JP2006194944A - Concentrated color developing composition for silver halide color photographic sensitive material and processing method for silver halide color photographic sensitive material using the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a concentrated color developing solution composition for a silver halide color photographic sensitive material which suppresses precipitation in a processing tank even under reduced replenishment or high temperature processing, keeps the preservability of a color developing agent even if the color developing agent is dissolved at high concentration, has improved storage stability when calcium ions are mixed, and enhances fog density stability, and to provide a processing method for a silver halide color photographic sensitive material using the composition. <P>SOLUTION: The concentrated color developing composition for a silver halide color photographic sensitive material is a one-part concentrate containing a compound represented by formula [1], an N-hydroxyalkyl substituted p-phenylenediamine color developing agent and a hydroxylamine derivative represented by the formula [2]: HO-N(R<SP>1</SP>)-L-A. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a novel color development concentrated composition for silver halide color photographic light-sensitive materials and a method for processing a silver halide color photographic light-sensitive material using the same. The present invention relates to a color development concentrated composition for a silver halide color photographic light-sensitive material having improved storage stability and fog density stability, and a method for processing a silver halide color photographic light-sensitive material using the same.

  The color developer composition is used for processing a silver halide color photographic light-sensitive material typified by a color photographic film, a color paper or the like that provides a target image. Such color developer compositions generally contain a color developing agent such as 4-amino-3-methyl-N- (2-methanesulfonamidoethyl) aniline as a reducing agent, and silver halide. It reacts with the color image forming coupler contained in the color photographic light-sensitive material to form a desired dye. Examples of color developing agents include those described in US Pat. Nos. 4,892,804, 4,876,174, 5,354,646, and 5,660,974. Various color developing compositions are described.

  When the silver halide color photographic light-sensitive material is continuously processed using the color development processing as described above, the processing consumed during the development reaction or taken out of the system by the processed silver halide color photographic light-sensitive material In order to replenish the liquid components, a replenishment method is generally performed in which a “color development replenisher” is added to the color developer in the processing tank. By adopting such a replenishing system, the development level and the stability of the color developing agent can be maintained.

  Further, as described above, the color developer contains a color developing agent and reacts with the coupler in the silver halide color photographic light-sensitive material to form a dye. Generally, the color developing agent itself is in the air. Since it is easily oxidized by oxygen, a method of adding an antioxidant called a preservative to a color developer is usually used. As preservatives for color developers, hydroxylamine derivatives have been known for a long time. For example, JP-A-1-298351 discloses mono- or di-substituted hydroxylamine derivatives. US Pat. No. 6,028,225 also discloses a similar preservative.

  In recent years, there has been an increasing demand for shortening processing time and reducing the replenishment amount for the purpose of environmental preservation. To achieve these purposes, a color developing agent is added to the color developer at a high concentration, or the processing temperature is increased. It is necessary to raise However, there are situations where the replenishment amount is low, the renewal rate of the color developer is lowered, and the color developer is liable to deteriorate during high-temperature processing. Under such conditions, it has been found that even if the preservative is used, sufficient preservability cannot be maintained with respect to the color developing agent.

  The color developer composition used for the preparation of the color developer is usually supplied to the user in three or more “parts” that are mixed immediately before use, or separated into a solution. By separating each composition into a plurality of parts, the chemical activity and solubility of the components can be maintained. For example, in the case of one part, it deteriorates when stored for a long time under alkaline conditions, Mutual reaction occurs. As such a color developer composition composed of three or more parts, for example, one part contains a color developing agent, the other part contains an alkali agent for maintaining alkalinity, and Another part contains preservatives and the like. By mixing all these parts and water, a homogeneous color developer can be obtained.

  There is a need in the photographic industry to reduce the number of parts used to prepare color developers, particularly replenishers, for example ready to use type solutions, concentrates or powders. Formulations and the like are commercially available in the art. Further, for example, EP 793,141 discloses a two-part color developing composition that can be supplied in solid or liquid form.

  In order to provide optimum processing performance, it is generally known that the concentration of processing solution components in a photographic processing tank must be kept within a certain range. The most important solvent in such photographic processing is water, and the solubility of both inorganic and organic salts used here in water is important. However, although the ready to use type solution is easy to use, it contains a large amount of water because all the components are at a target concentration, and the cost of production, transportation and storage is high. To that end, the photographic industry provides photographic processing compositions (including color developing compositions) in concentrated form so that manufacturers and users do not have to pay for shipping or storage for large amounts of water. There is a tendency to allow use in smaller containers. Furthermore, there is a need in the photographic industry for a processing composition that does not require the mixing of various ingredients (thus reducing mixing errors) and can be used immediately out of the container.

  On the other hand, other concentrated forms are, for example, drug pastes or slurries as described in European Patent Nos. 204,372 and 800,111. However, these proposed formulations currently have other drawbacks such as lack of homogeneity or a slow dissolution rate of solid components.

  Single formulations of color developing compositions that overcome the above problems are commercially available, but due to the presence of precipitates or multiple solvent phases, it is necessary to stir or mix well before use. Therefore, an appropriate apparatus for stirring the multiphase composition well is required.

  There is a continuing need in the photographic industry for a single composition color developer concentrate composition that is homogeneous, concentrated and stable. Such a color developing concentrate composition not only reduces the cost of transporting and storing a solution diluted with a large amount of water, but also eliminates the need to mix multiple parts or agitate the multi-phase composition. To provide attractive products.

  Various methods for solving the above-described problems have been proposed. For example, a method of dissolving a free base color developing agent in an organic solvent (for example, refer to Patent Document 1), or an alkylsulfonic acid is contained. A known color developing composition (see, for example, Patent Document 2) is known. Or the single part kit form isolate | separated into two layers of the part part of color developing agent and the other part with the organic solvent is also disclosed (for example, refer patent document 3).

However, the methods disclosed in each of the above-mentioned patent documents are effective for precipitation at low temperature storage, but have a problem in deterioration of the processing liquid composition during high temperature storage. It was found that precipitation occurred in the processing tank when blended and developed. In particular, it has been found that this tendency is accelerated when calcium ions are mixed in the dissolved water.
US Pat. No. 6,077,651 JP 2001-109115 A German Patent No. 19,916,933

  The present invention has been made in view of the above problems, and a first object thereof is for a silver halide color photographic light-sensitive material in which precipitation in a processing tank is suppressed even when low replenishment or high temperature processing is performed. A color developer concentrated composition and a method for processing a silver halide color photographic light-sensitive material using the same are provided. A second object is to provide a color developing agent having a high concentration even when the color developing agent is dissolved. It is an object of the present invention to provide a color developer concentrated composition for silver halide color photographic light-sensitive materials that has sufficient preservability. The third object is to provide a color developer concentrate composition for a silver halide color photographic light-sensitive material which has improved storage stability when calcium ions are mixed, and further has improved fog density stability, and halogenation using the same. It is to provide a method for processing a silver color photographic light-sensitive material.

