JP2006126417A - Concentrated blix solution composition for silver halide color photosensitive material - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a concentrated blix solution composition for a silver halide color photosensitive material which reduces container contamination at long-term storage. <P>SOLUTION: The concentrated blix solution composition for a silver halide color photographic sensitive material consists of a concentrated composition part, containing a bleaching agent and a concentrated composition part containing containing a fixing agent. The concentrated composition part, containing the bleaching agent, has pH 2.0-3.6 and contains a ferric complex salt of an aminopolycarboxylic acid and a nitrate, wherein the molar ratio between iron ions of the ferric complex salt and nitric acid ions of the nitrate is 1:2 to 1:6. The concentrated composition part, containing the bleaching agent, is housed in a container so that the container has a free volume of 3-30%, after housing. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a novel bleach-fixing solution concentrate composition for a silver halide color photographic light-sensitive material.

  In recent years, in the development processing of silver halide color photographic light-sensitive materials, silver halide color has been installed at the storefront of a photographic store in order to provide quick service to general users and streamline collection and delivery between the photographic store and a large-scale developer. An automatic developing processor called a minilab that performs processing of a photographic light-sensitive material has become widespread. If the processing agent used in the minilab is in the form of a liquid composition in which constituent chemicals are previously dissolved in a solvent such as water, when preparing the processing solution to be used, mixing and diluting with water are simple. There is an advantage that a treatment liquid can be prepared by a preparation operation, and it is often supplied in such a form. However, the form of the liquid composition requires a solvent such as water required for dissolving the processing agent component and a container for storing the composition, which is disadvantageous in terms of transportation costs. Therefore, the liquid composition is concentrated. In general, it is supplied in the form of a liquid concentrated composition with reduced volume.

  Further, the liquid concentrate composition used for bleach-fixing is a two-component composition having a higher stability than that of a single solution, that is, a concentrated composition part containing a bleaching agent (hereinafter also referred to as a bleaching agent part) and a fixing agent. Generally, it is composed of two parts of a concentrated composition part (hereinafter also referred to as a fixing agent part).

  On the other hand, in the development processing in the minilab, in addition to the above-mentioned convenience in transportation, as part of the user service, it is desired to reduce the replenishment for speeding up the development processing and reducing the amount of waste liquid generated during processing. In order to achieve low replenishment and speed-up in the bleach-fixing process where a bleach-fixing solution concentrate composition is used, it is necessary to increase the concentration of the bleaching agent and lower the pH to maintain the bleaching performance of the bleach-fixing solution. There is. When the pH of the fixing agent part is lowered, decomposition and precipitation of the fixing agent occur, and thus the pH of the fixing agent part cannot be lowered. However, when the pH of the bleach part is lowered and the concentration of the bleach is further increased, a fine black product is generated inside the container during storage in a high temperature environment such as summer, and this adheres to the inner wall of the container. As a result, there is a problem of reducing the commercial value. This container contamination cannot be easily removed by washing, making it difficult to recycle the waste container, and making it difficult to operate in terms of environmental protection.

For example, iron (III) / ethylenediamine disuccinic acid complex salt and / or iron (III) / ethylenediamine diglutamic acid complex salt as a bleaching agent against container stains resulting from the formation of black matter generated during high temperature storage Is disclosed as a one-part photographic bleach-fixing agent filled in a container having an oxygen supply rate of 10 ml / hr or less per liter of filler (see, for example, Patent Document 1). .) However, the technique described in Patent Document 1 requires a specific structure aminopolycarboxylic acid ferric complex salt and a container, and the proposed compounds and containers have high production costs and are economically disadvantageous. This makes general-purpose difficult. Further, the technology for increasing the concentration of the bleaching part under a low pH is composed of two parts, a concentrated composition part containing a bleaching agent and a concentrated composition part containing a fixing agent. Discloses a bleach-fixing solution concentrated composition for silver halide color photographic light-sensitive materials in which the pH, specific gravity, type of bleaching agent, bleaching agent concentration, and aminopolycarboxylic acid content are specified under specific conditions. For example, see Patent Document 2.) However, although the technique described in Patent Document 2 refers to the improvement of the precipitation property of the bleach-fixing solution concentrated composition, there is no mention or description regarding the solution of the container fouling which is the object effect of the present invention. .
JP 2000-98553 A JP 2004-53921 A

  The present invention has been made in view of the above problems, and an object of the present invention is to provide a bleach-fixing solution concentrated composition for a silver halide color photographic light-sensitive material with reduced container contamination during long-term storage.

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

(Claim 1)
A bleach-fixing solution concentrate composition for a silver halide color photographic light-sensitive material comprising two parts, a concentrated composition part containing a bleaching agent and a concentrated composition part containing a fixing agent, containing the bleaching agent The pH of the concentrated composition part is 2.0 to 3.6, contains aminopolycarboxylic acid ferric complex salt and nitrate, and contains moles of iron ions of the ferric complex salt and nitrate ions of the nitrate salt The ratio is 1: 2 to 1: 6, and the concentrated composition part containing the bleaching agent is stored in a container, and the porosity of the container after storage is 3 to 30%. A bleach-fixing solution concentrate composition for a silver halide color photographic light-sensitive material.

(Claim 2)
2. The bleach-fixing solution concentrated composition for a silver halide color photographic light-sensitive material according to claim 1, wherein the porosity is 5 to 20%.

(Claim 3)
The silver halide color photographic light-sensitive material according to claim 1 or 2, wherein the concentration of the ferric complex salt of aminopolycarboxylic acid is 0.4 mol / L or more and 1.0 mol / L or less. Bleach-fixing solution concentrate composition.

(Claim 4)
4. The concentrated composition part containing the bleaching agent contains at least one compound selected from the following general formulas (I) to (V): 4. A bleach-fixing solution concentrated composition for silver halide color photographic light-sensitive materials.

[Wherein, A ₁ and A ₂ each represents an aryl group or an aromatic heterocyclic group. However, the case where A ₁ is a triazinyl group is excluded. X represents a divalent linking group, and M represents a hydrogen atom, an alkali metal, an alkaline earth metal, ammonium or pyridinium. However, in the molecule | numerator represented by said general formula (I), group represented by -N = N- and -SH is not contained. n represents an integer of 2 to 4, and n X-A _2s may be the same or different, and r and s each represent an integer of 0 to 10, but r + s is 2 or more. When n is 2 and A ₁ is an aromatic heterocyclic group, the two X's each represent a divalent linking group other than N (R ₁ ), S or O, and R ₁ represents a hydrogen atom Or represents a C1-C6 alkyl group. ]

[Wherein, L ₁ and L ₂ each independently represents an aryl group, a heterocyclic group or an alkyl group, and at least one of them is an aryl group or a heterocyclic group. Y ₁ represents an amino group, a hydroxyl group, a halogen atom, a sulfo group, an alkylamino group or an alkoxy group. However, there is no conjugated bond between the two triazine rings. ]

[Wherein, L ₃ and L ₄ each independently represents an aryl group, a heterocyclic group or an alkyl group, and at least one of them is an aryl group or a heterocyclic group. R ₃ represents a hydrogen atom or an alkyl group. Y ₃ represents an amino group, a hydroxyl group, a halogen atom, a sulfo group, an alkylamino group or an alkoxy group. However, there is no conjugated bond between the two triazine rings. ]

[Wherein, R ₁₁ , R ₁₂ , R ₁₃ and R ₁₄ each represent a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group, and Q represents a hydrogen atom, a hydroxyl group, a thiol group, a carboxyl group, a sulfo group, —NR ₁₅ R ₁₆ , —OR ₁₇ or a halogen atom, and R ₁₅ , R ₁₆ and R ₁₇ each represent a hydrogen atom, an alkyl group, an aryl group or a hetero group. R ₁₁ and R ₁₂ , R ₁₃ and R ₁₄ , and R ₁₅ and R ₁₆ may be bonded to each other to form a ring. However, it contains at least one group represented by —SO ₃ M, —CO ₂ M or —OH in the molecule, where M represents a hydrogen atom, an alkali metal, an alkaline earth metal, ammonium or pyridinium. Also, three or more of R ₁₁ , R ₁₂ , R ₁₃ , R ₁₄ , R ₁₅ and R ₁₆ do not become an aryl group. Further, in the molecule represented by the general formula (IV), there is no conjugated bond between the two triazine rings, and no group represented by -N = N- is contained. ]

[Wherein, X ₁ , X ₂ , Y ₁ and Y ₂ are each an alkoxy group, an aryloxy group, a heterocyclic oxy group, a heterocyclic group, a hydroxyl group, an amino group, a chlorine atom, an alkyl group, an aryl group, or The group represented by general formula (Va) is represented. X and Y each represent NR ₄ , O or S, and R ₄ represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. L represents a phenylene group, a naphthyl group or a heterocyclic group. ]

[Wherein, R ₁ , R ₂ and R ₃ each represents an alkyl group, an aryl group or a heterocyclic group. ]

  According to the present invention, it is possible to provide a bleach-fixing solution concentrated composition for a silver halide color photographic light-sensitive material with reduced container contamination during long-term storage.

  Hereinafter, the best mode for carrying out the present invention will be described in detail.

  As a result of diligent investigations in view of the above problems, the present inventors have developed a silver halide color photographic light-sensitive material comprising two parts, a concentrated composition part containing a bleaching agent and a concentrated composition part containing a fixing agent. In the bleach-fixing solution concentrated composition for materials, the pH of the concentrated composition part containing the bleaching agent is 2.0 to 3.6, and contains aminopolycarboxylic acid ferric complex salt and nitrate, Concentrated composition part containing iron ions of ferric complex salt and nitrate ions of nitrate is 1: 2 to 1: 6, and containing the bleaching agent is stored in a container. When stored in a container for a long time with a bleach-fixing solution concentrated composition for a silver halide color photographic light-sensitive material, wherein the porosity of the container is 3 to 30%. The formation of degradation products in the concentrated composition It is greatly suppressed, As a result, it was possible to prevent the coloring of the storage container. Furthermore, by using the bleach-fixing solution concentrate composition of the present invention, it was possible to make processing suitability such as desilvering and recoloring during rapid processing possible.

  Hereinafter, the present invention will be described in detail.

