JP2005345688A - Coloring development single part concentrated composition for silver halide color photographic sensitive material, and processing method of silver halide color photographic sensitive material using it - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a coloring development concentrated composition for a silver halide color photographic sensitive material for obtaining always stable quality (sensitivity and gradation), even when performing continuous processing under the condition of a low processing amount even after being preserved over a long period of time, and to provide a processing method using it. <P>SOLUTION: The coloring development single part concentrated composition for the silver halide color photographic sensitive material does not contain hydroxylamine salt, and contains at least one selected from among compounds represented in general formula [I]: HO-N(R<SP>1</SP>)-L-A<SP>1</SP>and general formula [II]: HON(R<SP>3</SP>)CO-R<SP>4</SP>and general formula [III]. A mol content of sulfite is 3-10 times total mol content of the compounds represented in general formula [I], general formula[II] and general formula [III], and the specific gravity of the concentrated composition is 1.090-1.200. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a novel color development single-part concentrated composition for a silver halide color photographic light-sensitive material and a method for processing a silver halide color photographic light-sensitive material using the same.

  The color developing composition is used to process a silver halide color photographic light-sensitive material that provides a target image, such as a color film or a color paper. Such compositions generally contain a color developing agent such as 4-amino-3-methyl-N- (2-methanesulfonamidoethyl) aniline as a reducing agent. U.S. Pat. Nos. 4,892,804, 4,876,174, 5,354,646, and 5,660,974 describe various color developing compositions.

  At present, in the above processing method, in order to replenish the processing solution components consumed by the developing reaction in the processing process or brought out by the silver halide color photographic light-sensitive material to be processed, In general, it is processed by a replenishment method in which a “color developing replenisher” is added. By adopting such a replenishment method, the development level and the stability of the color developing agent are always maintained even when continuous processing is performed.

  The color developer is supplied to a user such as a developer in a form separated into three or more “parts” (or concentrated compositions) to be mixed immediately before use. Usually, in order to maintain the chemical activity and solubility of the constituent components, they are often supplied separately in a plurality of parts. If the materials constituting the color developer are stored together without separating them for a long time under alkaline conditions, they will deteriorate or react with each other. For this reason, one part contains a color developing agent, the other part contains a material for maintaining alkalinity (alkali agent), and another part contains an antioxidant or the like. It has been. In general, a homogeneous color developer can be obtained by sequentially mixing all these parts and water at the time of use.

  In recent years, there has been a desire in the photographic industry to reduce the number of parts used to prepare a color developer, particularly a color developer replenisher. Ready to use type solutions, concentrated compositions or powder mixtures are commercially available in the art. For example, European Patent Application Publication No. 793,141 describes a two-part color developing composition that can be supplied in either 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. In such photographic processing, the most important solvent is water, which becomes an important requirement for the solubility of the inorganic salts and organic salts used in water.

  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 has a problem that costs for production, transportation, storage and the like increase.

  To that end, in the photographic industry, manufacturers and users provide photographic processing compositions (including color developing compositions) in concentrated form so that they do not have to cost to transport or store large quantities of water, and more It is desirable to be able to use small containers. Further, there is a need for a composition that does not require mixing of the various components (thus reducing mixing errors) and can be used immediately after removal from the container (eg, known as an “autofill” processor). Yes.

  In recent years, as a color developing composition that has overcome the above problems, a single part (also referred to as a one-part, single-part preparation, or one-component kit) is commercially available, but a precipitate (eg, slurry, sludge, etc.) or a plurality of Due to the presence of the solvent phase, it is necessary to stir or mix well before use.

  Accordingly, there is a great need for a single-part color development concentrate composition that is homogeneous, concentrated and stable. Such a concentrated composition not only can reduce the cost of transporting and storing a solution diluted with a large amount of water, but also can be complicated such as mixing multiple parts or stirring a multi-phase composition. It reduces mixing errors and provides products that are attractive to users.

  In addition, single-part kits have poor storage stability and usually have a short expiration date. The reason for this is that, in addition to the occurrence of precipitation of constituents during long-term storage and the accompanying decrease in development processing ability, color deterioration of the storage container is caused. Even when the quality of the content composition is not deteriorated, if the storage container is markedly colored, the quality of the product is deteriorated.

  Conventionally, it has been considered that it is difficult to make a single part in a color developing solution for a color negative film using a hydroxyalkyl-substituted paraphenylenediamine-based color developing agent, and that it is essential to make multiple parts. Because it requires high precision control of development stability, the hydroxylamine salt itself used as an antioxidant for color developing agents also has a large effect on developability. A similar precaution is necessary. Further, hydroxylamine sulfate (hereinafter also referred to as HAS) has the following drawbacks or disadvantages. That is, under the Poisonous and Deleterious Substances Control Law, in order to handle and sell HAS, it is necessary to register a general sales business for poisonous and deleterious substances and set up a person in charge of handling it. At present, N, N-diethylhydroxylamine is widely used in place of HAS. However, since DEHA has a problem of lowering the color density and has a specific odor, when the development processing is performed in a general store called a minilab, this odor is generated in the working environment. In this respect, it is not preferable, and it is desired to remove as much as possible.

  In light of the current situation as described above, in general, in the color negative film color development concentrated composition kit, the hydroxylamine salt is supplied as a separate part from the other components, or the hydroxylamine salt is used as a single part. Various methods of using other antioxidants have been proposed. For example, the description of the Example using alternative preservatives other than a hydroxylamine salt is described (for example, refer patent document 1). In addition, a one-part color developing concentrate containing a color developer substance, an antioxidant, an anti-lime agent, a buffer system and an alkali has been proposed (see, for example, Patent Document 2), and a hydroxylamine salt is used. Although systems that are not used have been disclosed, they have a problem with storage stability.