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

(Claim 1)
One-part composition containing a compound represented by the following general formula [1] and containing a N-hydroxyalkyl-substituted p-phenylenediamine color developing agent and a hydroxylamine derivative represented by the following general formula [2] A color development concentrated composition for a silver halide color photographic light-sensitive material, characterized by being a concentrate.

[Wherein, R represents a hydrogen atom, an alkyl group, a haloalkyl group, a hydroxyalkyl group, a cycloalkyl group, or an aryl group, and R _{1 to} R ₄ are each independently —CX ₂ (OH) CHX ₁ —, X ₁ and X ₂ are each independently a hydrogen atom, a hydroxyl group, a hydroxyalkyl group, a substituted or unsubstituted alkyl group, or X ₁ and X ₂ together form a 5- to 8-membered carbocycle. Represents a carbon atom necessary for. n and m each represent an integer of 1 to 100. ]
General formula [2]
HO-N (R ¹ ) -LA
[In the formula, L represents an alkylene group, A represents a carboxyl group, a sulfo group, a phosphono group, a phosphinic acid residue, a hydroxyl group, an amino group, an ammonio group, a carbamoyl group, a sulfamoyl group, an alkylsulfonyl group, an alkoxyl group,- O— (B—O) _n —R ² having a carboxyl group, sulfo group, phosphono group, phosphinic acid residue, hydroxyl group, amino group, ammonio group, carbamoyl group, sulfamoyl group or alkylsulfonyl group as a substituent Represents an aryl group, B represents an alkylene group, R ² represents a hydrogen atom or an alkyl group, and n represents an integer of 1 to 4. R ¹ represents a hydrogen atom or an alkyl group. L and R ¹ may be linked to form a ring. ]
(Claim 2)
2. A color development concentrated composition for a silver halide color photographic material according to claim 1, wherein the molar ratio of the compound represented by the general formula [1] to sulfurous acid is 1: 1 to 1: 5. object.

(Claim 3)
The color development concentrated composition for a silver halide color photographic light-sensitive material according to claim 1 or 2, comprising a compound represented by the following general formula [3].

[Wherein R ^{3 to} R ⁶ are each a hydrogen atom, a halogen atom, a hydroxyl group, a sulfo group, a carboxyl group, an alkoxyl group, an alkoxycarbonyl group, a carbamoyl group, an alkyl group, an alkenyl group, an acyl group, an acyloxy group, a sulfamoyl group. Represents an acylamino group or a phenyl group. However, when R ³ represents a hydroxyl group or a hydrogen atom, R ⁵ is not a hydrogen atom. ]
(Claim 4)
4. The color development concentrated composition for a silver halide color photographic light-sensitive material according to claim 1, which is substantially free of bromide.

(Claim 5)
5. Halogenation that is imagewise exposed using a color developing solution prepared by diluting the color developing concentrated composition for a silver halide color photographic light-sensitive material according to any one of claims 1 to 4 three times or more. A method for processing a silver halide color photographic light-sensitive material, characterized by color-developing a silver color photographic light-sensitive material and then performing a desilvering step.

(Claim 6)
6. The method for processing a silver halide color photographic light-sensitive material according to claim 5, wherein the replenishing amount of the color developing solution is 300 to 500 ml per 1 m ^{2 of the} silver halide color photographic light-sensitive material.

  According to the present invention, even when low replenishment or high temperature processing is performed, the occurrence of precipitation in the processing tank is suppressed, and even when the color developing agent is dissolved at a high concentration, the color developing agent is sufficiently maintained. , And a color developing solution concentrated composition for a silver halide color photographic light-sensitive material with improved storage stability and improved fog density stability when mixed with calcium ions, and a silver halide color photographic light-sensitive material using the same Can be provided.

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

  As a result of intensive studies in view of the above problems, the present inventor contains a compound represented by the general formula [1], and contains an N-hydroxyalkyl-substituted-p-phenylenediamine color developing agent and the general formula. A color development concentrated composition for a silver halide color photographic light-sensitive material characterized by being a one-part composition (hereinafter also referred to as a single part) containing the hydroxylamine derivative represented by [2]. Even when replenishment or high-temperature processing is performed, the occurrence of precipitation in the processing tank is suppressed, and even when the color developing agent is dissolved at a high concentration, the color developing agent is sufficiently retained, and calcium ions are mixed in. The present inventors have found that a color developer concentrated composition for a silver halide color photographic light-sensitive material with improved storage stability and improved fog density stability can be realized. It is.

  Details of the present invention will be described below.

  The color developer concentrated composition for silver halide color photographic light-sensitive material of the present invention (hereinafter also simply referred to as color developer concentrated composition) contains one compound represented by the general formula [1]. Features.

In the general formula [1], R represents a hydrogen atom, an alkyl group, a haloalkyl group, a hydroxyalkyl group, a cycloalkyl group or an aryl group, and R _{1 to} R ₄ each independently represent —CX ₂ (OH) CHX ₁ X ₁ and X ₂ are each independently a hydrogen atom, a hydroxyl group, a hydroxyalkyl group, a substituted or unsubstituted alkyl group, or X ₁ and X _{2 taken} together are a 5- to 8-membered carbocyclic ring Represents the carbon atoms necessary to form n and m each represent an integer of 1 to 100.

  Specific examples of the compound represented by the general formula [1] according to the present invention are shown below, but the present invention is not limited only to these exemplified compounds.

In the color developing solution according to the present invention, the content of the compound represented by the general formula [1] according to the present invention is 2 × 10 ⁻⁴ mol / L or more and 1 × 10 ⁻¹ mol / L or less. Preferably there is.

In the color developer concentrated composition of the present invention, the compound represented by the general formula [1] according to the present invention contains 1 × 10 ⁻³ mol / L or more and 5 × 10 ⁻¹ mol / L or less. It is preferable.

  The color developer concentrated composition of the present invention preferably contains a sulfite, and examples thereof include sodium sulfite and potassium sulfite. By setting the molar ratio of the compound represented by the general formula [1] according to the present invention to sulfurous acid in the range of 1: 1 to 1: 5, it is preferable from the viewpoint of further achieving the object effect of the present invention.

  The color developer concentrated composition of the present invention is characterized by containing a hydroxylamine derivative represented by the general formula [2] together with the compound represented by the general formula [1].

  In the general formula [2], L and B each represent an alkylene group, preferably a linear or branched alkylene group having 1 to 10 carbon atoms, particularly preferably having 1 to 5 carbon atoms. Specifically, preferred examples include methylene, ethylene, trimethylene, n-propylene, and i-propylene. The alkylene groups represented by L and B include those having a substituent. Examples of the substituent include a carboxyl group, a sulfo group, a phosphono group, a phosphinic acid residue, a hydroxyl group, and an amino group (this amino group is an alkyl (preferably Include those having 1 to 5 carbon atoms and substituted), and among them, an alkoxyl group is preferable, among which a carboxyl group, a sulfo group, a phosphono group, and a hydroxyl group are particularly preferable examples.