  The bleach-fixing solution concentrated composition for silver halide color photographic light-sensitive materials of the present invention (hereinafter also simply referred to as the bleach-fixing solution concentrated composition of the present invention) contains a concentrated composition part containing a bleaching agent and a fixing agent. It consists of two parts with a concentrated composition part.

  First, the bleaching agent part according to the bleach-fixing solution concentrated composition of the present invention will be described.

  In the present invention, one of the features is that the pH of the bleaching agent part according to the present invention is 2.0 to 3.6, and more preferably 2.5 to 3.3.

  Moreover, in the bleaching agent part which concerns on this invention, aminopolycarboxylic acid ferric complex salt and nitrate are contained, and the content molar ratio of the iron ion of ferric complex salt and the nitrate ion of nitrate is 1: 2-1: 6 is one feature, and preferably in the range of 1: 3 to 1: 5.

  By containing the above pH range and iron ions and nitrate ions in the above molar ratio, coloring of the storage container can be suppressed, and furthermore, low replenishment and good processing suitability during rapid processing can be obtained.

  The content of the aminopolycarboxylic acid ferric complex salt is preferably in the range of 0.4 to 1.0 mol / L, more preferably 0.5 to 0.8 mol / L. Suppression of container expansion due to coloration of the water and generation of decomposition gas and the like, and good processability during low replenishment and rapid processing can be obtained.

  Examples of the aminopolycarboxylic acid ferric complex salts that can be used in the present invention include ethylenediamine disuccinic acid (S, S form), N- (2-carboxylateethyl) -L-aspartic acid, and beta-alanine diacetic acid. Aminopolyesters such as methyliminodiacetic acid, ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, 1,3-diaminopropanetetraacetic acid, propylenediaminetetraacetic acid, nitrilotriacetic acid, cyclohexanediaminetetraacetic acid, iminodiacetic acid, glycol etherdiaminetetraacetic acid The ferric complex salt with carboxylic acid can be mentioned, The sodium salt, potassium salt, lithium salt, or ammonium salt of these compounds can be mentioned.

  Among these compounds, ethylenediamine disuccinic acid (S, S form), N- (2-carboxylateethyl) -L-aspartic acid, ethylenediaminetetraacetic acid, 1,3-diaminopropanetetraacetic acid, methyliminodioxy A ferric complex salt of acetic acid is preferred from the viewpoint of good bleaching performance. These ferric complex salts may be used in the form of complex salts, for example, ferric sulfate, ferric chloride, ferric nitrate, ferric ammonium sulfate, ferric phosphate, and the amino acids described above. It may be complexed with a polycarboxylic acid in solution.

  The molar ratio of the aminopolycarboxylic acid and iron ion is preferably in the range of aminopolycarboxylic acid: iron ion = 1.001 to 1.10: 1.00 from the stability of the chelate structure. .

  In addition to the aminopolycarboxylic acid ferric complex salt according to the present invention, other known bleaching agents can be used in combination. Examples of bleaching agents that can be used in combination include ferric complex salts of organic acids such as citric acid, tartaric acid, malic acid, persulfates, hydrogen peroxide, and the like.

  Examples of the nitrate include ammonium nitrate, sodium nitrate and potassium nitrate. The range contained in the bleaching agent part is preferably 0.5 to 7.0 mol / L from the stability of the concentrated composition. is there.

  The bleach part according to the present invention includes various organic acid salts (for example, acetic acid, lactic acid, glycolic acid, succinic acid, maleic acid, malonic acid, citric acid, sulfosuccinic acid, citric acid to adjust to the above pH. , Tartaric acid, glutaric acid, lactic acid, etc.), organic bases (eg, imidazole, dimethylimidazole, etc.), 2-picolinic acid, kojic acid, and the like. The amount of these compounds added is preferably 0.05 to 3.0 mol, more preferably 0.2 to 1.0 mol, per liter of the prepared processing solution (tank solution (use solution), replenisher solution).

  In addition to the above compounds, halides such as chloride, bromide and iodide may be added as a rehalogenating agent for promoting the oxidation of silver. In addition, an organic ligand that forms a sparingly soluble silver salt may be added in place of the halide, and the halide can be added as an alkali metal salt or ammonium salt, or a salt of guanidine, amine, or the like. Specific examples include sodium bromide, potassium bromide, ammonium bromide, potassium chloride, guanidine hydrochloride and the like. The amount added is preferably in the range where the concentration when prepared as a treatment liquid is 0.01 to 2.0 mol per liter.

  In addition, it is preferable to use ammonium ions in the bleaching part according to the present invention when processing properties are considered. On the other hand, when emphasizing work environment, it is preferable that the ammonium ions are not substantially contained. preferable.

  In addition to the constitution specified above, the bleach part according to the present invention contains at least one compound selected from the general formulas (I) to (V), so that the harsh storage conditions are Therefore, it is preferable in that it can suppress the coloring of the storage container, which is the object effect of the present invention, and the expansion of the container due to the generation of decomposition gas and the like.

  Hereinafter, the compounds represented by formulas (I) to (V) according to the present invention will be described.

  First, the compound represented by the general formula (I) will be described.

In the general formula (I), A ₁ and A ₂ each represent an aryl group or an aromatic heterocyclic group, and the aryl group preferably has 6 to 20 carbon atoms, more preferably 6 to 10 carbon atoms. And particularly preferably an aryl group having 6 to 8 carbon atoms, such as a phenyl group, a naphthyl group, a 3-carboxyphenyl group, a 4-carboxyphenyl group, a 3,5-dicarboxyphenyl group, a 4-methoxyphenyl group, Examples include 2-sulfophenyl group, 4-sulfophenyl group, 5,7-disulfo-2-naphthyl group, 3,6-disulfo-2-naphthyl, and anthranyl group. The aromatic heterocyclic group preferably has 2 to 20 carbon atoms, more preferably 2 to 10 carbon atoms, and particularly preferably a 5- or 6-membered heterocyclic group having 2 to 8 carbon atoms. , 2-furyl group, 2-pyrimidinyl group, 3,5- (1,2,4-triazole) -diyl group, 3,5-isothiazolediyl group, 2,6-pyridinediyl group, 2,6-pyrazinediyl Group, 2,6-pyrimidinediyl group, 3,6-pyridazinediyl group, 1,4-phthalazinediyl group.

X represents a divalent linking group. For example, —CH (R ₁ ) —, —NR ₁ —, —S—, —O—, —CON (R ₁ ) —, —SO ₂ N (R ₁ ) — , -CO ₂ - include groups represented by, as the substituent represented by R _1, for example, include a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, examples of the alkyl group, for example, Examples include a methyl group, an ethyl group, an i-propyl group, and an n-propyl group. A group represented by —CON (R ₁ ) —, —SO ₂ N (R ₁ ) —, or —CO ₂ — is preferable. The —SO ₃ M group or —CO ₂ M group may be present in any of the molecules represented by the general formula (I). That, -SO ₃ M group or -CO ₂ M groups is bonded directly to A ₁ and / or A _2, or preferably present in a substituent on A ₁ and / or A _2. Alternatively, the —SO ₃ M group or —CO ₂ M group may be directly bonded to X or present in a substituent on X. Further, other substituents may be present on A ₁ and A ₂ . M is a hydrogen atom, an alkali metal, an alkaline earth metal, ammonium or pyridinium. Of these, alkali metals and alkaline earth metals are preferable, and Na and K are particularly preferable. Examples of the ammonium group include ammonium, triethylammonium, and tetrabutylammonium, among which ammonium is preferable. n represents an integer of 2 to 4, and r and s each represents an integer of 0 to 10. r and s are each preferably an integer of 1 to 6. R + s is 2 or more, preferably an integer of 2-6.

  Specific examples of the compound represented by formula (I) are shown below, but the present invention is not limited thereto.

  Next, the compounds represented by the general formulas (II) and (III) according to the present invention will be described in detail.

In the general formula (II) or (III), L ₁ and L ₂ each independently represents an aryl group, a heterocyclic group or an alkyl group, and L ₁ and L ₂ do not simultaneously become an alkyl group. L ₃ and L ₄ each independently represents an aryl group, a heterocyclic group or an alkyl group, and L ₃ and L ₄ do not simultaneously become an alkyl group. The aryl group, heterocyclic group and alkyl group include those having a substituent. However, the aryl group does not have a stilbene skeleton.

When L ₁ , L ₂ , L ₃ and L ₄ are each an aryl group, the carbon number thereof is preferably 6-20, more preferably 6-15, particularly preferably 6-10, A phenyl group, 4-methoxyphenyl group, 4-toluyl group, and naphthyl group are mentioned. The aryl group preferably has a water-soluble group. Examples of the water-soluble group include a sulfo group, a carboxyl group, a hydroxyl group, a carbamoyl group, and a sulfamoyl group, and a sulfo group and a carboxyl group are particularly preferable. Specifically, 3-carboxyphenyl group, 4-carboxyphenyl group, 2-sulfophenyl group, 4-sulfophenyl group, 2-methyl-4-sulfophenyl group, 2,5-disulfophenyl group, 4- Examples thereof include a sulfo-1-naphthyl group, a 6,8-disulfo-2-naphthyl group, and a 5,7-disulfo-2-naphthyl group.

When L ₁ , L ₂ , L ₃ and L ₄ 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. A monovalent group obtained by removing one hydrogen atom from a 5- or 6-membered aromatic or non-aromatic heterocyclic compound, such as 2-furyl group, 2-thienyl group, 2-pyrimidinyl group, 2 -A benzothiazolyl group is mentioned.

When L ₁ , L ₂ , L ₃ and L ₄ are each an alkyl group, the number of carbon atoms is preferably 1-20, more preferably 1-8, and particularly preferably 1-4, Examples thereof include a methyl group, an ethyl group, an isopropyl group, and a 2-methoxyethyl group. The alkyl group is preferably substituted with a water-soluble group. Examples of the water-soluble group include a sulfo group, a carboxyl group, a hydroxyl group, a carbamoyl group, and a sulfamoyl group, and the sulfo group, the carboxyl group, and the hydroxyl group include Particularly preferred, for example, sulfomethyl group, 2-sulfoethyl group, 1,2-dicarboxyethyl, 2-hydroxyethyl group, 3-hydroxypropyl group, 2-hydroxypropyl group, 2,3-dihydroxypropyl group, 3,4 -Dihydroxybutyl group, 2- (2-hydroxyethoxy) ethyl group, 2- [2- (2-hydroxyethoxy) ethoxy] ethyl group may be mentioned.

