ° C for 15 seconds Stabilization (4) 40.0 ° C for 15 seconds Drying 60-80 ° C for 30 seconds
Color developer: 10.0g diethylene glycol per liter
Sodium p-toluenesulfonate 10.0g
Potassium chloride 4.0g
Diethylenetriaminepentaacetic acid 6.0g
Triazinyl stilbene fluorescent whitening agent (IV-15) 1.0g
N, N-bis (sulfoethyl) hydroxylamine disodium salt 5.0 g
Potassium carbonate 28.0g
4-Amino-3-methyl-N-ethyl-N- (β-methanesulfonamidoethyl) aniline 2/3 sulfate 6.0 g
pH 10.00
Water was added to 1 L, and the pH was adjusted with potassium hydroxide solution or sulfuric acid.

Bleach-fixing solution: 0.20 mol of ethylenediaminetetraacetic acid ferric ammonium per liter
Ammonium thiosulfate 0.54 mol
Ammonium sulfite 0.15 mol
Succinic acid 20.0g
Nitric acid (67%) 10.0 g
pH 6.0
Water was added to 1 L, and the pH was adjusted with potassium hydroxide solution or sulfuric acid.

Stabilizing liquids (1) to (3): 1 g of ethylenediaminetetraacetic acid disodium 2.0 g per liter
Sodium sulfite 0.7g
Sodium benzenesulfinate 0.8g
Compounds of general formulas (I) to (III) (types listed in Table 3) Amounts listed in Table 3 pH 7.5
Water was added to 1 L, and the pH was adjusted using an aqueous ammonia solution or sulfuric acid.

Stabilizing liquid (4): 1 g ethylenediaminetetraacetic acid disodium 2.0 g
Sodium sulfite 0.7g
Sodium benzenesulfinate 0.8g
Compounds of general formulas (I) to (III) (types listed in Table 3) Amounts listed in Table 3 Absorbance adjusting compounds listed in Table 3 Added so that the absorbance at 440 nm becomes the value listed in Table 3 pH 7.5
Water was added to 1 L, and the pH was adjusted using an aqueous ammonia solution or sulfuric acid.

  From Table 3, when the compounds represented by the general formulas (I) to (III) according to the present invention are contained in the stabilizing solution, yellow stain immediately after the treatment is reduced, while yellow stain increase after storage is remarkable. become. On the other hand, by reducing the absorbance at 440 nm of the stabilizing solution (4), which is the final treatment bath, to a range of 0.05 to 0.5, both reduction of yellow stain immediately after treatment and reduction of yellow stain increase after storage are achieved. I understand that I can do it.

Example 2
Evaluation was performed in the same manner as in Example 1 except that the development processing conditions were changed as follows. However, forced deterioration preservation by light irradiation was extended to 10 days.

<< Development processing condition 2 >>
Processing step Processing temperature Processing time Color development 45.0 ° C 22 seconds Bleach fixing 42.5 ° C 22 seconds Stabilization (1) 40.0 ° C 12 seconds Stabilization (2) 40.0 ° C 12 seconds Stabilization (3) 40 0.0 ° C. 12 seconds Stabilization (4) 40.0 ° C. 12 seconds Drying 60-80 ° C. 30 seconds Table 4 shows the evaluation results.

From Table 4, the effect of the present invention is particularly remarkable when the amount of the compound represented by the general formulas (I) to (III) according to the present invention is 5 × 10 ⁻⁵ to 1 × 10 ⁻² mol. It turns out that it is.

Example 3
Experiment No. 2 of Example 2 In 2-3, the same evaluation was performed by changing the pH of the stabilizer (4) as shown in Table 5.

  The evaluation results are shown in Table 5.

  From Table 5, it can be seen that the effect of the present invention is particularly remarkable when the pH of the treatment liquid in contact with the liquid at the end of the treatment step is 4 to 9.

Example 4
In Example 2, the same evaluation was performed by changing the types of the compounds represented by the general formulas (I) to (III) according to the present invention as shown in Table 6. However, the addition amount of the compounds represented by the general formulas (I) to (III) is 0.001 mol / L, and the addition amount of EDTA-Fe is adjusted so that the absorbance at 440 nm is about 0.1, A stabilizing solution was prepared.