A is a carboxyl group, sulfo group, phosphono group, phosphinic acid residue, hydroxyl group, amino group, ammonio group, carbamoyl group, sulfamoyl group, alkylsulfonyl group, alkoxyl group, -O- (BO) _n -R. ² groups, an aryl group having a carboxyl group, a sulfo group, a phosphono group, a phosphinic acid residue, a hydroxyl group, an amino group, an ammonio group, a carbamoyl group, a sulfamoyl group, or an alkylsulfonyl group as a substituent, represented by A Amino group, ammonio group, carbamoyl group, sulfamoyl group, alkylsulfonyl group, alkoxyl group, —O— (B—O) _n —R ² group, and aryl group, amino group, ammonio group, carbamoyl group A sulfamoyl group or an alkylsulfonyl group having a substituent Including. Preferred examples of the substituent include an alkyl group (for example, methyl, 1,1-dimethyl-2-sulfoethyl, carboxyethyl, etc.) and a sulfo group.

  Preferable examples of the substituent substituted on the aryl group when A and A are an aryl group include a carboxyl group, a sulfo group, a hydroxyl group, a phosphono group, a carbamoyl group, an alkyl-substituted carbamoyl group, and an alkoxyl group. When each said group has an alkyl substituent, the preferable alkyl group is C1-C5, and especially a methyl group and an ethyl group are preferable.

  When A represents an ammonio group, the compound represented by the general formula [2] may be accompanied by sulfate ion, p-toluenesulfonate ion, chlorine ion, sulfite ion, etc. as a counter ion of the ammonio group. In addition, when L and A are accompanied by a substituent having an acid radical such as a carboxyl group, a sulfo group, a phosphono group, a phosphinic acid residue, or a hydroxyl group, the hydrogen of the acid radical is replaced with an alkali metal atom or an ammonium atomic group. May be.

  The aryl group represented by A is preferably phenyl. When A is an alkoxyl group, L is preferably substituted with a hydroxyl group, and 3-alkoxy-2-hydroxypropyl is preferred as -LA.

Specific examples of -LA include carboxymethyl group, carboxyethyl group, carboxypropyl group, sulfoethyl group, sulfopropyl group, sulfobutyl group, phosphonomethyl group, phosphonoethyl group, hydroxyethyl group, 3-methoxy-2-hydroxypropyl group , 3-ethoxy-2-hydroxypropyl group, 3-propoxy-2-hydroxypropyl group, p-carboxybenzyl group, — (CH ₂ CH ₂ ) ₂ H, — (CH ₂ CH ₂ ) ₃ H are preferred examples. Carboxymethyl group, carboxyethyl group, sulfoethyl group, sulfopropyl group, phosphonomethyl group and phosphonoethyl group can be mentioned as particularly preferred examples.

R ¹ represents a hydrogen atom or an alkyl group, and the alkyl group includes those having a substituent. The alkyl group is preferably a linear or branched one having 1 to 10 carbon atoms, particularly preferably 1 to 5 carbon atoms. Examples of the substituent of the alkyl group include a carboxyl group, a sulfo group, a phosphono group, a phosphinic acid residue, a hydroxyl group, an amino group, a carbamoyl group, a sulfamoyl group, an alkylsulfonyl group, an acylamino group, an alkylsulfonylamino group, and an arylsulfonylamino group. Preferred examples include a group, an alkoxycarbonyl group, an arylsulfonyl group, a nitro group, a cyano group and a halogen atom. The amino group, carbamoyl group, sulfamoyl group, alkylsulfonyl group, acylamino group, alkylsulfonylamino group, arylsulfonylamino group, alkoxycarbonyl group, and arylsulfonyl group mentioned as the above substituent include those having a substituent. Preferred examples of the substituent include an alkyl group and a sulfo group. The alkyl group contained or further substituted in these substituents preferably has 1 to 5 carbon atoms, and particularly preferably 1 to 3 carbon atoms.

Among them, R ¹ is preferably 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, or a hydroxyethyl group. Examples thereof include a hydrogen atom, a carboxymethyl group, a carboxyethyl group, a sulfoethyl group, a sulfopropyl group, a phosphonomethyl group, and a phosphonoethyl group.

Further, there may be two or more substituents for L, A, R ¹ and R ² .

L and R ¹ may be linked to form a ring. When L and R ¹ form a ring, L and R ¹ form a ring directly and A has a substituent, or A represents an amino group which may be alkyl-substituted, and the nitrogen atom of the amino group is L and R ¹ can also form a ring (for example, form a piperazine ring).

  A particularly preferred hydroxylamine derivative represented by the general formula [2] is a mono- or di-alkylhydroxylamine having 1 to 8 carbon atoms in total.

  Specific examples of the compound represented by the general formula [2] according to the present invention are shown below, but the present invention is not limited to these exemplified compounds.

_{(2-57) HON (-CH 2 CH} (OH) CH 2 (OH)) 2
(2-58) HON (isoC ₃ H ₇ ) CH ₂ CH ₂ SO ₃ H
The compound represented by the general formula [2] according to the present invention can be synthesized by alkylating a commercially available hydroxylamine (nucleophilic substitution reaction, addition reaction, Mannich reaction, etc.), for example, , West German Patent No. 1,159,634, “Inorganica Chimica Acta”, 93, (1984) p101 to 108, and the like. A more specific method for synthesizing a compound is described in JP-A-3-266837.

  The amount of the hydroxylamine derivative represented by the general formula [2] according to the present invention varies depending on the degree of concentration of the color developing concentrated composition, but both are 0.2 g to 100 g per liter of color developing processing solution, preferably Is 0.5 to 20 g.

  In the color developer concentrated composition of the present invention, the molar ratio of the compound represented by the general formula [1] and the hydroxylamine derivative represented by the general formula [2] is 1: 1 to 1:30. More preferably, it is the range of 1: 2 to 1:20.

  In the color developer concentrated composition of the present invention, the compound represented by the general formula [1], the hydroxylamine derivative represented by the general formula [2], and N-hydroxyalkyl-substituted- A p-phenylenediamine color developing agent is used.

  The N-hydroxyalkyl-substituted p-phenylenediamine color developing agent is a silver halide color photographic light-sensitive material compared with a paraphenylenediamine color developing agent having no water-soluble group such as N, N-diethyl-p-phenylenediamine. Not only has the advantages of no contamination of the material and low skin sensitization, but in particular, by combining with the compound represented by the general formula [1] according to the present invention, the object of the present invention is made more effective. Can be played.

  Specific examples of the N-hydroxyalkyl-substituted p-phenylenediamine color developing agent according to the present invention are shown below, but the present invention is not limited only to these exemplified compounds.

  Of the paraphenylenediamine color developing agents exemplified above, the exemplified compounds (C-1) and (C-2) are preferred for use in the present invention, and the exemplified compound (C-2) is particularly preferred. .