R ₃ represents a hydrogen atom or an alkyl group, and includes those having a substituent. When it is an alkyl group, it is preferable that it is C1-C20, More preferably, it is 1-8, Most preferably, it is a 1-4 alkyl group. Examples thereof include a methyl group, an ethyl group, an isopropyl group, and a 2-methoxyethyl group. The alkyl group may be substituted with a water-soluble group. Examples of the water-soluble group include a sulfo group, a carboxyl group, a hydroxyl group, a carbamoyl group, and a sulfamoyl group, and a sulfo group, a carboxyl group, and a hydroxyl group are particularly preferable. Preferably, for example, sulfomethyl group, 2-sulfoethyl group, 1,2-dicarboxyethyl, 2-hydroxyethyl group, 3-hydroxypropyl group, 2-hydroxypropyl group, 2,3-dihydroxypropyl group, 3,4- A dihydroxybutyl group, a 2- (2-hydroxyethoxy) ethyl group, and a 2- [2- (2-hydroxyethoxy) ethoxy] ethyl group may be mentioned.

Y ₁ represents an unsubstituted amino group, a hydroxyl group, a halogen, an alkylamino group or an alkoxy group which may be substituted, and the alkylamino group and alkoxy group which may be substituted are represented by the following general formulas (a) to (c ).

General formula (a)
-NH-R ₃₁
General formula (b)
-N (R ₃₁₎ -R ₃₂
Formula (c)
-O-R ₃₃
In the general formulas (a) to (c), R ₃₁ , R ₃₂ and R ₃₃ each represents an alkyl group, and the alkyl group preferably has 1 to 20 carbon atoms, more preferably 1 to 8, particularly Preferably it is 1-4 alkyl groups, 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, sulfomethyl group, 2-hydroxyethyl Group, 3-hydroxypropyl group, 2-hydroxypropyl group, 2-sulfoethyl group, 1,2-dicarboxyethyl group.

  Further, when the compounds represented by the general formula (II) and the general formula (III) have a carboxyl group or a sulfo group, these may be free forms or salts. Examples of the salt include alkali metals and alkaline earth metals. , Ammonium groups such as ammonium, triethylammonium, tetrabutylammonium and the like, and pyridinium, preferably alkali metals and alkaline earth metals, and more preferably sodium and potassium.

  Hereinafter, although the specific example of the compound represented by general formula (II) and general formula (III) which concerns on this invention is shown, this invention is not limited to these.

  When the compound represented by the general formula (II) or general formula (III) according to the present invention described above has a plurality of asymmetric carbons in the molecule, a plurality of stereoisomers exist for the same structure. The present invention shows all possible stereoisomers, and only one of a plurality of stereoisomers can be used, or several of them can be used as a mixture.

  Next, the compound represented by formula (IV) according to the present invention will be described.

In the general formula (IV), when R ₁₁ , R ₁₂ , R ₁₃ and R ₁₄ are each represented by an alkyl group, the alkyl group preferably has 1 to 20 carbon atoms, more preferably 1 -8, particularly preferably 1-4 alkyl groups, for example, methyl group, ethyl group, i-propyl group, n-propyl group, n-octyl group, sulfomethyl group, 2-hydroxyethyl group, 3-hydroxy group. Propyl 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- Examples include a pentahydroxyhexyl group.

When R ₁₁ , R ₁₂ , R ₁₃ and R 14 are each represented by an aryl group, the aryl group preferably has 6 to 20 carbon atoms, more preferably 6 to 10 carbon atoms, particularly preferably 6 to 8 carbon atoms. An aryl group, for example, phenyl group, naphthyl group, 3-carboxyphenyl group, 4-carboxyphenyl group, 3,5-dicarboxyphenyl group, 4-methoxyphenyl group, 2-sulfophenyl group, 4-sulfophenyl Groups.

When R ₁₁ , R ₁₂ , R ₁₃ and R ₁₄ are each represented by a heterocyclic group, the heterocyclic group preferably has 2 to 20 carbon atoms, more preferably 2 to 10 carbon atoms, particularly preferably. A monovalent group obtained by removing one hydrogen atom from a 5- or 6-membered aromatic or non-aromatic heterocyclic compound having 3 to 8 carbon atoms, such as a 2-furyl group, a 2-thienyl group, 2 -A pyrimidinyl group and 2-benzothiazolyl group are mentioned.

R ₁₁ , R ₁₂ , R ₁₃ and R ₁₄ are preferably a hydrogen atom, an alkyl group or an aryl group, more preferably a hydrogen atom, a methyl group, an ethyl group, an n-propyl group, a 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, 2,3-dihydroxypropyl group, 3,4-dihydroxybutyl group, phenyl group, 3-carboxyphenyl group, 4-carboxyphenyl group, 3,5-dicarboxyphenyl group, 4-methoxyphenyl group, 2- A sulfophenyl group and a 4-sulfophenyl group, more preferably a hydrogen atom, a methyl group, an ethyl group, a sulfomethyl group, -Hydroxyethyl 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-sulfophenyl group, more preferably hydrogen atom, methyl group, sulfomethyl group, 2-hydroxyethyl group, 2-sulfoethyl group, 2- (2-hydroxyethoxy) ethyl group, 2,3-dihydroxypropyl group , Phenyl group and 4-sulfophenyl group.

Q represents a hydrogen atom, a hydroxyl group, a thiol group, a carboxyl group, a sulfo group, —NR ₁₅ R ₁₆ , —OR ₁₇ or a halogen atom, and R ₁₅ , R ₁₆ and R ₁₇ are a hydrogen atom, an alkyl group and an aryl group, respectively. Alternatively, it represents a hetero group, and preferred examples thereof are the same as those for R ₁₁ , R ₁₂ , R ₁₃ and R ₁₄ .

R ₁₁ and R ₁₂ , R ₁₃ and R _14, and R ₁₅ and R ₁₆ may be bonded to each other to form a ring. When a ring is formed, the ring formed by the ring is a 5-membered or 6-membered ring A ring is preferred.

R ₁₁ , R ₁₂ , R ₁₃ , R ₁₄ , R ₁₅ , R ₁₆ and R ₁₇ are represented by —SO ₃ M, —CO ₂ M or —OH in the molecule of the compound of general formula (IV). It is chosen to contain at least one group. Here, M represents a hydrogen atom, an alkali metal, an alkaline earth metal, ammonium or pyridinium, and Na and K are particularly preferable among the alkali metals and alkaline earth metals. Examples of the ammonium group include an ammonium group, a triethylammonium group, and a tetrabutylammonium group. Most preferred as M is sodium and potassium. Further, three or more of R ₁₁ , R ₁₂ , R ₁₃ , R ₁₄ , R ₁₅ and R ₁₆ do not become an aryl group. Further, in the molecule of the compound of the general formula (IV), there is no conjugated bond between two triazine rings, and no group represented by -N = N- is contained.

  Hereinafter, although the specific example of a compound represented by general formula (IV) based on this invention is shown, this invention is not limited to these.

  The compound represented by the general formula (IV) 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 include 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 Inorganic bases such as potassium hydrogen can be mentioned. 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 ° C. to 150 ° C., and preferably in the range of −10 ° C. to 100 ° C. More specifically, the first stage is preferably -10 ° C to 10 ° C, the second stage is preferably 0 ° C to 40 ° C, and the third stage is preferably 40 ° C to 100 ° C.

  Next, the compound represented by the general formula (V) according to the present invention will be described.

In the general formula (V), X ₁ , X ₂ , Y ₁ and Y ₂ are each an alkoxy group, aryloxy group, heterocyclic oxy group, heterocyclic group, hydroxyl group, amino group, chlorine atom, alkyl group, An aryl group or a group represented by the general formula (Va) is represented. X and Y each represent NR ₃ , O or S, and R ₃ represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. L represents a phenylene group, a naphthyl group or a heterocyclic group.

Moreover, in the said general formula (Va), R < ₁ >, R < ₂ >, R < ₃ > represents an alkyl group, an aryl group, or a heterocyclic group, respectively, and these groups include what has a substituent.

If R _1, R ₂ and R ₃ are each represented by an alkyl group preferably has 1 to 20 carbon atoms as the alkyl group, more preferably 1-8, particularly preferably 1-4, for example, a 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.

When R ₁ , R ₂ and R ₃ are each represented by an aryl group, the aryl group preferably has 6 to 20 carbon atoms, more preferably 6 to 10 carbon atoms, particularly preferably 6 to 8 carbon atoms. , Naphthyl group, 3-carboxyphenyl group, 4-carboxyphenyl group, 3,5-dicarboxyphenyl group, 4-methoxyphenyl group, 2-sulfophenyl group, 4-sulfophenyl group, 2,4-disulfophenyl Groups.

When R ₁ , R ₂ and R ₃ are each represented by a heterocyclic group, the heterocyclic group preferably has 2 to 20 carbon atoms, more preferably 2 to 10 carbon atoms, particularly preferably 3 to 8 carbon atoms. 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.

In the general formula (V), when X ₁ , X ₂ , Y ₁ and Y ₂ are each a heterocyclic group or a heterocyclic oxy group, the heterocyclic moiety is a 5- or 6-membered aromatic or non-aromatic group, respectively. A monovalent 5-membered or 6-membered ring group obtained by removing one hydrogen atom bonded to a nitrogen atom from the nitrogen-containing heterocyclic compound is preferable. Examples of the ring include a pyrrolidine ring, a piperidine ring, a piperazine ring, and A morpholine ring is mentioned.

As the alkyl group, the alkyl part of the alkoxy group, the aryl group, and the aryl part of the aryloxy group, those shown as R ₁ , R ₂ , and R ₃ are preferable, and the same examples are exemplified.

X and Y each independently represent NR ₃ , O or S, and the substituent represented by R ₃ is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms (for example, a methyl group, an ethyl group, an i-propyl group, n-propyl group).

  The group represented by L includes those having a substituent as the phenylene group or naphthylene group, preferably having 6 to 20 carbon atoms, more preferably 6 to 15 and particularly preferably 6 to 11 phenylene group or 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 1,4-phenylene, 1,3-phenylene, 1,2-phenylene, 1,5-naphthylene, 5-carboxy-1,3-phenylene, 5-sulfo-1, - phenylene, more preferably 1,4-phenylene, 1,3-phenylene.