  The evaluation results are shown in Table 6.

  From Table 6, among the compounds represented by the general formula (I), the compounds represented by the general formula (II) or (III) are more preferable, and further represented by the general formulas (II-1) to (II-4). It can be seen that the compounds are particularly preferred.

Example 5
"Evaluation methods"
The automatic developing machine NPS-808GOLD manufactured by Konica Minolta Co., Ltd. was modified, and the photosensitive material produced in Example 1 was subjected to imagewise exposure and continuous processing (running processing) under the following processing conditions and processing solution. In the processing, the automatic developing machine was operated for 12 hours per day, and a total of 300 m ² of photosensitive material was run for 25 days at 12 m ² per day.

<< Development processing condition 3 >>
Processing step Processing temperature Processing time Tank capacity Replenishment amount Color development 45.0 ° C 22 seconds 12.5L 45ml / m ²
Bleach fixing 42.5 ° C 22 seconds 12.3L 35ml / m ²
Stabilization-(1) 40.0 ° C 15 seconds 11.8L
Stabilization-(2) 40.0 ° C 15 seconds 12.0L
Stabilization-(3) 40.0 ° C 15 seconds 12.5L 120ml / m ²
Drying 60 to 80 ° C. 30 seconds Stabilization is a countercurrent system from (3) → (2) → (1).

<Processing liquid composition>
The tank liquid and replenisher are shown below.

Color developer: per liter
Tank liquid Replenisher Diethylene glycol 10.0 g 10.0 g
Sodium p-toluenesulfonate 10.0 g 10.0 g
Potassium chloride 4.0 g −
Diethylenetriaminepentaacetic acid 6.0 g 6.0 g
Triazinyl stilbene fluorescent whitening agent (IV-15)
1.0g 1.0g
N, N-bis (sulfoethyl) hydroxylamine disodium salt
5.0g 11.0g
Potassium carbonate 28.0g 28.0g
4-Amino-3-methyl-N-ethyl-N- (β-methanesulfonamidoethyl) aniline 2/3 sulfate 6.0 g 12.0 g
Compounds of general formulas (I) to (III) (types listed in Table 7) Amounts listed in Table 7 pH 10.00 12.10
Water was added to 1 L, and the pH was adjusted with potassium hydroxide solution or sulfuric acid.

Bleach fixer: per liter
Tank liquid Replenisher Ferric ammonium tetraacetate 0.20 mol 0.37 mol
Ammonium thiosulfate 0.54 mol 1.00 mol
Ammonium sulfite 0.15 mol 0.25 mol
Succinic acid 20.0 g 38.0 g
Compounds of general formulas (I) to (III) (types listed in Table 7) Amounts listed in Table 7 Nitric acid (67%) 10.0 g 16.0 g
pH 6.0 4.8
Water was added to 1 L, and the pH was adjusted with potassium hydroxide solution or sulfuric acid.

Stabilizing liquid: per liter
Tank liquid = replenisher ethylenediaminetetraacetic acid disodium 2.0g
Sodium sulfite 0.7g
Sodium benzenesulfinate 0.8g
Triazinyl stilbene fluorescent whitening agent (IV-15) 1.0g
Exemplified Compound II-3-4 No addition or 0.001 mol
pH 7.5
Water was added to 1 L, and the pH was adjusted using an aqueous ammonia solution or sulfuric acid.

  After the running, the absorbance at 440 nm of the stabilization- (3) treatment solution, which is the final treatment bath, was measured. The photosensitive material prepared in Example 1 was subjected to wedge exposure according to a conventional method and developed under the above conditions. This is designated as sample A. Another sample A was prepared in the same procedure, and this was washed with running water at 35 to 40 ° C. for 10 minutes. This is designated as sample A '. Next, 1-hydroxyethylidene-1,1-diphosphonic acid trisodium was added to the stabilization- (3) treatment solution to adjust the absorbance at 440 nm to 0.30. Next, the photosensitive material similarly subjected to the wedge exposure was processed in the same manner. This is designated as Sample B. Another sample B was prepared in the same procedure, and this was washed with running water at 35 to 40 ° C. for 10 minutes. This is designated as Sample B '.