  The paraphenylenediamine color developing agent according to the present invention is usually used in the form of a salt such as hydrochloride, sulfate or p-toluenesulfonate.

The paraphenylenediamine color developing agent having a water-soluble group used in the present invention is usually preferably used in a range of 1 × 10 ⁻² to 2 × 10 ⁻¹ mol per color developing solution, From the viewpoint of processing, the range of 1.5 × 10 ⁻² to 2 × 10 ⁻¹ mol per color developing solution is more preferable.

  The color development concentrated composition of the present invention preferably contains a compound represented by the above general formula [3] in addition to the structure defined above.

In the general formula [3], R ^{3 to} R ⁶ are each a hydrogen atom, halogen atom, hydroxyl group, sulfo group, carboxyl group, alkoxyl group, alkoxycarbonyl group, carbamoyl group, alkyl group, alkenyl group, acyl group, acyloxy group. Represents a group, a sulfamoyl group, an acylamino group, or a phenyl group. The alkyl group and alkenyl group represented by R ^{3 to} R ⁶ preferably have 1 to 7 carbon atoms. In addition, the alkoxyl group, alkoxycarbonyl group, carbamoyl group, alkyl group, alkenyl group, acyl group, acyloxy group, sulfamoyl group, acylamino group, and phenyl group represented by R ^{3 to} R ⁶ include those each having a substituent. . When R ³ represents a hydroxyl group or a hydrogen atom, R ⁵ is not a hydrogen atom.

  Hereinafter, although the specific example of a compound represented by the said General formula [3] concerning this invention is shown, this invention is not limited only to these illustrated compounds.

(3-1) 4-Isopropyl-1,2-dihydroxybenzene (3-2) 1,2-dihydroxybenzene-3,5-disulfonic acid (3-3) 1,2,3-trihydroxybenzene-5 Carboxylic acid (3-4) 1,2,3-trihydroxybenzene-5-carboxymethyl ester (3-5) 1,2,3-trihydroxybenzene-5-carboxy-n-butyl ester (3-6) 5-t-butyl-1,2,3-trihydroxybenzene (3-7) 1,2-dihydroxybenzene-3,5,6-trisulfonic acid (3-8) 1,2-dihydroxybenzene-6 Chloro-3,5-disulfonic acid (3-9) 1,2-dihydroxybenzene-3,4,5,6-tetrasulfonic acid Among the compounds represented by the above general formula [3], particularly preferred in the present invention. Examples of commonly used compounds include Exemplified Compound (3-2) 1,2-dihydroxybenzene-3,5-disulfonic acid, and these can also be used as alkali metal salts such as sodium salts and potassium salts. Can do.

  The compound represented by the general formula [3] according to the present invention can be used in the range of 0.01 to 1.0 g, preferably 0.02 to 0.3 g, per liter of the color developing solution. More preferably, the amount is 0.05 to 0.2 g. By using the compound represented by the general formula [3] according to the present invention within the above-mentioned addition amount range, the object effect of the present invention can be further exhibited. .

  In addition, the compound represented by the general formula [3] according to the present invention may be used alone or in combination of two or more. In addition, aminopolyphosphonic acid such as aminotri (methylenephosphonic acid) or ethylenediaminetetraphosphoric acid, oxycarboxylic acid such as citric acid or gluconic acid, phosphonocarboxylic acid such as 2-phosphonobutane-1,2,4-tricarboxylic acid, tripolylin It may be used in combination with other chelating agents such as acid or polyphosphoric acid such as hexametaphosphoric acid.

  The color developer concentrated composition of the present invention preferably further contains a compound represented by the following general formula [4].

General formula [4]
HO— (W—O) _n —H
In the above general formula [4], W represents —CH ₂ CH ₂ —, —CH ₂ CH ₂ CH ₂ —, or —CH ₂ CH (CH ₃ ) —, and n represents an integer of 1-30.

  Hereinafter, although the specific example of a compound represented by the said General formula [4] concerning this invention is shown, this invention is not limited only to these illustrated compounds.

(4-1) Ethylene glycol (4-2) Diethylene glycol (4-3) Triethylene glycol (4-4) Tetraethylene glycol (4-5) Propylene glycol (4-6) Dipropylene glycol (4-7) Tri Propylene glycol (4-8) Polyethylene glycol # 200 (average molecular weight 200)
(4-9) Polyethylene glycol # 300 (average molecular weight 300)
(4-10) Polyethylene glycol # 400 (average molecular weight 400)
(4-11) Polyethylene glycol # 600 (average molecular weight 600)
(4-12) Polyethylene glycol # 1000 (average molecular weight 1000)
(4-13) Polypropylene glycol (average molecular weight 400)
(4-14) Polypropylene glycol (average molecular weight 700)
In the color developing solution according to the present invention, the compound represented by the general formula [4] is preferably contained in an amount of 10 g / L to 100 g / L. In the color development concentrated composition of the present invention, the compound represented by the above general formula [4] is preferably contained in an amount of 50 g / L to 700 g / L.

  The color development concentrated composition of the present invention is characterized by having a single-part configuration, but the concentration ratio is preferably 1.2 times or more and 10 times or less, particularly preferably 3.0 times or more, 10 times or less. If the concentration rate is 3.0 times or more, it is more preferable from the viewpoint of storage space and transportation and the effect of the present invention, and the upper limit is 5 times or less from the viewpoint of stability and solubility in the concentrated state. It is more preferable that

  The single part in the present invention includes a kit containing all the components (for example, alkali, developing agent, preservative, etc.) necessary for the color developing solution, that is, a color developing agent that has been widely used conventionally. For multi-parts that are composed of individual parts, such as parts that contain alkali-preserving parts (alkali agents), and parts that contain antioxidants, etc. The single part referred to in the present invention is one in which each color developing composition as described above is composed of one part.

  The highly concentrated color development concentrated composition of the single part composition of the present invention is a color developing solution (worker) diluted 1.2 times or more and 10 times or less, preferably 3.0 times or more and 10 times or less with water or the like. Solution) or a color development replenisher, and the imagewise exposed silver halide color photographic light-sensitive material is subjected to color development and then desilvered. Therefore, the concentration rate in the present invention can be defined as follows.

  Concentration rate = volume of color developing solution (worker solution) or color developing replenisher / volume of single-part color developing concentrated composition.

  Next, other components of the color development concentrated composition of the present invention will be described.

  In the color developer, in addition to the preservative according to the present invention described above, use of the preservative shown below is not limited. Preservatives refer to all compounds that reduce the degradation rate of an aromatic primary amine color developing agent by being included in a processing solution of a 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 And quaternary ammonium salts, nitroxy radicals, alcohols, oximes, diamide compounds, and condensed amines. These are disclosed in JP-A 63-4235, 63-30845, 63-21647, 63-44655, 63-53551, 63-43140, 63-56654, 63- 58346, 63-43138, 63-146041, 63-44657, 63-44656, 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.