  The group represented by L is preferably a heterocyclic group having 2 to 20 carbon atoms, more preferably 2 to 10 and even more preferably 2 to 8 carbon atoms, including those having a substituent. For example, 3,5- (1,2,4-triazole) -diyl group, 3,5-isothiazolediyl group, 2,6-pyridinediyl group, 2,6-pyrazinediyl group, 2,6-pyrimidinediyl Group, 3,6-pyridazinediyl group, 1,4-phthalazinediyl group.

  When the compound represented by the general formula (V) is each represented by a carboxyl group or a sulfo group, these may be in a free form or a salt form. Examples of the salt include ammonium, triethylammonium, tetrabutylammonium and the like. An ammonium group, an alkali metal, an alkaline earth metal, ammonium or pyridinium. Of these, preferred salts are ammonium, sodium and potassium.

  Hereinafter, although the specific example of a compound represented by general formula (V) which concerns on this invention is shown, this invention is not limited to these.

  In addition, when the compound represented by the general formula (V) 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. All stereoisomers are shown, and only one of the stereoisomers can be used, or several of them can be used as a mixture.

  Each compound represented by the general formulas (I) to (V) according to the present invention may be used alone, or two or more kinds may be mixed as necessary from the viewpoint of improving solubility. good. It can also be used in combination with a triazinyl stilbene compound. For example, tricycles described in JP-A-6-329936, JP-A-7-140625, JP-A-10-104809, and JP-A-2000-39690 can be used. An azinyl stilbene compound can also be used in combination. As commercially available compounds, for example, “Dyeing Note” 19th Edition (Color Dyeing) P.I. 165-P. 168 can be mentioned.

  Moreover, the addition amount of each compound represented by the general formula (I) to the general formula (V) according to the present invention is preferably 0.02 to 20 mmol per liter when prepared as a treatment liquid. Preferably it is 0.05-10 mmol, Most preferably, it is 0.1-5 mmol. In addition, the bleaching agent part may contain p-toluenesulfinic acid, m-carboxybenzenesulfinic acid, arylsulfinic acid such as sodium benzenesulfinate, and the like. It is preferable to make it contain in 0.02-1.0 mol / L (as the density | concentration of the prepared process liquid).

  Next, the fixing agent part constituting the bleach-fixing solution concentrated composition of the present invention in combination with the bleaching agent part will be described.

  The fixing agent part according to the present invention includes known fixing chemicals, that is, thiosulfates such as sodium thiosulfate and ammonium thiosulfate, thiocyanates such as sodium thiocyanate and ammonium thiocyanate, ethylenebisthioglycolic acid, 3, 6 -1 type or 2 types or more selected from water-soluble silver halide dissolving agents, such as thioether compounds, such as dithia-1,8-octanediol, and thioureas, can be contained. A special bleach-fixing solution comprising a combination of a fixing agent described in JP-A-55-155354 and a large amount of a halide such as potassium iodide can also be used. In the present invention, it is preferable to use thiosulfate, particularly ammonium thiosulfate.

  The concentration of the fixing chemical in the fixing agent part according to the present invention is preferably designed to be 0.3 to 3 mol per liter of the prepared solution when the bleach-fixing solution is prepared, and more preferably 0.5. Designed in the range of ~ 2.0 moles.

  Further, the fixing agent part according to the present invention includes sulfites (for example, sodium sulfite, potassium sulfite, ammonium sulfite, etc.), bisulfites (for example, ammonium bisulfite, sodium bisulfite, potassium bisulfite) as preservatives. , And the like, and metabisulfite (eg, potassium metabisulfite, sodium metabisulfite, ammonium metabisulfite, etc.) and the like. These compounds are preferably contained in an amount of about 0.02 to 1.0 mol / L (as the concentration of the prepared treatment liquid) in terms of sulfite ions. As a preservative, ascorbic acid, a carbonyl bisulfite adduct, a carbonyl compound, or the like may be added in addition to the above. In addition, arylsulfinic acid such as p-toluenesulfinic acid, m-carboxybenzenesulfinic acid, sodium benzenesulfinate and the like may be contained, and these compounds are converted into about 0.02-1.0 in terms of sulfinate ion. It is preferably contained in mol / L (as the concentration of the prepared treatment liquid).

  In the fixing agent part according to the present invention, it is preferable to use ammonium ions when considering the speed of processing. On the other hand, when emphasizing the work environment, it is preferable that substantially no ammonium ions are included. .

  In the fixing agent part according to the present invention, potassium hydroxide, sodium hydroxide, lithium hydroxide, lithium carbonate, sodium carbonate, potassium carbonate, an acidic or alkaline buffering agent, or the like can be added as an alkaline agent.

  In addition, the bleaching agent part and the fixing agent part according to the present invention may contain other various antifoaming agents, surfactants, polyvinyl pyrrolidone, fluorescent whitening agents, and the like as necessary.

  Further, the bleaching agent part and the fixing agent part according to the present invention do not need to be in a homogeneous liquid phase, and can be prepared as long as the treatment liquid can be prepared by diluting with water. Any of the slurry-like compositions containing the deposit and the suspension may be used. In the case of a homogeneous liquid phase composition, the concentration is preferably 1.1 or more from the viewpoint of handleability, more preferably 1.5 to 2.5, and the upper limit is 5 0.0 or less is preferable. In the case of a slurry composition, the concentration is 1.5 or more, preferably 1.5 to 8.0, more preferably 2.5 to 5.0, and the upper limit of the concentration is 10.0. It is preferable.

  In addition, from the suppression of coloring to the storage container, which is an object effect of the present invention, the bleaching agent part constituting the bleach-fixing solution concentrated composition of the present invention is filled in the container and has a porosity of 3 to 30%. One characteristic is that it is 5 to 20%.

  Next, the container filled with the bleach-fixing solution concentrated composition of the present invention will be described.

  The container filled with the bleach-fixing solution concentrate composition of the present invention preferably has a certain oxygen transmission rate in view of the stability of the bleach-fixing solution concentrate composition. In order to ensure oxygen permeability, it is not always necessary to select an oxygen permeable container material. For example, the air tightness may be relaxed by the structure of the container opening. A preferable oxygen permeability is an oxygen permeation amount of 4 ml or more per day.

  The material of the container may be any material, but a plastic material is preferable. Examples of the plastic material preferably used include the following general packaging materials.

(Group)
A: Polyolefin resin B: Polyethylene-vinyl acetate copolymer resin C: Ethylene-vinyl alcohol copolymer resin D: Polyamide resin E: Ceramic F: Acrylonitrile resin G: Polyethylene terephthalate resin H: Polyvinylidene halide Resin I: Polyhalogenated vinyl resin The resin used for the polyolefin resin layer is preferably polyethylene, low density polyethylene (hereinafter abbreviated as LDPE), medium density polyethylene (hereinafter abbreviated as MDPE) and high density polyethylene. Any of (hereinafter abbreviated as HDPE) can be used. The HDPE preferably used in the present invention has a density of 0.941 to 0.969. LDPE is synthesized by a high pressure polymerization method, and its density is 0.910 to 0.925.

  As the container used in the present invention, HDPE having the above-mentioned density range is preferably used. Further, the melt index of the HDPE (measured at a temperature of 190 ° C. and an extrusion pressure of 2.16 kg by the method defined in ASTM D1238). ) Is preferably 0.3 to 7.0 g / 10 min, more preferably 0.3 to 5.0 g / 10 min. When it is in this range, it is stable as a container for the bleach part according to the present invention. Although the preferable thickness of the container in this invention changes with materials, Preferably it is 0.1-2.0 mm, Especially preferably, it is 0.3-1.5 mm, More preferably, it is 0.4-1.0 mm.

  As the polyamide-based resin, nylon is preferably used in terms of piercing strength and pinhole resistance, and the thickness is preferably 3 to 50 μm, more preferably 5 to 30 μm. In particular, stretched nylon is preferred from the viewpoint of achieving the object effect of the present invention.

  Ceramic is an inorganic substance mainly composed of silicon oxide, and may be coated on polyethylene or polyethylene phthalate in a vacuum. Specific examples of these include GL type (ceramic vapor deposition film) manufactured by Toppan Printing Co., Ltd.

  Examples of the ethylene-vinyl alcohol copolymer resin include Kuraray manufactured by Kuraray Co., Ltd. and Everfilm (EF-XL, EF-F, EF-K).

  In addition, examples of the halogen in the polyvinyl halide resin and the polyvinyl halide resin include chlorine, fluorine, bromine, and the like, specifically, resins such as polyvinylidene chloride, polyvinylidene fluoride, and polyvinyl fluoride. It is done.

  However, in the present invention, from the viewpoint of environmental suitability, those that do not generate harmful gas during incineration are preferable, and among the group, A to G are preferably used, and those of A to F are particularly preferable.

  In the present invention, each resin used as the material of the container is the one described in “Plastic Film” (published by Nikkan Kogyo Shimbun, Gisaku Takahashi, supplemented on December 20, 1976). A satisfactory one can be used.

  These materials may be used by being molded alone, but a so-called multilayer film in which two or more kinds of materials are bonded together in a film form may be used. The shape of the wrapping material can take any configuration such as bottle type and pillow type.

  Although the production of the multilayer film is not particularly limited, for example, a method of adhering a film and a film with an adhesive, a method of adhering a film and a film with a molten resin, two or more kinds of resins together from a slit A so-called co-extrusion method and other commonly used film lamination methods can be used alone or in combination.

  Hereinafter, a bleach-fixing processing solution (use solution (tank solution), replenisher solution) in which the bleaching agent part and the fixing agent part of the bleach-fixing solution concentrated composition are mixed and water is added if necessary will be described.

  The bleaching agent concentration in the bleach-fixing solution is preferably 0.08 to 1.0 mol / L, more preferably 0.1 to 0.7 mol / L, and the fixing agent concentration is 0.3. -3 mol / L is preferable, More preferably, it is 0.5-2 mol / L. The pH range is preferably from 3 to 8, more preferably from 4 to 8, and not only high bleaching performance can be obtained, but also excellent processing performance can be obtained without the occurrence of stains. The above concentration and pH can be achieved by adjusting the dissolution ratio of each part of the bleach-fixing concentrated composition. Further, the pH may be adjusted with an additive. Examples of the additive include alkali ammonium hydroxide, potassium hydroxide, sodium hydroxide, lithium hydroxide, lithium carbonate, sodium carbonate, potassium carbonate and sulfuric acid, hydrochloric acid, etc. Or acids or buffers.