As a method for improving the storage stability of a color developer having a single-part configuration, the contents of hydroxyalkyl-substituted paraphenylenediamine color developer, sulfite and hydroxylamine salt are specified, and a specific structure is developed. A color development concentrated composition containing a chelating agent is disclosed (for example, see Patent Document 3). Also, it contains a paraphenylenediamine color developing agent having a hydroxyalkyl group in the amino group, hydroxylamine and sulfite, and is filled in a packaging material having an oxygen permeability of 50 ml / (m ² · day · atm) or less. A color development concentrated composition for a silver halide photographic light-sensitive material is disclosed (for example, see Patent Document 4). Furthermore, liquid color development containing a preservative having a specific structure and having a specific gravity of 1.05 to 1.13 is disclosed (for example, see Patent Document 5).

  According to the methods disclosed in Patent Documents 3 to 5, the storage stability of the single-part concentrated solution is drastically improved, and problems in a normal development state are not generated.

However, in recent years, digital photo-related growth has been intense, and as a result, development processing demand from conventional film cameras has been drastically reduced. Under such circumstances, even in a minilab shop or the like that has maintained a stable development quality level of a film developing machine by developing 20 to 30 films per day, only a few film development requests per day are requested. Not coming has become a daily routine. For this reason, the storage period of the development processing kit is prolonged, and in addition, a phenomenon in which the developing solution is gradually evaporated and concentrated by staying in the respective processing tanks of the automatic developing machine for a long time. As a result, it has become a new problem that the development quality level is not stabilized. This has been found to be particularly evident in a concentrated color developer kit that has been made into a single part and used after being stored for a long period of time after storage as the amount of processing decreases. I'm in a hurry.
JP 2001-100380 A JP 2000-314948 A JP 2003-255501 A JP 2003-255498 A JP-A-8-234389

  The present invention has been made in view of the above problems, and its purpose is to be always stable even when continuous processing is performed under low throughput conditions using a color development single-part concentrated composition stored for a long period of time. Provided are a color development single-part concentrated composition for a silver halide color photographic light-sensitive material capable of obtaining the obtained quality (sensitivity and gradation) and a method for processing a silver halide color photographic light-sensitive material using the same.

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

(Claim 1)
Substantially free of hydroxylamine salt, containing at least one selected from compounds represented by the following general formula [I], general formula [II] and general formula [III], and molar content of sulfite Is 3 to 10 times the total molar content of the compounds represented by the general formula [I], general formula [II] and general formula [III], and the specific gravity of the concentrated composition is 1.090 to 1 200. Color development single-part concentrated composition for silver halide color photographic light-sensitive material, characterized by being 200.

Formula [I]
HO-N (R ¹ ) -LA ¹
[In the formula, L represents an alkylene group, A ¹ 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 group, or 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 alkylene group, R ² represents a hydrogen atom or an alkyl group, n represents an integer of 1 to 4, and R ¹ represents a hydrogen atom or an alkyl group. L and R ¹ may be linked to form a ring. ]
General formula [II]
HON (R ³ ) CO-R ⁴
[Wherein, R ³ represents a hydrogen atom or an alkyl group, and R ⁴ represents an alkyl group or an aryl group. ]

[Wherein, R and R ′ each represent a saturated or unsaturated aliphatic hydrocarbon group having 1 to 6 carbon atoms. n represents an integer of 4 to 50,000. s represents 0 or 1.

When s takes 1, A ² represents the following formula 1.

In the formula, R ″ represents an alkylene group or alkanetriyl group having 2 to 8 carbon atoms. In the case of an alkylene group, q is 0, and in the case of an alkanetriyl group, it is 1. Represents a polymer represented by the general formula [III], m represents an integer of 0 to 30.]
(Claim 2)
2. The color developing single-part concentrated composition for a silver halide color photographic material according to claim 1, wherein the specific gravity of the concentrated composition is in the range of 1.110 to 1.180.

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

[Wherein R ₁ represents an alkyl group having 1 to 2 carbon atoms or a hydrogen atom, and R ₂ represents an alkyl group having 1 to 3 carbon atoms, a sulfonic acid group, a carboxyl group, a hydroxyl group, or a hydrogen atom. , R ₃ represents a hydrogen atom or a hydroxyl group. p represents an integer of 0 to 2, and r represents an integer of 1 to 3. A may be substituted with a hydrogen atom at any position of the benzene ring. Further, s represents 0 to 50, t represents an integer of 0 or 1, and u represents a number of 2 to 150. ]
(Claim 4)
The color developing single-part concentrated composition for a silver halide color photographic light-sensitive material according to any one of claims 1 to 3 is processed using a color developing use solution prepared by diluting with water at least twice. And a method for processing a silver halide color photographic light-sensitive material.

  According to the present invention, a stable quality (sensitivity and gradation) can always be obtained even when continuous processing is performed under low throughput conditions using a color development single-part concentrated composition stored for a long period of time. A color development single-part concentrated composition for a silver halide color photographic light-sensitive material and a method for processing 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 inventor has substantially no hydroxylamine salt and is represented by the following general formula [I], general formula [II] and general formula [III] In which the molar content of sulfite is 3 to 10 of the total molar content of the compounds represented by general formula [I], general formula [II] and general formula [III]. The color developing single-part concentrated composition for a silver halide color photographic light-sensitive material having a double density and a specific gravity of the concentrated composition of 1.090 to 1.200 enables low throughput even after long-term storage. The present inventors have found that a color development single-part concentrated composition for a silver halide color photographic light-sensitive material that can always provide stable quality (sensitivity and gradation) even when continuously processed under the conditions can be realized. It depends on you.

  Details of the present invention will be described below.

  The color development single-part concentrated composition for silver halide color photographic light-sensitive materials of the present invention (hereinafter also simply referred to as color development concentrated composition) contains substantially no hydroxylamine salt, and the above general formula [I] And at least one selected from compounds represented by general formula [II] and general formula [III].

  Details of the compounds represented by the general formulas [I] to [III] will be described below.

  First, the hydroxylamine derivative represented by the general formula (I) according to the present invention will be described.