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

  The color developing concentrated composition of the present invention preferably has a high pH in order to contain the color developing agent in a high concentration, and the preferred pH is in the range of 12.0 or more, more preferably 12.5. It is in the range of ˜13.5. The color developer and development replenisher prepared therefrom are preferably used at a pH of 9.5 or higher, more preferably from 9.7 to 12.5. Further, an alkali agent, a buffering agent, and if necessary, an acid can be contained so that the pH value can be maintained.

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

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

  Since the buffer is not a component that is reacted and consumed, the concentration thereof is preferably 0.01 to 2 mol, more preferably 0.1 to 0.5 mol, per liter for both the color developing solution and the replenisher. The amount of addition in the composition or concentrated composition is determined.

  An optional development accelerator can be added to the color development concentrated composition of the present invention as necessary. 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, etc. Amine compounds described in the report or specification, Japanese Patent Publication No. 37-16088, Japanese Patent Publication No. 42-25201, US Pat. No. 3,128,183, Japanese Patent Publication No. 41-11431, Japanese Patent Publication No. 42-23883, and US Pat. Polyalkylene oxide, other 1-phenyl-3-virazolitones or imidazoles represented in each publication or specification such as 3,532,501 can be added as necessary. The addition amount in the concentrated composition is determined so that the concentration thereof is 0.001 to 0.2 mol, preferably 0.01 to 0.05 mol, per liter for both the color developing solution and its replenisher. Is preferred.

  An optional antifoggant can be added to the color development concentrated composition of the present invention, if necessary. Examples of the organic antifoggant include benzotriazole, 6-nitrobenzimidazole, 5-nitroisoindazole, 5-methylbenzotriazole, 5-nitrobenzotriazole, 5-chloro-benzotriazole, 2-thiazolyl-benzimidazole, 2 -Representative examples include nitrogen-containing heterocyclic compounds such as thiazolylmethyl-benzimidazole, indazole, hydroxyazaindolizine, and adenine.

  In addition, a fluorescent whitening agent can be used in the color development concentrated composition of the present invention as necessary. As the optical brightener, a bis (triazinylamino) stilbene sulfonic acid compound is preferred. As the bis (triazinylamino) stilbene sulfonic acid compound, a known or commercially available niaminostilbene-based auto-enhancing agent can be used. As the known bis (triazinylamino) stilbene sulfonic acid compound, for example, compounds described in JP-A-6-329936, JP-A-7-140625, JP-A-10-14049 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 Hakkol BRK.

  As other bis (triazinylamino) stilbene sulfonic acid compounds, compounds I-1 to I-48 and JP-A-2001-2001 described in paragraphs [0038] to [0049] of JP-A No. 2001-281823 are disclosed. The compounds II-1 to II-16 described in paragraph Nos. [0050] to [0052] of JP-A-281823 can also be mentioned. The amount of the above-described fluorescent brightening agent to be added may be determined in the concentrated composition so that it becomes 0.1 to 0.1 mol per liter when used as a color developing solution and a replenisher thereof. preferable.

In the color developing solution for color negative film using the color developing concentrated composition of the present invention, bromine ion is usually 0.2 × 10 ^{−2 to} 15.0 × 10 ⁻² mol / liter, preferably 0.5. In many cases, it is contained in 10 × 10 ^{−2 to} 5.0 × 10 ⁻² mol / liter, but bromine ions are normally released as a by-product of development to the color development processing developer. The composition preferably contains substantially no bromide. Further, iodine ions are often contained in an amount of 0.2 × 10 ^{−3 to} 15.0 × 10 ⁻³ mol / liter, preferably 0.5 × 10 ^{−3 to} 5.0 × 10 ⁻³ mol / liter. In general, iodine ions are sometimes released to the developer as a by-product of development, and conversely, they may be absorbed and consumed by undeveloped silver halide. In order to maintain the above, it may not be necessary to add to the replenisher, or may be added to the replenisher. Further, when bromide ions are contained in the color paper color developing solution using the color developing concentrated composition of the present invention, it is 1.0 × 10 ⁻³ mol / liter or less. In the development concentrated composition, it is preferable that bromide is not substantially contained.

In the present invention, the color development processing temperature that can be applied in the processing method is preferably 30 to 55 ° C., more preferably 35 to 55 ° C. when the photosensitive material to be developed is color paper. Preferably it is 38-45 degreeC. The color development processing time is preferably from 5 to 90 seconds, more preferably from 15 to 60 seconds. The replenishment amount is preferably small, but 15 to 600 ml per 1 m ^{2 of} the light-sensitive material is suitable, preferably 15 to 120 ml, particularly preferably 30 to 60 ml. On the other hand, in the case of color development processing of a color negative film, the development temperature is preferably 20 to 55 ° C, more preferably 30 to 55 ° C, and further preferably 35 to 45 ° C. The color development processing time is preferably 20 seconds to 6 minutes, more preferably 30 to 220 seconds.

In the processing method of the silver halide color photographic light-sensitive material of the present invention, a smaller replenishment amount is preferable, but 100 to 800 ml per 1 m ^{2 of} the light-sensitive material is suitable, preferably 200 to 500 ml. In particular, the replenishment amount of the color developing solution is preferably 300 to 500 ml. In the present invention, the color development time refers to the time from when the photosensitive material enters the color developer to the next processing step (for example, bleach-fixing solution). When processed by an automatic developing machine or the like, the time during which the photosensitive material is immersed in the color developer (so-called submerged time) and the photosensitive material leave the color developer, and the solution is prepared for the next processing step. The total of both the time for transporting outside (so-called crossover time) is called color development time. The crossover time is preferably 10 seconds or less, more preferably 5 seconds or less.

The color development concentrated composition of the present invention having the above-described configuration is preferably contained in a container having an oxygen permeability of 50 ml / (m ² · day · atm) or less, and an oxygen permeability coefficient of 20 ml / (m ² · atm · day) It is more preferable to package with the following packaging material. In particular, when stored for a long period of time, the formation of precipitates inside the container is reduced, and the influence of the outside air can be remarkably improved. As a result, the color developing composition and the packaging container can be kept stable for a long period of time.

As the form of the container applicable to the storage of the color development concentrated composition of the present invention, it is possible to use a container having any form in which airtightness is maintained, such as a bottle container form, a pillow form, and a standing pouch form. Among these, the color development concentrated composition of the present invention has a characteristic that the generation of decomposition gas and the like is suppressed even when stored for a long period of time, and therefore, it is preferable to use a flexible container having excellent handleability.

The material of the container according to the present invention may be any material such as paper, glass, plastic, etc., but the lower limit of oxygen permeability may be zero, but the lower limit based on practical container sealing is 0.1 ml / It is about (m ² · day · atm).

  The measurement of the oxygen permeability coefficient in the present invention can be determined according to a method defined in JIS 1707 according to a conventional method.