  Next, the color development processing step using the bleach-fixing solution concentrated composition of the present invention will be described.

  The color development processing to which the concentrated composition of the bleach-fixing solution of the present invention is applied comprises a color development step, a bleach-fixing step, a rinse, a water washing or stabilization step, and a drying step. An auxiliary process such as a process can be inserted. Further, the bleach-fixing solution concentrated composition of the present invention is used in a bleach-fixing step.

  A specific configuration example of the bleach-fixing step is given below.

1) Bleaching fixing 2) Bleaching-bleaching fixing 3) Bleaching-washing-bleaching fixing 4) Bleaching-bleaching fixing-fixing These steps may be divided into a plurality of baths if necessary, and may adopt a cascade system. A preferred process is 1).

The bleach-fixing solution concentrated composition of the present invention can remarkably reduce the replenishing solution replenished to the bleach-fixing use solution, and the amount thereof is 20 to 20 to 1 m ^{2 of} silver halide color photographic light-sensitive material. 100 ml is preferable, More preferably, it is 35 ml-100 ml. A smaller amount of replenishment in the color development step is preferred from the viewpoint of reducing the amount of waste liquid, and is usually 15 to 200 ml, preferably 15 to 120 ml, particularly preferably 30 to 1 m ^{2 of} silver halide color photographic light-sensitive material. 60 ml. The replenishing amount of the rinsing solution (washing water and / or stabilizing solution) is preferably 200 ml or less, more preferably 180 ml or less, per 1 m ^{2 of the} silver halide color photographic light-sensitive material.

  The color development time (that is, the time for performing the color development step) is preferably 45 seconds or less, more preferably 30 seconds or less, still more preferably 26 seconds or less, and 6 seconds or more from the viewpoint of rapidity. Similarly, the bleach-fixing time (that is, the time for performing bleach-fixing) is preferably 45 seconds or shorter, more preferably 30 seconds or shorter, and even more preferably 25 seconds or shorter and 6 seconds or longer.

  Similarly, in the rinsing (washing or stabilization), the rinsing time (that is, the time for performing the rinsing step) is preferably 90 seconds or shorter, more preferably 30 seconds or shorter, and even more preferably 30 seconds or shorter and 6 seconds or longer.

  The color development time refers to the time from when the silver halide color photographic light-sensitive material enters the color developer until it enters the bleach-fixing solution, which is the next processing step. For example, when processed by an automatic processor, the time during which the silver halide color photographic light-sensitive material is immersed in a color developer (so-called submerged time) and the color development of the silver halide color photographic light-sensitive material are developed. The total of both the time during which the solution is left and conveyed in the air toward the next processing step, the bleach-fix solution (so-called air time), is called color development time. Similarly, the bleach-fixing time refers to the time from when the silver halide color photographic light-sensitive material enters the bleach-fixing solution until the next rinsing, washing or stabilizing bath. Further, the rinsing (washing or stabilization) time is the time during which the silver halide color photographic light-sensitive material is in the rinsing solution (washing or stabilizing solution) and in the solution for the drying process (so-called in-solution solution). Say time).

  Each processing solution temperature in the color development step, the bleach-fixing step, and the rinsing (washing or stabilizing) step is generally 30 to 40 ° C., but is preferably 38 to 60 ° C., more preferably 40 to 50 ° C. for rapid processing. It is.

  From the viewpoint of reducing the amount of water taken into the image film of the silver halide color photographic light-sensitive material, the drying step is performed immediately after the rinsing (washing or stabilizing) step of the color development process, with a squeeze roller or cloth. It is also possible to speed up drying by absorbing moisture. Of course, drying can be accelerated by increasing the temperature or changing the shape of the spray nozzle to increase the drying air. Furthermore, as described in JP-A-3-157650, drying can be accelerated by adjusting the blowing angle of the dry air to the silver halide color photographic light-sensitive material and by the method of removing the exhaust air.

  The amount of rinse solution (washed or stabilized) varies widely depending on the characteristics of the silver halide color photographic light-sensitive material (for example, depending on the material used such as coupler), application, temperature, number of tanks (number of stages), and various other conditions. Can be set. Of these, the relationship between the number of rinsing (flushing or stabilizing) tanks and the amount of water in the multi-stage countercurrent system is the Journal of the Society of Motion Picture and Television of Motion of Motion. (Picture and Television Engineers) Vol. 64, p. It can be determined by the method described in 248-253 (May 1955). Usually, the number of stages in the multistage counter-current system is preferably 3 to 15, particularly 3 to 10. In addition, when the multi-stage countercurrent system is used, the amount of liquid can be greatly reduced, but due to an increase in the residence time of water in the tank, there are problems such as bacteria breeding and the generated suspended matter adheres to the photosensitive material. Therefore, as the solution, a rinsing (washing or stabilizing) solution containing an antibacterial / antifungal agent described later is preferable.

  Next, other processing solutions and components used in the development processing step together with the bleach-fixing solution concentrate composition of the present invention will be described. In addition, the processing liquid concentrated composition including the above-described bleach-fixing liquid concentrated composition is mixed with a solvent such as water at a ratio determined in use to prepare a working liquid (tank liquid) or a replenishing liquid. In this specification, unless there is a special meaning which distinguishes a tank liquid and a replenisher, both are expressed collectively as a process liquid.

  First, a color developing solution used in the color developing process will be described.

  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. Is not to be done.

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- (hydroxymethyl) pyrrolidine 16) N- (4-Amino-3-methylphenyl) -3-pyrrolidinecarboxamide Among the above p-phenylenediamine derivatives, particularly preferred compounds 5), 6), 7), 8) and 12). Among them, exemplary compounds 5) and 8) are preferable. These p-phenylenediamine derivatives may be in the form of a salt such as sulfate, hydrochloride, sulfite, naphthalene disulfonate, p-toluenesulfonate, or the free base type as described above. The concentration of the color developing agent in the working solution is added so as to be 2 to 200 mmol, preferably 6 to 100 mmol, more preferably 10 to 40 mmol per liter of the developing solution.

  An organic preservative may be added to the color developing solution. The organic preservative refers to all organic compounds that reduce the deterioration rate of the color developing agent by being contained in the processing solution of the photosensitive material. That is, organic compounds having a function to prevent air oxidation of the color developing agent, such as hydroxamic acids, hydrazides, phenols, α-hydroxy ketones, α-amino ketones, saccharides, monoamines, diamines, polyamines , Quaternary ammonium salts, nitroxy radicals, alcohols, oximes, diamide compounds, condensed amines and the like are particularly effective organic preservatives. 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, U.S. Pat.Nos. 3,615,503, 2,494,903, JP-A 52- No. 143,020, Japanese Patent Publication No. 4,830,496 and the like. Moreover, as another organic preservative, the compound represented by the following general formula (X) or (Y) can also be contained.

  In the general formula (X), L represents an alkylene group that may be substituted, A represents a carboxyl group, a sulfo group, a phosphono group, a hydroxyl group, an amino group that may be alkyl-substituted, or an ammonio that may be alkyl-substituted. A carbamoyl group that may be alkyl-substituted, a sulfamoyl group that may be alkyl-substituted, a sulfonyl group that may be alkyl-substituted, a hydrogen atom, an alkoxyl group, or —O— (B—O) n—R ′ , R and 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 general formula (X), L is preferably a linear or branched alkylene group having 1 to 10 carbon atoms, and 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 phosphinic acid 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 phosphinic acid 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, and a carboxyl group, a sulfo group, a hydroxyl group, Preferred examples include a phosphono group and an optionally substituted carbamoyl 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, a linear or branched alkyl group having 1 to 10 carbon atoms, and 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, or -O- ( B—O) n—R ′ and the like. 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 representative compound example is shown below among the compounds represented by general formula (X), this invention is not limited to these compounds.

  Next, the compound represented by formula (Y) will be described.

  In the general formula (Y), R and R ′ each represent a saturated or unsaturated aliphatic hydrocarbon having 1 to 6 carbon atoms. In this case, these hydrocarbons may be substituted with a hydroxyl group, a carboxyl group, a sulfone group or the like. Moreover, you may contain bivalent coupling groups, such as a carbonyl group. n represents an integer of 4 to 50,000. s represents 0 or 1. If s takes 1, A is

Represents. R ″ represents an alkylene group having 2 to 8 carbon atoms or an alkanetriyl group which may be substituted with a hydroxyl group. In the case of an alkylene group, q is 0, and in the case of an alkanetriyl group, q is 1. In the case of 1, B represents a polymer represented by the general formula (Y), and the general formula (Y) has a three-dimensional structure, and m represents an integer of 0 to 30.

  A compound represented by the general formula (Y) in which s is 0, for example, poly (N-hydroxyalkyleneimine) can be easily synthesized by a known method. As a representative example, “Journal of Chemical Society” (J. Chem. Soc.), 75, 1009 (1899), J. Chem. Chem. Soc. , 1963, 3144, etc., and a method of oxidizing and synthesizing poly (alkyleneimine) by a secondary amine oxidation method using a hydrogen peroxide solution. Since the crude poly (N-hydroxyalkyleneimine) synthesized by this method does not contain a component that affects photographic characteristics, it can be used as it is as a color developer composition without purification. Further, in combination with the reaction described in “Macromolecules”, 21, 1995 (1988) and the like, the primary amine which is the terminal group of poly (alkyleneimine) is changed to a secondary amine, thereby further improving the reaction. A method of synthesizing poly (N-hydroxyalkyleneimine) having excellent performance is also included. Examples of other methods include a synthesis method by reaction of hydroxylamine and dihalogenated alkylene, to which the method described in JP-A-3-259145 is applied. Hereinafter, although the representative compound example is shown among the compounds represented by general formula (Y), this invention is not limited to these compounds.