In the general formula [I], L represents an alkylene group, and A ¹ 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, or an alkylsulfonyl group. , Alkoxyl group, —O— (B—O) n—R ² group, or carboxyl group, sulfo group, phosphono group, phosphinic acid residue, hydroxyl group, amino group, ammonio group, carbamoyl group, sulfamoyl group as a substituent Alternatively, it represents an aryl group having an alkylsulfonyl group, B represents an alkylene group, R ² represents a hydrogen atom or an alkyl group, n represents an integer of 1 to 4, and R ¹ represents a hydrogen atom or an alkyl group. L and R ¹ may be linked to form a ring.

  Furthermore, the compound represented by the general formula [I] will be described in detail.

  In the said general formula [I], as L and B, a C1-C10 linear or branched alkylene group is preferable, and a C1-C5 thing is especially preferable. Specific 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 ¹ is 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 group or 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, and represented by A Amino group, ammonio group, carbamoyl 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, sulfamoyl group or alkylsulfonyl group has a substituent Including things. Preferred examples of the substituent include an alkyl group (for example, each group such as methyl, 1,1-dimethyl-2-sulfoethyl, carboxyethyl) and a sulfo group.

In the case where A ¹ and A ¹ are an aryl group, preferred examples of the substituent substituted on the 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. It is done. 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 ¹ represents an ammonio group, the compound represented by the general formula [I] may be accompanied by sulfate ion, p-toluenesulfonate ion, chlorine ion, sulfite ion and the like as a counter ion of the ammonio group. In addition, when L and A ¹ are accompanied by a substituent having an acid group such as a carboxyl group, a sulfo group, a phosphono group, a phosphinic acid residue, or a hydroxyl group, the hydrogen of the acid group is placed as an alkali metal atom or an ammonium atom group. It may be replaced. The aryl group represented by A ¹ is preferably phenyl. When A ¹ is an alkoxyl group, L is preferably substituted with a hydroxyl group, and 3-alkoxy-2-hydroxypropyl is preferred as -LA ¹ . The alkyl group represented by R ^1, preferably from 1 to 4 carbon atoms.

Specific examples of -LA ¹ include carboxymethyl group, carboxyethyl group, carboxypropyl group, sulfoethyl group, sulfopropyl group, sulfobutyl group, phosphonomethyl group, phosphonoethyl group, hydroxyethyl group, 3-methoxy-2-hydroxy Propyl group, 3-ethoxy-2-hydroxypropyl group, 3-propoxy-2-hydroxypropyl group, p-carboxybenzyl group, —CH ₂ CH ₂ —O— (CH ₂ CH ₂ O) ₂ H, —CH ₂ CH ₂ —O— (CH ₂ CH ₂ O) ₃ H can be mentioned as a preferred example, and carboxymethyl group, carboxyethyl group, sulfoethyl group, sulfopropyl group, phosphonomethyl group and phosphonoethyl group are mentioned as particularly preferred examples. Can do.

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 straight chain or branched chain group having 1 to 10 carbon atoms, and 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, preferable R ¹ includes a hydrogen atom, carboxymethyl group, carboxyethyl group, carboxypropyl group, sulfoethyl group, sulfopropyl group, sulfobutyl group, phosphonomethyl group, phosphonoethyl group, and hydroxyethyl group, and particularly preferred examples. 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. There may be two or more substituents for each of L, A ¹ , 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 have A ¹ as a substituent, or A ¹ represents an amino group which may be alkyl-substituted, and the nitrogen of the amino group L and R ¹ can also form a ring (for example, piperazine ring formation) through an atom. Particularly preferred hydroxylamine derivatives are mono- or di-alkylhydroxylamines having 1 to 8 carbon atoms in total.

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

(I-57) HON (-CH 2 CH (OH) CH 2 (OH)) 2
(I-58) HON (isoC ₃ H ₇ ) CH ₂ CH ₂ SO ₃ H
Next, the compound represented by the general formula [II] will be described.

General formula [II]
HON (R ³ ) CO-R ⁴
In the general formula [II], R ³ represents a hydrogen atom or an alkyl group, and R ⁴ represents an alkyl group or an aryl group.

The alkyl group represented by R ³ , the alkyl group represented by R ⁴ , and the aryl group include those each having a substituent, and the substituent is the substituent of L described in the above general formula [I]. Can be mentioned as examples.

  Hereinafter, although the specific example of a compound represented by general formula [II] is shown, this invention is not limited to these illustrated compound parts.

(II-1) CH ₃ N (OH) CO (CH ₂ ) ₃ OH
(II-2) HN (OH) COCH ₂ CH ₂ CH (CH ₃ ) OH
(II-3) HN (OH) CO-PhCOOH (o)
Next, the compound represented by the general formula [III] will be described.

  In the general formula [III], R and R ′ each represent a saturated or unsaturated aliphatic hydrocarbon having 1 to 6 carbon atoms. These hydrocarbon groups include those having a substituent, and preferred substituents are a hydroxyl group, a carboxyl group, a sulfone group, and the like, and may contain a divalent linking group such as a carbonyl group. n represents an integer of 4 to 50,000. s represents 0 or 1, but s is preferably 1.

When s takes 1, A ² represents Formula 1 above. R ″ represents an alkylene group having 2 to 8 carbon atoms or an alkanetriyl group, including those substituted with a hydroxyl group. In the case of an alkylene group, q is 0, and in the case of an alkanetriyl group, 1 When q is 1, B represents a polymer represented by the general formula [III], the general formula [III] has a three-dimensional structure, and m represents an integer of 0 to 30.

  A compound represented by the general formula [III] in which s is 0, for example, poly (N-hydroxyalkyleneimine) can be easily synthesized by a known method. As a representative example, hydrogen peroxide described in “Journal of Chemical Society (J. Chem. Soc.), 75, 1009 (1899), J. Chem. Soc., 1963, 3144”, etc. An example is a method of synthesizing poly (alkyleneimine) by oxidizing a secondary amine using water. Since the crude poly (N-hydroxyalkyleneimine) synthesized by this method does not contain a component that affects photographic characteristics, it has an advantage that 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 applying the method described in JP-A-3-259145.