  In the processing method of a silver halide color photographic light-sensitive material using the color development concentrated composition of the present invention, the exposed silver halide color photographic light-sensitive material is diluted with the color developing solution concentrated liquid of the present invention. Subsequent to the used color processing step (color developer), bleaching step (bleaching solution), fixing step (fixing solution) or bleach-fixing step (bleaching fixing solution), stabilization step (stabilizing solution), and then drying. .

  Further, development processing can be continuously performed while replenishing a replenishing color developer, a replenishing bleaching solution, a replenishing fixing solution, a replenishing bleach-fixing solution, a replenishing stabilizing solution, or the like.

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

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

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

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

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

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

  Bleaching solutions, fixing solutions, and bleach-fixing solutions generally contain sulfites such as sodium sulfite, potassium sulfite, ammonium sulfite, and sodium metabisulfite as preservatives. In addition, ascorbic acid and carbonyl A bisulfite adduct or a carbonyl compound may be added.

  Furthermore, you may add a buffering agent, a fluorescent whitening agent, a chelating agent, an antifoamer, an antifungal agent, etc. as needed. The ammonium cation concentration in the bleaching solution, the fixing solution, and the bleach-fixing solution is preferably 50 mol% or less with respect to the total cations from the viewpoint of workability, but from the viewpoint of processability, the ammonium cation concentration is 50 mol% or more. It is preferable that there is.

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

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

  Next, the rinsing or stabilizing process and the treatment liquid used therein will be described.

  Rinsing or stabilizing solution used in the stabilization step includes chelating agents (ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, 1-hydroxyethylidene-1,1-diphosphonic acid, etc.), buffering agents (potassium carbonate, borate, acetate, Phosphates, etc.), antifungal agents (Dearside 702 (manufactured by Dearborn, USA), p-chloro-m-cresol, benzoisothiazolin-3-one, etc.), fluorescent brighteners (triazinyl stilbene compounds, etc.) ), Antioxidants (ascorbate, etc.), water-soluble metal salts (zinc salt, magnesium salt, etc.) and the like, which are usually contained in the stabilizing solution, can be used as appropriate.

Further, the rinse or stabilizing solution may contain arylsulfinic acid such as p-toluenesulfinic acid and m-carboxybenzenesulfinic acid from the viewpoint of liquid storage stability, and may contain sulfite, bisulfite or metabisulfite. It is preferable to contain a salt. Any organic or inorganic substance may be used as long as it releases sulfite, but inorganic salts are preferred. Preferred specific compounds include sodium sulfite, potassium sulfite, ammonium sulfite, ammonium bisulfite, potassium bisulfite, sodium bisulfite, sodium metabisulfite, potassium metabisulfite, ammonium metabisulfite and the like. These salts are preferably added in an amount of at least 1 × 10 ⁻³ mol / L or more in the stabilizing solution, more preferably from 5 × 10 ⁻³ mol / L to 5 × 10 ⁻² mol. / L to be added.

  4-10 are preferable and, as for the preferable pH of a stabilization process, More preferably, it is 5-8.

  The temperature of the stabilization step can be variously set depending on the use and characteristics of the silver halide color photographic light-sensitive material to be processed, but is generally preferably 15 to 45 ° C, more preferably 20 to 40 ° C. Although the time can be set arbitrarily, a shorter time is desirable from the viewpoint of reducing the processing time. The time is preferably 5 seconds to 1 minute 45 seconds, more preferably 10 seconds to 1 minute. However, when the silver halide color photographic light-sensitive material is color paper, the time required for the stabilization processing step is 8 to 26 seconds. In addition, when the silver halide color photographic light-sensitive material is a color negative film, the time required for the stabilization process is preferably 10 to 40 seconds.

  A smaller replenishment amount is preferable from the viewpoint of running cost, reduction of discharge amount, handling property, and the like.

A specific preferable replenishing amount is preferably 0.5 to 50 times, more preferably 3 to 40 times the amount of silver halide color photographic light-sensitive material, which is brought from the previous bath per unit area. Alternatively, the amount is preferably 1 liter or less per 1 m ^{2 of} silver halide color photographic light-sensitive material, more preferably 500 ml or less. The replenishment may be performed continuously or intermittently.

  In the treatment method of the present invention, the structure of the stabilization process using the stabilizing liquid may be composed of one tank or two or more layers, preferably two or more tanks. It is preferable to use a configured multi-stage countercurrent system.

  Multi-stage counter-current system is a method of conveying silver halide photographic light-sensitive materials in a stabilizing tank divided into a plurality of stages, while the stabilizing solution overflows into each multi-stage divided stabilizing tank from the downstream to the upstream in the conveying direction of the photosensitive material. It is a system that flows along the road and performs a stabilization process.

  The silver halide color photographic light-sensitive material applicable to the processing method using the color development 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 movie film, etc. can be mentioned.

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

  The specific constitution of the silver halide color photographic light-sensitive material applicable to the processing method using the color development concentrated composition of the present invention is described in detail in, for example, the following Research Disclosure (hereinafter abbreviated as RD). It is described and can be used as a reference.

  The silver halide emulsion is, for example, Research Disclosure (hereinafter abbreviated as RD) No. 17643, pp. 22-23 (December 1979), “1. Emulsion preparation and types”, and RD No. 18716, p.648, “Photophysics and Chemistry” by Grakide, published by Paul Monter (P. Glkides, Chimie et Physiquegraph, Paul Montel, 1967), “Photographic Emulsion Chemistry” by Duffin, published by Focal Press (GF). Daufin, Photographic Emulsion Chemistry Focal Press 1966), “Production and Coating of Photoemulsions” by Zerikman et al., Published by Focal Press (V. L. Zelikman et al., Making and coating Photo 19). Can be prepared using methods. As the emulsion, monodispersed emulsions described in US Pat. Nos. 3,574,628 and 3,665,394 and British Patent 1,413,748 are also preferable.

The silver halide emulsion can be subjected to physical ripening, chemical ripening and spectral sensitization. The additive used in such a process is RDNo. 17643, RDNo. 18716 and RDNo. 308119 (hereinafter abbreviated as RD17643, RD18716, and RD308119, respectively). The description part is shown below. In addition, each numerical value described below represents the described page.
[Item] [Page of RD308119] [RD17643] [RD18716]
Chemical sensitizer 996 III-A 23 648
Spectral sensitizer 996 IV-AA,
B, C, D, 23-24 648-649
H, I, J Item Supersensitizer 996 IV-AE, J Item
23-24 648-649
Antifoggant 998 VI 24-25 649
Stabilizer 998 VI 24-25 649
Known photographic additives that can be used in the silver halide color photographic light-sensitive material of the present invention are also described in the RD. The following is a relevant description.
[Item] [Page of RD308119] [RD17643] [RD18716]
Anti-turbidity agent 1002 VII-I Item 25 650
Dye Image Stabilizer 1001 VII-J Item 25
Brightener 998V 24
UV absorber 1003VIII-I,
Item XIII-C 25-26
Light absorber 1003VIII 25-26
Light scattering agent 1003VIII
Filter dye 1003VIII 25-26
Binder 1003IX 26 651
Antistatic agent 1006XIII 27 650
Hardener 1004X 26 651
Plasticizer 1006XII 27 650
Lubricant 1006XII 27 650
Activating agent / Coating aid 1005XI 26-27 650
Matting agent 1007XVI
Developer (contained in silver halide color photographic materials)
1001XXB Various couplers can be used in the photosensitive layer according to the present invention, and specific examples thereof are described in the above RD. The following is a relevant description.