  The blue reflection density (Dmin) of the lowest density part of samples A, A ′, B, and B ′ was measured with a densitometer manufactured by X-rite, and the yellow stain immediately after the treatment was evaluated by the following equation.

(Yellow stain of sample A) = (Dmin of sample A) − (Dmin of sample A ′)
(Yellow stain of sample B) = (Dmin of sample B) − (Dmin of sample B ′)
Further, for samples A and B, forced degradation storage was performed by irradiating 70,000 lx light for 7 days with ATLAS Ci4000 Xenon Weather Ometer, and the blue reflection density (Dmin) of the lowest density part was measured in the same manner. The increase in yellow stain was evaluated by the following formula.

(Yellow stain increase after storage) = (Dmin of sample after storage) − (Dmin before storage)
Table 7 shows the evaluation results.

  From Table 7, good results are obtained when the compounds represented by the general formulas (I) to (III) according to the present invention are contained and the absorbance at 440 nm of the final treatment bath is within the range of the present invention. You can see that

It is a block diagram of a general automatic processor used for color paper processing.

Explanation of symbols

8 Automatic developing machine 110 Color developing tank 120 Bleach fixing tank 130A Stabilizing tank (1)
130B Stabilization tank (2)
130C Stabilization tank (3)
160 Drying room

Claims (6)

In the method for processing a photosensitive material, the processing solution in contact with the photosensitive material at the end of the processing step contains a compound represented by the following general formula (I), and the absorbance at 440 nm of the processing solution is 0.05 to A processing method of a photosensitive material, characterized in that it is 0.5.

(In the formula, A ₁ and A ₂ each independently represent a hydrogen atom, a halogen atom, an aryl group, a heterocyclic group or an alkyl group, and Y represents a hydrogen atom, a thiol group, a halogen atom, a carboxyl group, a sulfo group, a hydroxylamino group. A group, —NR ₁ R ₂ , —SR ₃ or —OR ₃ ; W ₁ represents a single bond, —O—, —S— or —NR ₄ —, and W ₂ represents —O—, —S—. Or represents —NR ₄ —, wherein R ₁ , R ₂ , R ₃ and R ₄ each represents a hydrogen atom, an alkyl group, an alkenyl group, an aryl group or a heterocyclic group, R ₁ and R ₂ , R ₄ and A ₁ And R ₄ and A ₂ may be bonded to each other to form a ring, provided that the molecule represented by the general formula (I) does not have an azo group or a diaminostilbene structure. .) 2. The processing of a photosensitive material according to claim 1, wherein the concentration of the compound represented by the general formula (I) is 5 × 10 ⁻⁵ to 1 × 10 ⁻² mol per liter of the processing solution. Method. 3. The method for processing a photosensitive material according to claim 1, wherein the processing solution contains an iron salt. 4. The method for processing a photosensitive material according to claim 1, wherein the processing solution has a pH of 4 to 9. 5. The photosensitive material according to claim 1, wherein the compound represented by the general formula (I) is a compound represented by the following general formula (II) or (III). Processing method.

Wherein X ₁ , X ₂ , Y ₁ and Y ₂ are each independently —N (R ₁ ) R ₂ , —OR ₃ , —SR ₃ , a heterocyclic group, a hydroxyl group, a hydroxylamino group or a halogen atom. Z ₁ and Z ₂ each represent —NR ₄ —, —O— or —S—, L represents an arylene group, an alkylene group, an alkenylene group or a heterocyclic group, and R ₁ and R ₂ each represent hydrogen. Represents an atom, an alkyl group, an aryl group or a heterocyclic group, R ₃ represents an alkyl group, an aryl group or a heterocyclic group, and R ₄ represents a hydrogen atom, an aryl group, a heterocyclic group or an alkyl group, R ₁ and R ₂ may be bonded to form a nitrogen-containing heterocycle, provided that the molecule represented by the general formula (II) does not have an azo group or a diaminostilbene structure.