  Moreover, the synthesis example of the compound represented by the general formula [III] in which s takes 1 such as the exemplified compound (III-14) shown below is shown below.

  174 g (1.0 mol) of diethylene glycol diglycidyl ether and 66 g (1.0 mol) of 50% aqueous hydroxylamine solution were mixed with 450 ml of water, and heated and stirred at 60 ° C. for 2 hours. When the concentration of the hydroxylamino group in the obtained aqueous solution was determined using a Fering solution, it was confirmed that 0.109 mol / 100 g of hydroxylamino group was contained. Further, when unreacted hydroxylamine was measured by liquid chromatography, it was confirmed that it did not remain. The aqueous solution obtained has almost no odor.

  Hereinafter, typical examples of the compound represented by the general formula [III] are shown, but the present invention is not limited to these compounds.

  In the present invention, among the compounds exemplified above, more preferred compounds include I-2, I-4, I-6, I-7, I-56, I-57, II-3 and III-1. Can be mentioned.

  The compounds represented by the general formulas [I] to [III] according to the present invention described above represent alkyl-substituted hydroxylamines, but this compound group does not include hydroxylamine salts. In order to achieve the effects of the present invention, it is characterized by substantially not containing a hydroxylamine salt.

  In addition, the color development concentrated composition of the present invention is characterized by containing a sulfite. The sulfite used in the present invention may be any organic or inorganic substance as long as it releases sulfite, but is preferably an inorganic salt. Preferred compounds include sodium sulfite, potassium sulfite, potassium bisulfite, sodium bisulfite, sodium metabisulfite, potassium metabisulfite and the like.

In the color developing solution, the compound represented by the general formulas [I] to [III] according to the present invention is preferably 1 × 10 ⁻³ mol / L or more, and preferably 1 × 10 ⁻¹ mol / L. More preferably, it is contained in a color developing concentrated composition, and it is preferably 1 × 10 ⁻² mol / L or more and 5 mol / L or less, particularly 5 × 10 ⁻² mol / L. The content is preferably 1 mol / L or less.

  In the color development concentrated composition of the present invention, the molar content of sulfite is the total molar content of the compounds represented by the general formulas [I], [II] and [III] described above. It is one of the characteristics that it exists in the range of 3-10 times, and the sensitivity fluctuation | variation after preserve | saving for a long period which is the target effect of this invention can be suppressed effectively. More preferably, by setting the range to 4 to 8 times, the sensitivity fluctuation range can be further reduced.

  The color developing agent used in the color developing concentrated composition of the present invention is a p-phenylenediamine color developing agent, and is a known p-phenylenediamine derivative. Representative examples are shown below, but are limited thereto. is not.

1) N, N-diethyl-p-phenylenediamine 2) 4-amino-3-methyl-N, N-diethylaniline 3) 4-amino-N- (β-hydroxyethyl) -N-methylaniline 4) 4 -Amino-N-ethyl-N- (β-hydroxyethyl) aniline 5) 4-amino-3-methyl-N-ethyl-N- (β-hydroxyethyl) aniline 6) 4-amino-3-methyl-N -Ethyl-N- (3-hydroxypropyl) aniline 7) 4-Amino-3-methyl-N-ethyl-N- (4-hydroxybutyl) aniline 8) 4-Amino-3-methyl-N-ethyl-N -(Β-Methanesulfonamidoethyl) aniline 9) 4-Amino-N, N-diethyl-3- (β-hydroxyethyl) aniline 10) 4-Amino-3-methyl-N-ethyl-N- (β- Me Xylethyl) aniline 11) 4-Amino-3-methyl-N- (β-ethoxyethyl) -N-ethylaniline 12) 4-Amino-3-methyl-N- (3-carbamoylpropyl) -Nn-propyl -Aniline 13) 4-amino-N- (4-carbamoylbutyl) -Nn-propyl-3-methylaniline 14) N- (4-amino-3-methylphenyl) -3-hydroxypyrrolidine 15) N- (4-Amino-3-methylphenyl) -3- (hydroquinmethyl) pyrrolidine 16) N- (4-amino-3-methylphenyl) -3-pyrrolidinecarboxamide Among the p-phenylenediamine derivatives, particularly preferred Illustrative compounds 5), 6), 7), 8) and 12), among which exemplary compounds 5) and 8) are preferred. These p-phenylenediamine derivatives are in the form of salts such as sulfates, hydrochlorides, sulfites, naphthalene disulfonates, p-toluenesulfonates, or the free base type (hereinafter referred to as free form). It is also called). The concentration of the p-phenylenediamine color developing agent in the color developer is preferably 2 to 200 mmol, more preferably 6 to 100 mmol, and particularly preferably 10 to 40 mmol per liter. It is done. Moreover, it is preferable that the density | concentration in a concentrated composition is 0.05 mol-1.0 mol per liter, More preferably, it is 0.07-0.6 mol per liter. From the viewpoint of achieving a sufficient color density when used in the processing of a photosensitive material as a color development replenisher or color development processing solution, and obtaining the long-term stability of the concentrated composition, the above concentration range is preferable.

  In addition, the color development concentrated composition of the present invention preferably contains a compound represented by the above general formula [IV] in addition to the above-described configuration from the viewpoint of further achieving the object effect of the present invention. .

In the general formula [IV], R ₁ represents an alkyl group having 1 or 2 carbon atoms (for example, a methyl group or an ethyl group) or a hydrogen atom, and R ₂ represents a linear or branched alkyl group having 1 to 3 carbon atoms. Group (this alkyl group includes those having a substituent, for example, methyl group, ethyl group, propyl group, (i) propyl group, hydroxymethyl group, sulfomethyl group, hydroxyethyl group, sulfoethyl group, disulfoethyl group, dihydroxyethyl group) Group, 1-hydroxypropyl group, 2-hydroxypropyl group, 1-sulfopropyl group, 2-sulfopropyl group, trihydroxy (i) propyl group, 1,2-disulfopropyl group), sulfonic acid group, carboxyl group Represents a hydroxy group and a hydrogen atom, and R ₃ represents a hydrogen atom or a hydroxy group.

  p represents an integer of 0 to 2, and r represents an integer of 1 to 3. A may be substituted with a hydrogen atom at any position of the benzene ring. Further, s represents 0 to 50, t represents an integer of 0 or 1, and u represents a number of 2 to 150.