[Item] [Page of RD308119] [RD17643]
Yellow Coupler 1001 VII-D Item VIIC-G Item Magenta Coupler 1001 VII-D Item VIIC-G Cyan Coupler 1001 VII-D Item VIIC-G Item Colored Coupler 1002 VII-G Item VIIG Item DIR Coupler 1001VII-F Item VIIF Item BAR Coupler 1002VII- Item F Release of other useful residues 1001VII-F Item Coupler Alkali-soluble coupler Item 1001VII-E The above additives can be added by the dispersion method described in RD308119XIV.

  In the silver halide color photographic light-sensitive material according to the present invention, auxiliary layers such as a filter layer and an intermediate layer described in the above-mentioned item RD308119VII-K can be provided.

  The silver halide color photographic light-sensitive material according to the present invention can have various layer structures such as a normal layer, a reverse layer, and a unit structure described in the above-mentioned item RD308119VII-K.

  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 Color Developing Concentrated Composition >>
The following additives were sequentially mixed and dissolved to prepare color developing concentrated compositions 1-1 to 1-10.

[Composition of color development concentrated composition: amount added per 5 L of color development replenisher]
Sodium sulfite The amount of addition shown in Table 1 Potassium carbonate 200 g
Diethylenetriaminepentaacetic acid 5sodium 15g
Potassium bromide 0.15g
Compounds represented by general formula [1] (types listed in Table 1) Addition amounts listed in Table 1 Compounds represented by general formula [2] (types listed in Table 1) Addition amounts listed in Table 1 Color developing agent: 30 g of sulfate of Exemplified Compound (C-3)
pH 10.20
It was made up to 1 L with water so that the concentration rate was 5 times with water, and the pH was adjusted with 50% sulfuric acid or potassium hydroxide. For example, when a color developing replenisher is prepared by finishing 1 L of a color developing concentrated composition with water to 5 L, the concentration rate becomes 5 times.

<< Evaluation of Color Developing Concentrated Composition >>
[Evaluation of storage stability 1: Measurement of residual ratio of color developing agent]
Each of the color development concentrated compositions prepared above is put in a sealed container and stored in a thermostatic bath at 50 ° C. for one month, and then the unprocessed color development concentrated composition and the color development developed after the storage are processed. The color developing agent (sulfate of Exemplified Compound (C-3)) in the concentrated composition was measured according to the following method, and the color developing agent residual ratio was determined by the following formula.

  The color developing agent (sulfate of Exemplified Compound (C-3)) was quantified using a liquid chromatography method (HPLC method) and separated by an HPLC apparatus using a reversed-phase column and subjected to quantitative analysis. Subsequently, the color developing agent residual ratio was measured according to the following formula, and this was used as a measure of the storage stability of the color developing concentrated composition.

Residual rate of color developing agent = (color developing agent amount of storage processed product / color developing agent amount of unprocessed product) × 100 (%)
[Evaluation of storage stability 2: Evaluation of precipitation resistance]
The liquid state of each color developing concentrated composition that had been subjected to a storage treatment for 1 month in the 50 ° C. constant temperature bath was visually observed to confirm the presence or absence of precipitates.

  The results obtained as described above are shown in Table 1.

  As is clear from the results shown in Table 1, the color development concentrated composition of the present invention containing the compound represented by the general formula [1] and the compound represented by the general formula [2] Even after storage in a high temperature environment of 50 ° C., it can be seen that the color developing agent residual rate is high and no precipitate is observed, which is excellent in storage stability under high concentration conditions. Moreover, it turns out that it is more preferable to make the molar ratio of the compound represented by General formula [1] and sulfurous acid into the range of 1: 1-1: 10, especially 1: 1-1: 5.

Example 2
<< Preparation of Color Developing Concentrated Composition >>
In the preparation of the color developing concentrated composition 1-4 described in Example 1, the color developing concentrated composition was similarly prepared except that the compound represented by the general formula [3] was added as described in Table 2. 2-1 to 2-6 were prepared.

<< Evaluation of Color Developing Concentrated Composition >>
Evaluation of storage stability 1 of the color development concentrated compositions 2-1 to 2-6 prepared above and the color development concentrated composition 1-4 prepared in Example 1 in the same manner as described in Example 1. (Measurement of residual ratio of color developing agent) and coloring resistance were evaluated according to the following method.

[Evaluation of storage stability 3: Evaluation of coloring resistance]
According to the method described in Example 1, the color development state of each color developing concentrated composition that had been stored for 1 month in a constant temperature bath at 50 ° C. was visually observed, and the color resistance was evaluated according to the following criteria. .

○: Colored state almost similar to that of the unprocessed color development concentrated composition. Δ: Slightly advanced compared to the unprocessed color development concentrated composition, but in a practically acceptable range. Table 2 shows the results obtained as described above, in which strong coloring was observed as compared with the processed color developing concentrated composition.

  As is apparent from the results shown in Table 2, the color development concentrated composition having the constitution defined in the present invention is allowed to coexist with the compound represented by the general formula [3] according to the present invention, thereby increasing the temperature environment. It can be seen that the residual ratio of the color developing agent after being stored below is further improved, and in addition, the color resistance is improved.

Example 3
<Development processing>
According to the following method, a processing tank solution and a replenisher for a color negative film were prepared.

[Each treatment composition]
(Color development replenisher 1)
The color developing replenisher 1 was prepared by diluting the color developing concentrated composition 1-4 described in Example 1 with water 5 times.

(Color development tank solution 1)
The color developing replenisher 1 was diluted to 70% (1.43 times), 1.1 g of potassium bromide was added per liter, and the pH was adjusted to 10.1 with sulfuric acid to prepare a color developing processing tank solution 1. .

(Color development replenisher 2)
The color developing replenisher 2 was prepared by diluting the color developing concentrated composition 1-3 described in Example 1 5 times with water.

(Color development tank solution 2)
The color developing replenisher 2 was diluted to 70% (1.43 times), 1.1 g of potassium bromide was added per liter, and the pH was adjusted to 10.1 with sulfuric acid to prepare a color developing processing tank liquid 2. .

(Bleaching solution per 1L)
Treatment tank solution Replenisher 3-propylenediamine tetraferric sodium acetate 133g 190g
3-propylenediaminetetraacetic acid 5 g 7 g
Ammonium bromide 60g 90g
Maleic acid 40g 60g
Succinic acid 10g 15g
pH 4.5 3.5
Water was added to 1 L, and the pH was adjusted with aqueous ammonia or 50% sulfuric acid.