(In the formula, L ₁₂ and L ₁₃ may be the same or different and each represents an aryl group or a heterocyclic group; Q represents a hydrogen atom, a thiol group, a carboxyl group, a sulfo group, —NR ₅ R ₆ , —OR; ₇ represents a hydroxylamino group or a halogen atom, and R ₅ , R ₆ and R ₇ each represents a hydrogen atom, an alkyl group, an aryl group or a hetero group, and R ₅ and R ₆ are bonded to each other to form a ring. However, the molecule represented by the above general formula (III) contains at least one group represented by —SO ₃ M, —CO ₂ M or —OH, where M is hydrogen. Represents an atom, an alkali metal, an alkaline earth metal, ammonium or pyridinium, and does not have an azo group or a diaminostilbene structure in the molecule represented by the general formula (III). 6. The method for processing a photosensitive material according to claim 5, wherein the compound represented by the general formula (II) is a compound represented by the following general formulas (II-1) to (II-4): .

(In the formula, R _{11 to} R ₁₈ each independently represents a hydrogen atom, an alkyl group, an aryl group, or a heterocyclic group. L ₁ represents a phenylene group or a naphthylene group. Among R _{11 to} R ₁₈ , three or more. R ₁₁ and R ₁₂ , R ₁₃ and R ₁₄ , R ₁₅ and R ₁₆ , R ₁₇ and R ₁₈ may be bonded to each other to form a ring, provided that the general formula (II included in the molecule represented by _{-1), -SO 3 M, -CO} 2 M, based on containing at least one represented by -OH. here, M is an alkali metal ion, an alkaline earth metal ion (In addition, the compound represented by the general formula (II-1) does not contain a group represented by —N═N— or a diaminostilbene structure in the molecule.)

(In the formula, R _{21 to} R ₂₈ each independently represents a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group. L ₂ represents a phenylene group, a naphthylene group, an alkylene group or a heterocyclic group. Ra represents an alkyl group. Represents an aryl group or a heterocyclic group, and Rb represents a hydrogen atom, an alkyl group or an aryl group, R ₂₁ and R ₂₂ , R ₂₃ and R ₂₄ , R ₂₅ and R ₂₆ , R ₂₇ and R ₂₈ are bonded to each other. However, the compound represented by the general formula (II-2) contains at least one group represented by —SO ₃ M, —CO ₂ M, —OH in the molecule. Here, M represents an alkali metal ion, an alkaline earth metal ion or an ammonium ion, and the compound represented by the general formula (II-2) has a —N═N— or diaminostilbene structure in the molecule. Does not contain.)

(In the formula, R _{31 to} R ₃₄ each independently represents a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group. L ₃ represents a phenylene group, a naphthylene group, an alkylene group or a heterocyclic group. A ₃₁ , A ₃₂ each independently represents an alkoxy group, an aryloxy group, a heterocyclic oxy group, an alkylthio group, an arylthio group, a heterocyclic thio group or a hydroxylamino group, R ₃₅ and R ₃₆ each independently represent a hydrogen atom, an alkyl group, R ₃₁ and R ₃₂ , R ₃₃ and R ₃₄ may combine with each other to form a ring, provided that the compound represented by formula (II-3) is a molecule -SO ₃ M, -CO ₂ M, containing at least one group represented by -OH within. here, M represents an alkali metal ion, an alkaline earth metal ion or an ammonium ion. Luo, a compound represented by Formula (II-3) does not contain a group represented by -N = N-in a molecule.)

(Wherein L ₄ represents a phenylene group, a naphthylene group or an alkylene group. X ₁ represents an oxygen atom or a sulfur atom, X ₂ represents an oxygen atom, a sulfur atom or —NH—. A ₄₁ , A ₄₂ , A ₄₃ and A ₄₄ are each independently an alkoxy group, aryloxy group, heterocyclic oxy group, alkylthio group, arylthio group, heterocyclic thio group, hydroxylamino group, or —NR ₄₁ R ₄₂ (R ₄₁ and R ₄₂ are each independently Represents a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group, and R ₄₁ and R ₄₂ may be bonded to each other to form a ring), but represented by the general formula (II-4) _{compounds, -SO 3 M, -CO 2 M} , containing at least one of the groups represented by -OH in the molecule. here, M represents an alkali metal ion, an alkaline earth metal ion or an ammonium ion Further, the compound represented by Formula (II-4), does not contain a group or a diaminostilbene structure represented by -N = N-in a molecule.)

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