Other organic preservatives include various metals described in JP-A-57-44148 and 57-53749, salicylic acids described in JP-A-59-180588, triethanolamine and triiamine. Alkanolamines described in JP-A No. 54-3532, such as sopanolamine, polyethyleneimines described in JP-A-56-94349, US Pat. No. 3,746,544, etc. An aromatic polyhydroxy compound or the like may be contained as necessary. The color developing composition of the organic preservative is preferably contained at 1 × 10 ⁻³ mol or more and 1 × 10 ⁻¹ mol or less per liter. In addition, the color developer may contain a small amount of sulfite ions or may not substantially contain sulfite ions depending on the type of silver halide color photographic light-sensitive material to be used. It is preferable to include. Moreover, you may contain a small amount of hydroxylamine. Hydroxylamine (usually used in the form of hydrochloride or sulfate, but omits the salt form below) acts as a developer preservative like sulfite ion, but at the same time hydroxylamine itself has silver developing activity. Therefore, it is necessary to keep the addition amount small.

  The color developer may contain an arylsulfinic acid such as benzenesulfinic acid, p-toluenesulfinic acid, m-carboxybenzenesulfinic acid.

  The pH of the color developing solution is preferably 9.0 to 13.5, and the pH of the replenisher is preferably 9.0 to 13.5. Therefore, the color developing solution and its replenisher may contain an alkali agent, a buffering agent and, if necessary, an acid so that the pH value can be maintained.

  Examples of the buffer for maintaining the pH 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 salt, 2-amino-2-methyl-1,3-provandiol salt, valine salt, proline salt, trishydroquinaminomethane salt, lysine salt, etc. Can be used. Carbonate, phosphate, tetraborate, and hydroxybenzoate are particularly excellent in buffering ability in a high pH range of pH 9.0 or higher, and even when added to a color developer, they adversely affect photographic performance (fogging). Etc.) and is a particularly preferable buffer because it is inexpensive.

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

  The addition amount of the buffer is preferably 0.01 to 2 mol, more preferably 0.1 to 0.5 mol per liter for both the color developing solution and its replenisher.

  For example, calcium or magnesium precipitation inhibitors or various chelating agents that are also stability improvers can be added to the color developing solution as other color developer components. 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. These chelating agents may be used in combination of two or more as required. Further, the amount of these chelating agents may be an amount sufficient to sequester metal ions in the color developer. For example, 0. It is added so as to be about 1 to 10 g.

  If necessary, an arbitrary development accelerator can be added to the color developing solution. 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 neo ether 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, U.S. Pat. Nos. 2,494,903, 3,128,182, and 4,230,796, which are described in JP-A-56-156826 and JP-A-52-43429. No. 3,253,919, Japanese Patent Publication No. 41-11431, U.S. Pat. Nos. 2,482,546, 2,596,926, and 3,582,346. Or the amine compounds described in the specification, JP-B-37-16088, JP-A-42-25201, U.S. Pat. No. 3,128,183, JP-B-41-11431, JP-A-42-23883 and U.S. Pat. , 532, 501 and the like, polyalkylene oxides represented in the respective publications and specifications, other 1-phenyl-3-virazolitones or imidazoles can be added as necessary. The added amount in the composition is determined so that the concentration of both the color developer and its replenisher is 0.001 to 0.2 mol, preferably 0.01 to 0.05 mol, per liter.

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

  Various surfactants such as alkyl sulfonic acid, aryl sulfonic acid, aliphatic carboxylic acid, and aromatic carboxylic acid may be added to the color developing solution as necessary. Their concentration is preferably 0.0001 to 0.2 mol per liter for both the color developer and its replenisher, and more preferably 0.001 to 0.05 mol.

  In the color developing solution, a fluorescent brightening agent can be used as necessary. As the optical brightener, a bis (triazinylamino) stilbene sulfonic acid compound is preferred. As the bis (triazinylamino) stilbene sulfonic acid compound, known or commercially available products 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-10-14049 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 HakkolBRK are preferred.

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

In the color developing solution when the silver halide color photographic light-sensitive material is a color negative film, it is usually preferable to contain 0.2 × 10 ^{−2 to} 15.0 × 10 ⁻² mol / liter of bromine ions, more preferably. Is often contained in an amount of 0.5 × 10 ^{−2 to} 5.0 × 10 ⁻² mol / liter, but bromine ions are usually released into the working solution as a by-product of development. Is often unnecessary to add. Further, iodine ions are preferably contained in an amount of 0.2 × 10 ^{−3 to} 15.0 × 10 ⁻³ mol / liter, more preferably 0.5 × 10 ^{−3 to} 5.0 × 10 ⁻³ mol / liter. Although often contained, iodine ions are also usually released as a by-product of development into the working solution, so that it is often unnecessary to add to the replenisher.

The color developing solution used when the silver halide color photographic light-sensitive material is color paper usually contains 3.5 × 10 ^{−2 to} 1.5 × 10 ⁻¹ mol / liter of chlorine ions, Chlorine ions are usually released into the working solution as a by-product of development, and therefore often need not be added to the replenisher.

  Next, the process liquid of a rinse, water washing, or a stabilization process is demonstrated.

If necessary, the following additives can be appropriately used for the rinsing, washing or stabilizing treatment liquid. For example, isothiazolone compounds and siabendazoles described in JP-A-57-8542, chlorinated disinfectants such as sodium chlorinated isocyanurate described in JP-A 61-120145, JP-A 61-267761 Benzotriazole, copper ion, etc., described in the publication, Hiroshi Horiguchi, “Chemistry of Antibacterial and Antifungal” (1986) Sankyo Publishing, Hygiene Technology Association, “Microbial Decontamination, Sterilization, Antifungal Technology” (1982) Disinfectant and chelating agent (ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, 1-hydroxyethylidene-1,1-diphosphone described in the Industrial Technology Association of Japan, Antibacterial and Antifungal Society, “Encyclopedia of Antifungal and Antifungal Agents” (1986) Acid), buffer (potassium carbonate, borate, acetate, phosphate, etc.), optical brightener (triazinyl stilbene compound, etc.), antioxidant (ASCO) Bottles salt, etc.), water-soluble metal salt (zinc salt, magnesium salt, etc.), a bisulfite or metabisulfite salts such as bisulfite. The sulfite may be any organic or inorganic substance as long as it releases sulfite ions, but is preferably an inorganic salt. 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. These salts preferably be an amount such that at least 1 × 10 ^-3 mol / L or more in the treatment solution is added, more preferably 5 × 10 ^-3 mol / L~5 × 10 ^-2 mol / It is added to become L. The pH is preferably in the range of 4.0 to 10.0. A pH adjusting agent for adjusting to the pH can also be contained. The pH adjuster may be any of commonly known alkali agents or acid agents. Further, aldehydes such as formaldehyde, acetaldehyde and pyrubinaldehyde which inactivate the magenta coupler remaining in the silver halide color photographic light-sensitive material to prevent dye fading and stain formation, and methylol described in US Pat. No. 4,786,583 Compounds, hexamethylenetetramine, hexahydrotriazines described in JP-A-2-153348, formaldehyde bisulfite adduct described in US Pat. No. 4,921,779, European Patent Publication No. 504,609, Azolylmethylamines described in No. 519, 190 and the like may be added. Moreover, the method of reducing calcium and magnesium as described in Unexamined-Japanese-Patent No. 62-288838 can also be used for a rinse or a stabilization bath.

  In the foregoing, the bleach-fixing solution concentrated composition of the present invention and the development processing method using the bleach-fixing solution concentrated composition have been described. Next, the developing processing apparatus for performing the developing process will be described.

  The development processing according to the present invention is preferably performed using an automatic developing machine.

  Hereinafter, an automatic processor preferably used in the present invention will be described.

  In the automatic processor according to the present invention, the linear velocity of conveyance is preferably 100 mm / second or less, more preferably 27.8 mm / second to 80 mm / second, and particularly preferably 27.8 mm / second to 50 mm / second. is there.

  In the automatic paper color developer transport system, the color paper is cut to the final size before development processing (sheet-type transport method), and the paper is developed with a long roll and cut to the final size after processing (cine). Mold conveyance system). The cine type conveyance method is preferably a sheet type conveyance method because a photosensitive material of about 2 mm is wasted between images.

The treatment liquid according to the present invention is preferably a treatment tank and a replenishment liquid tank, and the area (opening area) where the liquid comes into contact with air is preferably as small as possible. For example, when the opening ratio is a value obtained by dividing the opening area (cm ² ) by the liquid tank (cm ³ ) in the tank, the opening ratio is preferably 0.08 (cm ⁻¹ ) or less, more preferably 0.01 ( cm ⁻¹ ) or less.

  In order to reduce the area in contact with air, it is preferable to provide solid or liquid air non-contact means floating on the liquid surface in the treatment tank and the replenishment tank.

  Specifically, it is preferable to cover a plastic float or the like on a liquid surface or a liquid that does not mix with the processing liquid and does not cause a chemical reaction. As examples of the liquid, liquid paraffin, liquid saturated hydrocarbon and the like are preferable. In the present invention, in order to perform processing quickly, the air time when the silver halide color photographic light-sensitive material moves between the processing solutions, that is, the crossover time is preferably as short as possible, preferably 10 seconds or less. Preferably it is 7 seconds or less, More preferably, it is 5 seconds or less. Further, in order to shorten the crossover time and prevent the mixing of the processing liquid, a crossover rack structure provided with a mixing prevention plate is preferable. As a method for eliminating the crossover time at all, it is particularly preferable to use a submerged conveyance structure using a blade described in JP-A-2002-55422. In this method, a crossover time can be reduced to zero by providing a blade between processing tanks to prevent liquid leakage and allowing the photosensitive material to pass therethrough. It is particularly preferable to install a porous pleated filter in the circulation system and a circulation system in which the liquid circulation direction described in JP-A-2002-339383 is flowed downward in the submerged conveyance structure using this blade. It is preferable to perform so-called evaporation correction in which water corresponding to the evaporation amount of the processing liquid is supplied to each processing liquid according to the present invention. In particular, it is preferable in a color developer and a bleach-fix solution.