  Specific compounds represented by the general formula [IV] are shown below.

  Among the specific compounds shown above, IV-2, IV-3, IV-4, IV-5, IV-6, IV-9, IV-13, and IV-17 are preferable, and IV is more preferable. -2, IV-3, IV-4, and IV-5.

  The addition amount of the compound represented by the general formula [IV] is preferably 0.05 to 10 g, more preferably 0.1 to 1 g, per liter of the color developing concentrated composition.

  The pH of the color development concentrated composition of the present invention is preferably 9 or more and 12 or less.

  The color development concentrated composition of the present invention is characterized in that the specific gravity value is in the range of 1.090 to 1.200. If the specific gravity value is less than this, it is difficult to form a sufficient concentrated composition in terms of user handling, and if the specific gravity value exceeds the upper limit range, sufficient results cannot be obtained with the development stability of the effect of the present invention. . A more preferable specific gravity value range is 1.110 to 1.180.

  In the processing method of the present invention, processing is performed using a color developing use solution prepared by diluting the color developing concentrated composition having the single-part composition of the present invention with water at least twice (concentration rate of at least twice). Furthermore, the upper limit is preferably 10 times or less, more preferably 5 times or less, from the viewpoint of stability and solubility in the concentrated state.

  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 present invention is a halogenated product that is imagewise exposed by preparing a color development processing solution (worker solution) or color development replenisher solution diluted 2 to 10 times with water or the like. The silver color 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 used in the color development concentrated composition of the present invention will be described.

  It is not intended to limit the use of a known preservative in the color development concentrated composition of the present invention as long as the objective effects of the present invention are not impaired.

  The pH of the color developer is preferably from 9.0 to 13.5, and the pH of the replenisher is preferably from 9.0 to 13.5. For this reason, the color developer and the replenisher thereof can contain an alkali agent, a buffer agent and, if necessary, an acid so that the pH value can be maintained.

  In the color development concentrated composition of the present invention, it is preferable to use the following buffering agent from the viewpoint of maintaining the pH when a color development processing solution is prepared. 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 9.0 or higher, and even if 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 of the color developing solution and its replenisher is 0.01 to 2 mol, preferably 0.1 to 0.5 mol, per liter. The amount of addition in the composition or concentrated composition is determined.

  As the other components, for example, calcium and magnesium precipitation inhibitors and various chelating agents that are also stability improvers can be added to the color development concentrated composition of the present invention. For example, nitrilotriacetic acid, diethylenetriaminepentaacetic acid, ethylenediaminetetraacetic acid, N, N, N-trimethylenephosphonic acid, ethylenediamine-N, N, N ′, N′-tetramethylenesulfonic acid, transsirohexasidiaminetetraacetic acid, 1,2-diaminopropan tetraacetic acid, glycol ether diamine tetraacetic acid, ethylenediamine orthohydroxyphenylacetic acid, ethylenediamine disuccinic acid (SS form), N- (2-carboxylateethyl) -L-aspartic acid, β-alanine diacetic acid, 2-phosphonobutane-1,2,4-tricarboxylic acid, 1-hydroxyethylidene-1,1-diphosphonic acid, N, N′-bis (2-hydroxybenzyl) ethylenediamine-N, N′-diacetic acid, 1,2 -Dihydroxybenzene-4,6-disulfonic acid and the like It is. 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 during color developer processing. For example, 0. 1 per liter. It is added so as to be about 1 to 10 g.

  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 added amount in the composition or concentrated composition is such that the concentration of the color developing solution and its replenisher is 0.001 to 0.2 mol, preferably 0.01 to 0.05 mol, per liter. Is preferably determined.

  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 the color development concentrated composition of the present invention, a fluorescent whitening agent can be used as necessary. As the optical brightener, a bis (triazinylamino) stilbene sulfonic acid compound is preferred. As the bis (triazinylamino) sturbene 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 addition amount of the above-mentioned optical brightener is determined in the composition or the concentrated composition so that both the color developing solution and the replenisher thereof are 0.1 to 0.1 mol per liter. Is preferred.

  In the color developing concentrated composition of the present invention, the pH is set high in order to contain the color developing agent in a high concentration, and it is usually in the range of 11.0 to 13.5, preferably 12.0 to It is in the range of 13.5, more preferably in the range of 12.5 to 13.5. The color developer and development replenisher prepared therefrom are used at a pH of 9.5 or higher, more preferably from 10.0 to 12.5.

In the color developing solution, bromine ions are usually 0.2 × 10 ^{−2 to} 15.0 × 10 ⁻² mol / liter, preferably 0.5 × 10 ^{−2 to} 5.0 × 10 ⁻² mol / liter. In many cases, however, bromine ions are usually released as a by-product of development into the color developing developer, so that it is often unnecessary to add to the replenisher. 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.

  The color development processing temperature that can be applied in the processing method of the present invention is preferably 20 to 55 ° C., more preferably 30 to 55 ° C., and still more preferably in the case of color negative film color development processing. Is 38-45 ° C. The color development processing time is preferably 20 seconds to 6 minutes, more preferably 30 to 200 seconds.

A smaller replenishing amount is preferred, but 100 to 800 ml per 1 m ^{2 of} the light-sensitive material is suitable, preferably 200 to 500 ml, particularly preferably 250 to 400 ml. The color development time referred to in the present invention means the time from when the photosensitive material enters the color developer until it enters the bleaching solution in the next processing step. For example, in the case of processing with 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 leaves the color developer, and proceeds to the next processing step. The total of both the time for transporting outside the liquid (so-called crossover time) is called the color development time. The crossover time is preferably 10 seconds or less, more preferably 5 seconds or less.