(Fixing solution: per liter)
Treatment tank liquid = replenisher ammonium thiosulfate 200g
Sodium sulfite 15g
Ethylenediaminetetraacetic acid disodium 2g
Imidazole 10g
pH 7.0
(Stabilizing liquid: per liter)
Treatment tank liquid = replenisher m-hydroxybenzaldehyde 1.0 g
Ethylenediaminetetraacetic acid disodium 0.3g
β-cyclodextrin 0.2g
KOH 0.2g
pH 8.0
Water was added to make a total volume of 1 L, and the pH was adjusted with 50% sulfuric acid or aqueous ammonia.

[Processing conditions]
<Processing process><Tankcapacity><Processingtime><Processingtemperature><Replenishmentamount>
Color development 16.4L 3min 15sec 38.0 ° C 450ml / m ²
Bleaching 5.0L 45 seconds 35.0 ° C 130ml / m ²
Fixing-1 5.0L 45 seconds 35.0 ° C * 1
Fixing-2 5.0L 45 seconds 35.0 ° C 600ml / m ²
Stabilization-1 4.0L 30 seconds 35.0 ° C * 2
Stabilization-2 4.0L 30 seconds 35.0 ° C * 3
Stabilization-3 4.0L 30 seconds 35.0 ° C 1000ml / m ²
Drying-1 minute 00 seconds 60.0 ° C-
* 1) Cascade flow from fixing-2 to fixing-1 * 2) Cascade flow from stabilization-2 to stabilization-1 * 3) Cascade flow from stabilization-3 to stabilization-2 [continuous processing]
Using the color development replenisher 1 / color development replenisher 1 and the color development replenisher 2 / color development replenisher 2 respectively, the continuous treatments 3-1 and 3-2 were performed according to the processing conditions indicated above. The color negative film used for the continuous processing is Konica Color Centuria 800, Centuria 400, Centuria 100 each 35 mm size, 24 shots (above, manufactured by Konica Minolta Photo Imaging) at a ratio of 50:25:25, For each of these color negative films, a standard daylight scene photographed using a commercially available single-lens reflex camera was used.

  In accordance with the above conditions, each color negative film that has been photographed is processed at a rate of 50 as the number per day, and continuously until the color developer replenisher is replenished in an amount equivalent to twice the color developer tank volume (also referred to as 2R). Processed. In the above-described continuous processing, an automatic developing machine KP-46QA manufactured by Konica Minolta Photo Imaging Co. was used as a developing processor.

<Evaluation of processing characteristics>
In the above continuous processing, at the end of the 2R continuous processing, the Konica Color Centuria 400 (described above) subjected to wedge exposure is processed, and a transmission densitometer (manufactured by X-rite) is used for each sample subjected to the phenomenon processing. Then, the maximum density and the minimum density (fog density) by each blue light were measured. The results obtained are shown in Table 3.

  As is apparent from the results shown in Table 3, continuous processing 3-2, which was performed continuously using the color development concentrated composition having the structure defined in the present invention, was changed to continuous processing 3-1 as a comparative example. On the other hand, it can be seen that the maximum density is high and the increase in fog density is suppressed.

Example 4
In the continuous process 3-2 described in Example 3, the continuous processes 4-1 to 4 were similarly performed except that the dilution rate of the color developer replenisher and the replenishment amount of the color developer replenisher were changed as shown in Table 4. In the same manner as described in Example 3, the maximum density and the minimum density (fogging density) by blue light after continuous treatment were measured. Table 4 shows the obtained results.

As is clear from the results shown in Table 4, the maximum density is increased and the fog density is increased by performing the replenishment amount of the color developer replenisher as 300 to 500 ml per m ² of color negative film as continuous processing. It turns out that it is suppressed.

Claims (6)

One-part composition containing a compound represented by the following general formula [1] and containing a N-hydroxyalkyl-substituted p-phenylenediamine color developing agent and a hydroxylamine derivative represented by the following general formula [2] A color development concentrated composition for a silver halide color photographic light-sensitive material, characterized by being a concentrate.

[Wherein, R represents a hydrogen atom, an alkyl group, a haloalkyl group, a hydroxyalkyl group, a cycloalkyl group, or an aryl group, and R _{1 to} R ₄ are each independently —CX ₂ (OH) CHX ₁ —, X ₁ and X ₂ are each independently a hydrogen atom, a hydroxyl group, a hydroxyalkyl group, a substituted or unsubstituted alkyl group, or X ₁ and X ₂ together form a 5- to 8-membered carbocycle. Represents a carbon atom necessary for. n and m each represent an integer of 1 to 100. ]
General formula [2]
HO-N (R ¹ ) -LA
[In the formula, L represents an alkylene group, A represents a carboxyl group, a sulfo group, a phosphono group, a phosphinic acid residue, a hydroxyl group, an amino group, an ammonio group, a carbamoyl group, a sulfamoyl group, an alkylsulfonyl group, an alkoxyl group,- O— (B—O) _n —R ² having a carboxyl group, sulfo group, phosphono group, phosphinic acid residue, hydroxyl group, amino group, ammonio group, carbamoyl group, sulfamoyl group or alkylsulfonyl group as a substituent Represents an aryl group, B represents an alkylene group, R ² represents a hydrogen atom or an alkyl group, and n represents an integer of 1 to 4. R ¹ represents a hydrogen atom or an alkyl group. L and R ¹ may be linked to form a ring. ] 2. A color development concentrated composition for a silver halide color photographic material according to claim 1, wherein the molar ratio of the compound represented by the general formula [1] to sulfurous acid is 1: 1 to 1: 5. object. The color development concentrated composition for a silver halide color photographic light-sensitive material according to claim 1 or 2, comprising a compound represented by the following general formula [3].

[Wherein R ^{3 to} R ⁶ are each a hydrogen atom, a halogen atom, a hydroxyl group, a sulfo group, a carboxyl group, an alkoxyl group, an alkoxycarbonyl group, a carbamoyl group, an alkyl group, an alkenyl group, an acyl group, an acyloxy group, a sulfamoyl group. Represents an acylamino group or a phenyl group. However, when R ³ represents a hydroxyl group or a hydrogen atom, R ⁵ is not a hydrogen atom. ] 4. The color development concentrated composition for a silver halide color photographic light-sensitive material according to claim 1, which is substantially free of bromide. 5. Halogenation that is imagewise exposed using a color developing solution prepared by diluting the color developing concentrated composition for a silver halide color photographic light-sensitive material according to any one of claims 1 to 4 three times or more. A method for processing a silver halide color photographic light-sensitive material, characterized by color-developing a silver color photographic light-sensitive material and then performing a desilvering step. 6. The method for processing a silver halide color photographic light-sensitive material according to claim 5, wherein the replenishing amount of the color developing solution is 300 to 500 ml per 1 m ^{2 of the} silver halide color photographic light-sensitive material.