  A specific method for replenishing such water is not particularly limited, but a monitor water tank different from the bleach-fixing tank described in JP-A-1-254959 and 1-2254960 is installed. The amount of water evaporation in the monitor tank is calculated, the amount of water evaporation in the bleach-fixing tank is calculated from the amount of water evaporation, and the water level sensor is used to replenish the bleach-fixing tank in proportion to this amount of evaporation. Or an evaporation correction method using an overflow sensor is preferred. The most preferable evaporation correction method is to predict and add water corresponding to the amount of evaporation, and is described on page 26, right column, line 26 to page 3, left column, page 28 of the Japan Institute of Invention and Innovation, No. 94-49925. As described above, the amount of water calculated by a coefficient determined in advance based on information on the operation time, stop time, and temperature control time of the automatic processor is added. Further, a device for reducing the evaporation amount is also required, and it is required to reduce the opening area and adjust the air volume of the exhaust fan. For example, the preferred aperture ratio of the color developer is as described above, but it is preferable to reduce the aperture area in the other processing solutions as well.

As means for reducing the evaporation amount, it is particularly preferable to “keep the humidity of the upper space of the treatment tank at 80% RH or higher” described in JP-A-6-110171, and the evaporation prevention described in FIGS. It is particularly preferred to have a rack and roller automatic cleaning mechanism. Exhaust fans in order to prevent dew condensation at the temperature control is attached normally, a preferable exhaust amount per minute 0.1 m ³ to 1 m ^3, particularly preferably at 0.2m ³ ~0.4m ³ is there. The drying conditions of the silver halide color photographic light-sensitive material also affect the evaporation of the processing solution. The drying method is preferably a ceramic hot air heater is preferably min 4m ³ to 20 m ³ as feed air volume, particularly 6m3~10m3 is preferred. The thermostat for preventing the heating of the ceramic warm air heater is preferably operated by heat transfer, and the mounting position is preferably attached leeward or upwind through the radiating fin or the heat transfer portion. The drying temperature is preferably adjusted according to the water content of the light-sensitive material to be processed. The optimum temperature is 45 to 55 ° C. for an APS format and 35 mm wide film, and 55 to 65 ° C. for a brownie film. The drying time is preferably 5 seconds to 2 minutes, more preferably 5 seconds to 60 seconds.

  A replenishment pump is used for replenishing the processing solution, but a bellows type replenishment pump is preferred. In addition, as a replenishment method, the treatment liquid concentrated composition may be added directly to the treatment tank, and water corresponding to the dilution ratio may be added directly to the treatment tank, and the treatment liquid concentrated composition is dissolved in the replenishment tank. It may be diluted and replenished as a replenisher, or the treatment liquid concentrated composition may be automatically dissolved and diluted in a replenisher tank using an automatic preparation device and replenished as a replenisher. As a method for improving the replenishment accuracy, it is effective to reduce the diameter of the liquid feeding tube to the replenishing nozzle in order to prevent backflow when the pump is stopped. A preferable inner diameter is 1 to 8 mm, and a particularly preferable inner diameter is 2 to 5 mm.

  Various component materials are used in the automatic processor, and preferred materials are described below.

  The tank material such as the treatment tank and the temperature control tank is preferably modified PPO (modified polyphenylene oxide) or modified PPE (modified polyphenylene ether) resin. Examples of the modified PPO include “Noryl” manufactured by GE Plastics Japan, and the modified PPE includes “Zylon” manufactured by Asahi Kasei Kogyo, “Iupiace” manufactured by Mitsubishi Gas Chemical, and the like. Moreover, these materials are suitable for parts that may come into contact with the processing liquid such as processing racks and crossovers.

  Resin such as PVC (polyvinyl chloride), PP (polypropylene), PE (polyethylene), TPX (polymethylpentene) is suitable for the roller material of the processing section. These materials can also be used for other processing liquid contact portions. In addition, PE resin is preferable also for the material of the replenishment tank by blow formation.

  PA (polyamide), PBT (polybutylene terephthalate), UHMPE (ultra high molecular weight polyethylene), PPS (polyphenylene sulfide), LCP (fully aromatic polyester resin, liquid crystal polymer) ) Etc. are suitable.

  PA resin is polyamide resin such as 66 nylon, 12 nylon, and 6 nylon, and those containing glass fiber or carbon fiber are strong against swelling by the treatment liquid and can be used.

  Further, high molecular weight products such as MC nylon and compression formed products can be used without fiber reinforcement. UHMPE resin is suitable for unreinforced products. “Lubema”, “Hi-X Million” manufactured by Mitsui Petrochemical Co., Ltd., “New Light” manufactured by Sakushin Kogyo Co., Ltd., “Sunfine” manufactured by Asahi Kasei Kogyo Co., Ltd. Is suitable. The molecular weight is preferably 1,000,000 or more, more preferably 1,000,000 to 5,000,000. The PPS resin is preferably glass fiber or carbon fiber reinforced. Examples of the LCP resin include “Victrex” manufactured by ICI Japan, “Econol” manufactured by Sumitomo Chemical, “Zider” manufactured by Nippon Oil Co., Ltd., “Vectra” manufactured by Polyplastics, and the like. In particular, the material of the conveyor belt is preferably ultrahigh strength polyethylene fiber or polyvinylidene fluoride resin described in JP-A-4-151656. As a soft material such as a squeeze roller, a foamed vinyl chloride resin, a foamed silicon resin, and a foamed urethane resin are suitable. Examples of the urethane foam resin include “Rubicel” manufactured by Toyo Polymer Co., Ltd. EPDM rubber, silicon rubber, Viton rubber and the like are preferable as rubber materials such as a pipe joint, an agitation jet pipe joint, and a sealing material. The treatment liquid concentrated composition used in the present invention may be used in the form of a cartridge that is combined into a set, in addition to individually forming the treatment liquid concentrated composition for each step into a product form. In this case, it is preferable that the automatic developing machine has an apparatus that can mount cartridges in a batch.

  Next, a silver halide color photographic light-sensitive material (hereinafter sometimes simply referred to as “photosensitive material”) to which the bleach-fixing solution concentrated composition of the present invention is applied will be described.

The silver halide color photographic light-sensitive material applicable to the processing method using the bleach-fixing concentrated composition of the present invention includes a wide variety of photographic elements having a silver halide light-sensitive layer on a support, such as a color negative film, a color A reversal film, a color paper, a color display, a color movie film, etc. can be mentioned, but a color paper is preferred.
Moreover, as commercially available color papers, FUJICOLOR Crystal Archive paper, FUJICOLOR SUPER FA paper (above, manufactured by Fuji Photo Film Co., Ltd.), Kodak EKTACOLOR EDGE paper, Kodak EKTACOLOR Royal Paper (above, manufactured by Eastman Co., L Examples of the product group include, but are not limited to, paper, AGFACOLOR Prestige paper (manufactured by AGFA), and KONICACOLOR QA paper (manufactured by Konica Minolta Photo Imaging) (all trade names).

  EXAMPLES Hereinafter, the present invention will be specifically described with reference to examples, but the present invention is not limited thereto. In addition, although the display of "part" or "%" is used in an Example, unless otherwise indicated, "part by mass" or "mass%" is represented.

Example 1
<< Preparation of bleach part: Filling volume 1000ml >>
Bleach parts 1-1 to 1-39 were prepared by adding 1 type of aminopolycarboxylic acid diiron complex salt and adding amount thereof, and adding nitric acid in a combination shown in Table 1 to 1 L. The pH was adjusted using an aqueous ammonia solution and hydrogen peroxide so that the pH shown in Table 1 was reached when water was added.

  Next, each bleaching agent part was filled and sealed in a hard bottle container made of high-density polyethylene so as to have the porosity described in Table 1.

[Evaluation of Bleach Part: Evaluation of Container Coloring Resistance]
Each bleaching part filled in the container was stored at 55 ° C. for 1.5 months, and then the bleaching part was discharged from the container and the inside was washed twice with 50 ml of water. Next, the degree of contamination of the inner wall of the container was visually observed, and the container coloring resistance was evaluated according to the following criteria.

◎: No contamination of the inner wall of the container is observed. ○: Slight adhesion of the inner wall of the container is observed, but it is in a good state. △: Contamination of the inner wall of the container is observed, but is practically acceptable. X: Visible dirt adheres to the entire inner wall of the container, which is a problematic level as a commercial value. Table 1 shows the evaluation results obtained as described above.

  The details of the aminopolycarboxylic acid diiron complex salt described in Table 1 with abbreviations are as follows.

Compound A: EDTA-Fe · NH ₄ (ethylene ammonium tetraacetate)
Compound B: s, s-EDDS-Fe.NH ₄ (ethylene ammonium ethylenediamine disuccinate)
Compound C: DTPA-Fe · NH ₄ (diethylenetriamineammonium pentaacetate)
Compound _{D: PDTA-Fe · NH 4} (1,3- propylenediamine tetraacetic acid iron ammonium)
In the above description, s, s- represents the s, s form of optical isomers.

  As apparent from the results shown in Table 1, the bleaching agent part of the present invention in which the pH, the molar ratio of iron ions and nitrate ions, and the porosity satisfy the requirements defined in the present invention, It turns out that it is excellent in container coloring tolerance. Moreover, it turns out that the said effect is exhibited more favorably by making a porosity into 2-20% among the combinations of this invention.

Example 2
Bleach parts 2-1 to 2-16 were prepared in the same manner as in the preparation of bleach part 1-4 described in Example 1, except that the respective compounds listed in Table 2 were added.

  After the bleaching agent-containing parts 2-1 to 2-16 prepared above and the bleaching agent part 1-4 prepared in Example 1 were stored at 65 ° C. for one month, the containers were colored in the same manner as in Example 1. The container expansion resistance was evaluated according to the evaluation of resistance and the following method.

[Evaluation of container expansion resistance]
The swelling state of the container after storage at 65 ° C. for 1 month was visually observed, and the container swelling resistance was evaluated according to the following criteria.

○: No expansion of the container before and after storage is observed. Δ: Swelling of the container is slightly observed compared with that before storage, but it is a practically acceptable level. Table 2 shows the results obtained from the above, which is a level where swelling is observed and liquid leakage is a concern.

  As apparent from the results shown in Table 2, by adding the compounds represented by the general formulas (I) to (V) according to the present invention to the bleaching agent part that satisfies the requirements defined in the present invention, It can be seen that the container coloring resistance during high-temperature storage is further improved and the container expansion resistance is also excellent.

Example 3
<< Preparation of bleach part and evaluation of container coloring resistance and container expansion resistance >>
In the same manner as in the bleaching agent part 1-4 described in Example 1, except that the addition amount of ethylenediaminetetraacetic acid ferric ammonium (EDTA-FeNH ₄ ) was changed as shown in Table 3, bleaching agent part 3 After preparing -1 to 3-7, the container was filled in the same manner as described in Example 1, and then evaluated for container coloring resistance and container expansion resistance in the same manner as described in Examples 1 and 2. Went. The obtained results are shown in Table 3.