  In the processing method of the silver halide color photographic light-sensitive material of the present invention, the exposed silver halide color photographic light-sensitive material is subjected to a color processing step (color developer) using the color developing solution concentrate of the present invention. Subsequently, it is dried through a bleaching step (bleaching solution), a fixing step (fixing solution), and a stabilizing step (stabilizing solution).

  Further, it is possible to carry out development processing continuously while replenishing a replenishing color developer, a replenishing bleaching solution, a replenishing fixing solution, a replenishing stabilizing solution, and the like.

  In the method for processing a silver halide color photographic light-sensitive material of the present invention, any bleaching agent can be used as the bleaching agent used in the bleaching solution, and particularly an organic complex salt of iron (III) (for example, ethylenediaminetetraacetic acid, Aminopolycarboxylic acids such as diethylenetriaminepentaacetic acid, nitrilotriacetic acid, cyclohexanediaminetetraacetic acid, complex salts such as aminopolyphosphonic acid, phosphonocarboxylic acid and organic phosphonic acid) or organic acids such as citric acid, tartaric acid, malic acid; Persulfate; hydrogen peroxide is preferred.

  Of these, iron (III) complex salts of ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, 1,3-diaminopropanetetraacetic acid, and 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.

  Various compounds can be used in the bleaching solution 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 may contain a rehalogenating agent such as bromide (eg, potassium bromide) or chloride (eg, potassium chloride) or iodide (eg, ammonium iodide). One or more inorganic acids, organic acids and alkali metals having pH buffering capacity such as borax, sodium metaborate, acetic acid, sodium acetate, sodium carbonate, potassium carbonate, citric acid, sodium citrate, tartaric acid as required Ammonium salts or corrosion inhibitors such as ammonium nitrate and guanidine can be added.

  Fixing agents used in the fixing solution are known fixing agents, that is, thiosulfates such as sodium thiosulfate and ammonium thiosulfate; thiocyanates such as sodium thiocyanate and ammonium thiocyanate; ethylenebisthioglycolic acid, 3, 6 -Water-soluble silver halide solubilizers such as thioether compounds such as dithia-1,8-octanediol and thioureas, and these can be used alone or in combination. In the present invention, it is preferable to use thiosulfuric acid, particularly ammonium thiosulfate. The amount of the fixing agent per liter is preferably 0.3 to 2 mol, and more preferably 0.5 to 1.0 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 and the fixing solution may contain various other fluorescent brightening agents, antifoaming agents or surfactants, and organic solvents such as polyvinylpyrrolidone and methanol.

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

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

Further, the replenishment rate of the bleaching processing solution can be applied to the processing method of the present invention 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 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. 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 a stable 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 ions, but inorganic salts are preferred. Preferred specific compounds include sodium sulfite, potassium sulfite, ammonium sulfite, ammonium bisulfite, potassium bisulfite, sodium bisulfite, sodium metabisulfite, potassium metabisulfite, ammonium metabisulfite and the like. These salts are preferably added in an amount of at least 1 × 10 ⁻³ mol / L or more, more preferably 5 × 10 ⁻³ mol / L to 5 × 10 ⁻² mol / L in the stabilizing solution. It is added to become L.

  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 stabilization process using the stabilizing liquid may be composed of one tank or two or more tanks, 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 of the present invention includes a wide variety of photographic elements having a silver halide light-sensitive layer on a support, such as color negative film, color reversal film, color paper, and color. Although a movie film etc. can be mentioned, It is preferable to apply to the process of a color negative film especially.

  The silver halide color photographic light-sensitive material according to the present invention mainly comprises a yellow dye-forming coupler-containing blue-sensitive silver halide emulsion layer, a magenta dye-forming coupler-containing green light-sensitive silver halide emulsion layer on a support. It has a photographic constituent layer comprising at least one each of a red-sensitive silver halide emulsion layer containing a cyan dye-forming coupler and a non-photosensitive hydrophilic colloid layer. The silver halide emulsion layer containing the yellow dye-forming coupler is a yellow coloring layer, the silver halide emulsion layer containing the magenta dye-forming coupler is 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.

  Hereinafter, typical components of the silver halide color photographic light-sensitive material will be described.

  For example, the details are described in the following Research Disclosure (hereinafter abbreviated as RD) and can be referred to.

  For example, RDNo. 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 Photographic Emulsions” by Zerikman et al., Published by Focal Press (V.L. 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. However, the present invention is limited to these examples.
<< Preparation of Color Developing Concentrated Composition >>
[Preparation of color developing concentrated composition 1]
Sodium sulfite (hereinafter also referred to as SS) 0.04 mol Potassium carbonate 40 g
Preservative (Exemplary Compound I-7) 0.02 mol Potassium bromide 0.5 g
N-ethyl-N- (hydroxyethyl) -3-methyl-4-aminoaniline sulfate (hereinafter also referred to as CD-4) 6.5 g
Diethylenetriaminepentaacetic acid sodium salt 5.0 g
pH 10.35
Finished to 400 ml with water. The pH was adjusted with 50% sulfuric acid or potassium hydroxide.

[Preparation of color developing concentrated compositions 2 to 26]
In the preparation of the color developing concentrated composition 1, the same amount except that the addition amount (number of moles) of sodium sulfite, the kind and the addition amount (number of moles) of the preservative and the finishing amount are changed as shown in Table 1. Thus, color development concentrated compositions 2 to 26 were prepared.

  In Table 1, HAS is hydroxylamine sulfate, and DEHA is diethylhydroxylamine.

<Forced deterioration treatment of color developing concentrated composition>
Each color developing concentrated composition 1 to 26 prepared above was filled in a glass container and sealed, and then stored in a thermostatic bath at 50 ° C. for 2 months to perform a forced deterioration treatment. A development concentrated composition was obtained.

<Preparation of color developing solution>
Each of the unprocessed color developing concentrated compositions prepared above and each color developing concentrated composition subjected to forced deterioration processing are diluted under the following conditions A to C, respectively, and then the following additives are added to the unprocessed color developing concentrated compositions. Further, color developing solutions 1A, 1B, 1C to 26A, 26B, and 26C having been subjected to forced deterioration treatment were prepared.