<Evaluation of desilvering and recoloring properties>
Each bleaching agent part before storage and a fixing agent part prepared from the following additives were mixed at a ratio of 1: 1 and diluted 1.5 times with water to prepare a bleach-fixing replenisher. In addition, when diluting with water, a pH adjuster (ammonia aqueous solution or nitric acid) was added to adjust the pH so that the pH was 4.8.

[Fixing agent part composition]
Ammonium sulfite 1.0 mol
Ammonium thiosulfate 1.7 mol
45g succinic acid
pH 5.7
Water was added to 1 L, and the pH was adjusted using an aqueous ammonia solution or nitric acid.

[Development processing]
Next, using each of the prepared bleach-fixing replenishers, development processing was performed under the following conditions.

  The development running process was performed by modifying a printer processor NPS-808GOLD manufactured by Konica Minolta Photo Imaging Co., Ltd. so as to satisfy the following processing conditions. In addition to the bleach-fixing tank solution, each tank solution shown below is filled in the processing tank, and Konica Minolta QA Paper Centuria for Digital (manufactured by Konica Minolta Photo Imaging) is continuously developed, and each replenisher is pumped quantitatively. It was done by replenishing with. The bleach-fixing tank solution was prepared by diluting each of the prepared bleach-fixing replenishers to 70% and adjusting the pH to 6.0 with aqueous ammonia.

  In the running process, each bleach-fixing replenisher prepared above is used, and the amount of each bleach-fixing replenisher replenished in the bleach-fixing liquid is twice the amount (12.5 L) of the bleach-fixing tank ( The processing was performed at a processing amount equivalent to 0.22 rounds per day until 2 rounds). In addition, after running, the Centuria for Digital Paper was subjected to wedge exposure according to a conventional method, and this sample was processed to evaluate the color recovery property and desilvering property according to the method described later.

(Processing conditions)
Processing process Processing temperature Processing time Tank capacity Replenishment amount
(° C) (seconds) (L) (ml / m ² )
Color development 42.5 25 12.5 40
Bleach fixing 40.0 25 12.3 40
Stabilization-1 38.0 25 11.8
Stabilization-2 38.0 25 11.8
Stabilization-3 38.0 25 11.8 170
Dry 60-80 25
In addition, about the crossover time, all the process processes were performed in 3 second, and the stabilization process was made into the multistage countercurrent system of stabilization-3->stabilization-2-> stabilization-1.

(Processing liquid composition)
The color developer and stabilizing solution tanks and replenishers were prepared as follows.

<Color developer: per liter>
Tank liquid Replenisher Polyethylene glycol # 4000 15.0 g 15.0 g
Sodium p-toluenesulfonate 10.0 g 10.0 g
Potassium chloride 4.0 g −
4-Amino-3-methyl-N-ethyl-N- (β-methanesulfonamidoethyl) aniline sulfate 6.0 g 12.0 g
N, N-bis (sulfoethyl) hydroxylamine disodium salt
4.0g 8.0g
Potassium carbonate 33.0g 33.0g
Diethylenetriaminepentaacetic acid 11.0 g 11.0 g
pH 10.20 12.40
Water was added to 1 L, and the pH was adjusted with potassium hydroxide or 50% sulfuric acid.

<Stabilizing liquid: per 1L>
Tank liquid = replenisher 1-hydroxyethylidene-1,1-diphosphonic acid trisodium 3.0 g
Ethylenediaminetetraacetic acid 1.5g
o-Phenylphenol 0.1g
Sodium sulfite 0.5g
Chino Pearl SFP (Ciba Geigy) 0.6g
pH 7.5
Water was added to 1 L, and the pH was adjusted with an aqueous ammonia solution or 50% sulfuric acid.

[Evaluation of processing characteristics]
(Evaluation of color recovery)
The cyan reflection density DR ₁ of the maximum density portion of the wedge sample subjected to the above development processing was measured using a reflection densitometer (X = rite 310, manufactured by Gretag Macbeth), and then added to the following rebleaching solution at 35 ° C. at 3 ° C. After being immersed for a minute, washed with water and dried, the cyan density DR ₂ of the maximum density part was again measured using the reflection densitometer, and a cyan density difference ΔDR was determined according to the following formula, which was used as a measure of the color recovery. The smaller the absolute value of ΔDR, the better the color recovery.

Cyan density difference ΔDR = (cyan density DR ₁ before rebleaching) − (cyan density DR ₂ after rebleaching)
<Rebleaching solution composition>
800ml water
Ethylenediaminetetraacetic acid ferric ammonium 0.075 mol
pH 7.0
Water was added to 1 L, and the pH was adjusted with ammonia or 50% sulfuric acid.

[Evaluation of desilvering properties]
The amount of residual silver (μg / cm ² ) in the maximum density part of the developed processed wedge sample was measured using a fluorescent X-ray measuring device, and this was used as a measure of desilvering property. It shows that it is excellent in desilvering property, so that residual silver amount is small.

  Table 3 shows the measurement results obtained as described above.

As is clear from the results shown in Table 3, using a bleaching agent part in which the concentration of EDTA-FeNH ₄ (aminopolycarboxylic acid ferric complex salt) is in the range of 0.4 mol / L to 1.0 mol / L. As a result of preparing and fixing the bleach-fixing replenisher, good bleaching performance (desilvering and recoloring properties) can be obtained even under low replenishment and rapid processing conditions, and resistance to container coloration at high temperature storage of the bleach part It turns out that it is excellent in container expansion | swelling tolerance. Furthermore, when the concentration of EDTA-FeNH _{4 in} the bleaching agent part is in the range of 0.5 mol / L to 0.8 mol / L, it can be seen that the bleaching performance, container coloring resistance at high temperature storage and container expansion resistance are excellent. .

Claims (4)

A bleach-fixing solution concentrate composition for a silver halide color photographic light-sensitive material comprising two parts, a concentrated composition part containing a bleaching agent and a concentrated composition part containing a fixing agent, containing the bleaching agent The pH of the concentrated composition part is 2.0 to 3.6, contains aminopolycarboxylic acid ferric complex salt and nitrate, and contains moles of iron ions of the ferric complex salt and nitrate ions of the nitrate salt The ratio is 1: 2 to 1: 6, and the concentrated composition part containing the bleaching agent is stored in a container, and the porosity of the container after storage is 3 to 30%. A bleach-fixing solution concentrate composition for a silver halide color photographic light-sensitive material. 2. The bleach-fixing solution concentrated composition for a silver halide color photographic light-sensitive material according to claim 1, wherein the porosity is 5 to 20%. The silver halide color photographic light-sensitive material according to claim 1 or 2, wherein the concentration of the ferric complex salt of aminopolycarboxylic acid is 0.4 mol / L or more and 1.0 mol / L or less. Bleach-fixing solution concentrate composition. 4. The concentrated composition part containing the bleaching agent contains at least one compound selected from the following general formulas (I) to (V): 4. A bleach-fixing solution concentrated composition for silver halide color photographic light-sensitive materials.

[Wherein, A ₁ and A ₂ each represents an aryl group or an aromatic heterocyclic group. However, the case where A ₁ is a triazinyl group is excluded. X represents a divalent linking group, and M represents a hydrogen atom, an alkali metal, an alkaline earth metal, ammonium or pyridinium. However, in the molecule | numerator represented by said general formula (I), group represented by -N = N- and -SH is not contained. n represents an integer of 2 to 4, and n X-A _2s may be the same or different, and r and s each represent an integer of 0 to 10, but r + s is 2 or more. When n is 2 and A ₁ is an aromatic heterocyclic group, the two X's each represent a divalent linking group other than N (R ₁ ), S or O, and R ₁ represents a hydrogen atom Or represents a C1-C6 alkyl group. ]

[Wherein, L ₁ and L ₂ each independently represents an aryl group, a heterocyclic group or an alkyl group, and at least one of them is an aryl group or a heterocyclic group. Y ₁ represents an amino group, a hydroxyl group, a halogen atom, a sulfo group, an alkylamino group or an alkoxy group. However, there is no conjugated bond between the two triazine rings. ]

[Wherein, L ₃ and L ₄ each independently represents an aryl group, a heterocyclic group or an alkyl group, and at least one of them is an aryl group or a heterocyclic group. R ₃ represents a hydrogen atom or an alkyl group. Y ₃ represents an amino group, a hydroxyl group, a halogen atom, a sulfo group, an alkylamino group or an alkoxy group. However, there is no conjugated bond between the two triazine rings. ]

[Wherein, R ₁₁ , R ₁₂ , R ₁₃ and R ₁₄ each represent a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group, and Q represents a hydrogen atom, a hydroxyl group, a thiol group, a carboxyl group, a sulfo group, —NR ₁₅ R ₁₆ , —OR ₁₇ or a halogen atom is represented, and R ₁₅ , R ₁₆ and R ₁₇ each represent a hydrogen atom, an alkyl group, an aryl group or a hetero group. R ₁₁ and R ₁₂ , R ₁₃ and R ₁₄ , and R ₁₅ and R ₁₆ may be bonded to each other to form a ring. However, it contains at least one group represented by —SO ₃ M, —CO ₂ M or —OH in the molecule, where M represents a hydrogen atom, an alkali metal, an alkaline earth metal, ammonium or pyridinium. Also, three or more of R ₁₁ , R ₁₂ , R ₁₃ , R ₁₄ , R ₁₅ and R ₁₆ do not become an aryl group. Further, in the molecule represented by the general formula (IV), there is no conjugated bond between the two triazine rings, and no group represented by -N = N- is contained. ]

[Wherein, X ₁ , X ₂ , Y ₁ and Y ₂ are each an alkoxy group, an aryloxy group, a heterocyclic oxy group, a heterocyclic group, a hydroxyl group, an amino group, a chlorine atom, an alkyl group, an aryl group, or The group represented by general formula (Va) is represented. X and Y each represent NR ₄ , O or S, and R ₄ represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. L represents a phenylene group, a naphthyl group or a heterocyclic group. ]

[Wherein, R ₁ , R ₂ and R ₃ each represents an alkyl group, an aryl group or a heterocyclic group. ]