[Dilution conditions]
A: Diluted with water so that the concentration of CD-4 was 5.0 g / L (reference conditions)
B: diluted with water so that the concentration of CD-4 was 6.0 g / L (concentrated 1.2 times with respect to reference condition A)
C: diluted with water so that the concentration of CD-4 was 7.0 g / L (concentrated 1.4 times with respect to reference condition A)
〔Additive〕
Sodium bromide 1.3g / L
Potassium bicarbonate 3.7g / L
Potassium carbonate 2.3g / L
Potassium iodide 3.0mg / L
pH 10.05
The pH was adjusted with 50% sulfuric acid or potassium hydroxide.

<Development processing conditions>
Using Centuria 200, a color negative film manufactured by Konica Minolta Photo Imaging Co., Ltd., with white exposure through an optical wedge, each of the unprocessed and forced-degraded color developers A, B, and C prepared above was used. The development processing was performed according to the following conditions.

[Processing conditions]
<Processing process><Processingtime><Processingtemperature>
Color development 3 minutes 15 seconds 38.5 ° C
Bleach 45 seconds 38.0 ° C
Fixing-1 45 seconds 38.0 ° C
Fixing-2 45 seconds 38.0 ° C
Stability-1 30 seconds 38.0 ° C
Stable-2 30 seconds 38.0 ° C
Stable-3 30 seconds 38.0 ° C
Dry 1 min 00 sec 55.0 ° C
The composition of the processing solution excluding the color development used in the above processing steps is as follows.

<Bleaching solution: per liter>
1,3-propylenediamine tetraacetic acid ferric sodium salt 133g
1,3-propylenediaminetetraacetic acid 5 g
60g ammonium bromide
Maleic acid 40g
Imidazole 10g
pH 4.5
Water was added to bring the total volume to 1 L, and the pH was adjusted with aqueous ammonia or 50% sulfuric acid.

<Fixing solution per 1L>
200g ammonium thiosulfate
Sodium sulfite 15g
Ethylenediaminetetraacetic acid disodium 2g
pH 7.0
Water was added to make the total volume 1 L, and the pH was adjusted with 50% sulfuric acid or aqueous ammonia.

<Stabilized liquid: per 1L>
m-Hydroxybenzaldehyde 1.0g
Ethylenediaminetetraacetic acid disodium 0.6g
β-cyclodextrin 0.2g
Potassium carbonate 0.2g
pH 8.5
Water was added to make the total volume 1 L, and the pH was adjusted with 50% sulfuric acid or aqueous ammonia.

<Evaluation of processing stability>
For the sample developed according to the above method, the magenta density was measured through a green filter with a transmission densitometer manufactured by X-rite, and the horizontal axis: exposure amount (Log E), and the vertical axis represents the magenta density (D ), The exposure dose point 1 with the minimum magenta density (Dmin) +0.3 and the exposure dose point 2 corresponding to the density +1.5 from the exposure dose point 1 are connected by a straight line. The slope (tan θ) was determined and defined as the gamma value γ.

  Next, for each of the color developing solutions A, B, and C, gamma according to the following equation is obtained from γ1 obtained using the untreated color developing solution and γ2 obtained using the color developing solution that has been subjected to the forced deterioration processing. The rate of change was determined.

Gamma variation rate (%) = {(γ2-γ1) / γ1} × 100
The results obtained as described above are shown in Table 1.

  As is clear from the results shown in Table 1, the color developer concentrate having the structure defined in the present invention has a developability with or without forced deterioration treatment compared to the comparative example, at the standard density (A) and the concentration condition (B , C), the gamma fluctuation rate is 10% or less, indicating good development stability. The effect of the present invention can be exhibited when the amount of sulfite added is 3 times or more and 10 times or less with respect to the amount of the compound of the general formulas [I] to [III]. It can be seen that the development stability under the high concentration condition is improved by setting the range to 8 times from 1.

  Furthermore, when the specific gravity value of the color developing concentrate is 1.09 or less, the concentration is twice or less, and therefore it does not substantially function as a concentrated composition. Therefore, as an effect of the present invention as a concentrated composition, Needs to be in the range of 1.090 to 1.200. It can be seen that the range of 1.100 to 1.180 is preferable in that the development stability in a highly concentrated solution is improved.

Example 2
In the preparation of the color developer concentrate 3 described in Example 1, color developer concentrates 2-1 to 2-12 were prepared in the same manner except that the additives listed in Table 2 were added. In the same manner as described, after forced degradation treatment, development treatment and processing stability were evaluated by the same method, and the results obtained are shown in Table 2.

  In addition, the detail of the compound of Table 2 is as follows.

  Compound C: sodium dodecylbenzenesulfonate

  As is apparent from the results shown in Table 2, by adding a compound represented by the general formula [IV] according to the present invention to the color developing concentrate having the constitution defined in the present invention, the standard condition A On the other hand, it can be seen that the processing stability is further improved in the condition B concentrated 1.2 times and the condition C concentrated 1.4 times. In addition, as an addition amount of the compound represented by general formula [IV], the range of 0.05-10 g / L is preferable, More preferably, it is the range of 0.1-1 g / L.

Example 3
<< Exposure and development process >>
Using an automatic processor KP-46QA manufactured by Konica Minolta Photo Imaging Co., Ltd., and using the processing conditions having the following constitution, Konica Color Centuria Super 800, Centuria Super 400, Centuria Super 100 (above, Konica Minolta) Photographic imaging) film with a size of 24 mm and a standard outdoor daylight scene taken using a single-lens reflex camera. The ratio of 4: 4: 2 is 10 per day. Processing was performed one by one, and continuous processing was performed until the color developer was replenished twice as much as the processing tank capacity.

<Development processing>
[Color development replenisher]
Each color developer that has been subjected to forced deterioration treatment after filling the color developing concentrate 3 described in Example 1 into a glass container and sealing it, and then storing the container in a thermostatic bath at 50 ° C. for 2 months. A solution obtained by diluting 400 ml of the concentrated composition to 1 L was used as a color development replenisher.

[Color development starting solution: per liter]
Sodium sulfite 2.0g
Potassium carbonate 40.0g
Diethylenetriaminepentaacetic acid 5sodium 4.0 g
Potassium bromide 1.5g
Potassium iodide 2.0mg
Preservative (Sodium salt of Exemplified Compound I-7) 5.0 g
N-ethyl-N- (hydroxyethyl) -3-methyl-4-aminoaniline sulfate
4.5g
pH 10.00
Finished to 1 L with water and adjusted pH with 50% sulfuric acid or potassium hydroxide.

[Bleaching solution per liter]
Initiating liquid Replenisher 1,3-propanediamine tetraferric ammonium ammonium acetate 133 g 190 g
1,3-propanediaminetetraacetic acid 5 g 7 g
Ammonium bromide 60g 90g
Maleic acid 40g 60g
Imidazole 10g 15g
pH 4.5 3.5
Finished to 1 L with water, pH was adjusted with aqueous ammonia or 50% sulfuric acid.

[Fixing solution per liter]
Starter replenisher Ammonium thiosulfate 200g 400g
Sodium sulfite 15g 30g
Ethylenediaminetetraacetic acid disodium 2g 4g
pH 7.0 7.0
Water was added to make the total volume 1 L, and the pH was adjusted with 50% sulfuric acid or aqueous ammonia.

[Stabilizer: per liter]
Initiating liquid Replenisher m-hydroxybenzaldehyde 1.0 g 20 g
Ethylenediaminetetraacetic acid disodium 0.6g 12g
β-cyclodextrin 0.2g 4g
Potassium carbonate 0.2g 4g
pH 8.5 9.0
Water was added to make the total volume 1 L, and the pH was adjusted with 50% sulfuric acid or aqueous ammonia.

[Development processing conditions]
<Processing process><Processingtime><Processingtemperature><Replenishment amount * 1><Tankcapacity>
Color development 3 minutes 15 seconds 38.0 ° C 20.1 ml 16.4L
Bleach 45 seconds 38.0 ° C 5.0 ml 3.9 L
Fixing-1 45 seconds 38.0 ° C * 2 3.9L
Fixing-2 45 seconds 38.0 ° C 33.0 ml 3.9 L
Stability-1 30 seconds 38.0 ° C * 3 3.9L
Stable-2 30 seconds 38.0 ° C * 4 3.9L
Stability-3 30 seconds 38.0 ° C 40.0 ml 3.9 L
Dry 1 min 00 sec 55.0 ° C
* 1: Replenisher volume per color film 35mm, 24 shots * 2: Cascade from fixing-2 to fixing-1 * 3: Cascade from stable-2 to stable-1 * 4: From stable-3 to stable- Cascade to 2 《Evaluation of processing stability》
After the continuous treatment according to the above method, the treatment stability was evaluated in the same manner as in the method described in Example 1. As a result, each treatment solution was processed under the low treatment amount condition of 10 treatments per day. After the continuous processing was carried out until the concentration estimated by the specific gravity value was replenished twice as much as the color of the processing tank relative to the start of continuous processing, Although it was 30 times, the gamma fluctuation rate at the start of continuous processing and at the end of continuous processing is within 3.5%, and it is excellent in processing stability even if continuous processing is performed for a long time under low processing conditions. I was able to confirm that.

Claims (4)

Substantially free of hydroxylamine salt, containing at least one selected from compounds represented by the following general formula [I], general formula [II] and general formula [III], and molar content of sulfite Is 3 to 10 times the total molar content of the compounds represented by the general formula [I], general formula [II] and general formula [III], and the specific gravity of the concentrated composition is 1.090 to 1 200. Color development single-part concentrated composition for silver halide color photographic light-sensitive material, characterized by being 200.
Formula [I]
HO-N (R ¹ ) -LA ¹
[In the formula, L represents an alkylene group, A ¹ 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 group, or 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 alkylene group, R ² represents a hydrogen atom or an alkyl group, n represents an integer of 1 to 4, and R ¹ represents a hydrogen atom or an alkyl group. L and R ¹ may be linked to form a ring. ]
General formula [II]
HON (R ³ ) CO-R ⁴
[Wherein, R ³ represents a hydrogen atom or an alkyl group, and R ⁴ represents an alkyl group or an aryl group. ]

[Wherein, R and R ′ each represent a saturated or unsaturated aliphatic hydrocarbon group having 1 to 6 carbon atoms. n represents an integer of 4 to 50,000. s represents 0 or 1.
When s takes 1, A ² represents the following formula 1.

In the formula, R ″ represents an alkylene group or alkanetriyl group having 2 to 8 carbon atoms. In the case of an alkylene group, q is 0, and in the case of an alkanetriyl group, it is 1. Represents a polymer represented by the general formula [III], m represents an integer of 0 to 30.] 2. The color developing single-part concentrated composition for a silver halide color photographic material according to claim 1, wherein the specific gravity of the concentrated composition is in the range of 1.110 to 1.180. The color development single-part concentrated composition for a silver halide color photographic light-sensitive material according to claim 1 or 2, further comprising a compound represented by the following general formula [IV].

[Wherein R ₁ represents an alkyl group having 1 to 2 carbon atoms or a hydrogen atom, and R ₂ represents an alkyl group having 1 to 3 carbon atoms, a sulfonic acid group, a carboxyl group, a hydroxyl group, or a hydrogen atom. , R ₃ represents a hydrogen atom or a hydroxyl group. p represents an integer of 0 to 2, and r represents an integer of 1 to 3. A may be substituted with a hydrogen atom at any position of the benzene ring. Further, s represents 0 to 50, t represents an integer of 0 or 1, and u represents a number of 2 to 150. ] The color developing single-part concentrated composition for a silver halide color photographic light-sensitive material according to any one of claims 1 to 3 is processed using a color developing use solution prepared by diluting with water at least twice. And a method for processing a silver halide color photographic light-sensitive material.