JP2005316252A - One-part concentrated composition for color development replenisher for color photographic sensitive material and processing method - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a practical-cost one-part concentrated composition for a color development replenisher which has such temporal stability as not to precipitate or deposit constituents of the composition, does not cause contamination of a developing tank and racks, has satisfactory color development activity, and causes no edge stain to a cross section of a support of a photosensitive material to be processed. <P>SOLUTION: The one-part concentrated composition for a color development replenisher for the color photographic sensitive material contains (A) 0.08-0.12 mol/l of a p-phenylenediamine color developing agent, (B) 0.06-0.16 mol/l of a substituted hydroxylamine derivative of a specific structure, and (C) 0.05-1.0 mol/l of ethylene glycol, (D) shows a pH of 12.5-12.8 when diluted by adding 3.84 times as much water as the composition, and (E) does not substantially contain an alkanolamine. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a one-part concentrated processing composition for color development for a silver halide color photographic light-sensitive material, a color development replenisher prepared therefrom, and a processing method using the same.

  In recent years, automatic development processing machines called minilabs that are installed at the photographic store front and process photographic photosensitive materials have become widespread for quick service to general users and rationalization of collection and delivery between photographic stores and processing shops. . If the development processing agent for minilabs is in the form of a liquid composition in which constituent processing chemicals are previously dissolved in a solvent such as water, the processing solution can be prepared by simple preparation operations such as mixing and dilution with water before use. Therefore, it is often supplied in this form. However, the form of the liquid composition is disadvantageous in terms of transportation cost because it involves a solvent such as water for dissolving the processing agent component, ie, processing chemicals, and a container for storing the composition. In general, the supply is performed in the form of a liquid concentrated treatment composition having a reduced volume (referred to in the art as “concentrate” instead of “rich”).

  In addition, the liquid concentration treatment agent is often composed of a plurality of composition units rather than a single liquid composition for reasons such as stability over time, concentration, and handleability. The composition units constituting these concentrated compositions are called parts.

  Regarding the color development processing composition, if the processing composition is composed of a plurality of parts, it is advantageous in that the stability of the composition can be improved and further thickening and volume reduction can be achieved. There are disadvantages such as not only simple water dilution but also the mixing of a plurality of concentrated liquids, and the large number of composition containers increases the work load and the environmental burden in the treatment of used containers. Therefore, even if it is a single configuration (hereinafter referred to as a one-part configuration, which is synonymous with a one-component configuration), if the stability over time is ensured and enriched, the convenience becomes extremely high.

  From the above viewpoint, the development of a concentrated composition for a color developing replenisher with a one-part composition has been conducted in the past, and it has actually been introduced to the market. It is easy to operate, handle, reduce waste, and economically. However, it is also in line with market needs trends, but on the other hand, it is not enough to meet market demands in the following points, and in fact the concentrated treatment composition with multiple parts may be selected. is there.

  Problems with the one-part composition for the color developer replenisher include firstly that the components of the composition are likely to precipitate during storage, and secondly, from the concentrated composition. The phenomenon that the prepared developer replenisher crawls along the inner wall or rack of the replenish tank occurs, which causes precipitation of replenisher components and contamination of the processing tank, and thirdly, the photosensitive material to be processed tends to be insensitive. Fourthly, the so-called edge contamination is easily attached to the cross section of the support of the photosensitive material to be processed, and fifthly, the cost as a processing agent does not reach the required level of the market.

As for the first problem, for example, Patent Document 1 is an alkanolamine, Patent Document 2 is an arylamine, Patent Document 3 is an anionic surfactant, and Patent Document 4 is an aromatic sulfonic acid. It is disclosed that when added to a developing composition, precipitation during storage over time is prevented.
As for the second problem, for example, Patent Document 5 discloses that the presence of dialkylhydroxylamine and hydroxyalkylamine suppresses the phenomenon of creeping up and prevents replenisher component precipitation and processing tank contamination. Yes.
Regarding the third problem, Patent Document 6 discloses that the presence of para-toluenesulfonic acid enhances color developability.
Regarding the fourth problem, Patent Document 7 discloses that the presence of alkylene glycols and alkylsulfonic acids suppresses both edge contamination and contamination of processing tanks and racks.

As described above, each of the problems of the concentrated liquid processing composition has some solution to all of the above first to fourth even if a solution is found in spite of the finding of solutions. However, it is not enough to reach a sufficient level and cannot be a complete solution.
Under such circumstances, Patent Document 8 describes development replenishment in which a specific pH range, specific gravity range, and high-concentration color developing agent are contained after combining the above-described compounds such as specific benzenesulfonic acid or lactam. It is disclosed that the liquid composition is a composition that can solve the above first to fourth problems. However, since the composition shown in Patent Document 8 is intended for rapid processing, the cost of the processing agent is increased by increasing the concentration of the color developing agent and increasing the pH, and the composition for general-purpose processing. There are obstacles to this.

The above-mentioned prior art relating to the invention of this application includes the following documents.
Japanese Patent Laid-Open No. 6-194797 Japanese Patent Laid-Open No. 7-114163 JP 7-043874 A JP-A-7-239541 JP-A-4-443 JP-A-7-311453 JP 2001-109115 A Japanese Patent Laid-Open No. 2004-54024

  The object of the present invention is to provide a technology that meets the requirements related to the processing quality in the color lab market described above. Specifically, first, the components of the composition are precipitated during storage. There is no aging stability, and secondly, the developer tank and rack are not smudged by the developer that crawls the tank wall during processing, and thirdly, the color developing activity is sufficient, and fourthly processed. It is another object of the present invention to provide a one-part concentrated composition for a color development replenisher having practical cost, which is satisfied that no edge stains are generated on the cross section of the support of the photosensitive material.

The above object is achieved by the present invention having the following constitution.
1. A one-part concentrated composition for a color development replenisher for a color photographic light-sensitive material, which satisfies the following compositional requirements.
(A) Contains 0.08 to 0.12 mol / L of p-phenylenediamine color developing agent.
(B) The substituted hydroxylamine derivative represented by the following general formula (I) is contained in an amount of 0.06 to 0.16 mol / L.

In the formula, L represents an alkylene group which may be substituted, A represents a carboxy group, a sulfo group, a phosphono group, a hydroxy group, an amino group which may be alkyl-substituted, and R represents a hydrogen atom or may be substituted. Represents an alkyl group.
(C) It contains 0.05 to 1.0 mol / L of ethylene glycol.
(D) The pH when diluted 3.84 times with water is 12.5 to 12.8.
(E) It contains substantially no alkanolamine.

2. 2. The one-part concentrated composition for a color development replenisher for a color photographic light-sensitive material as described in 1 above, wherein the ethylene glycol is a combination of at least diethylene glycol and polyethylene glycol having a molecular weight of 200 to 600.
3. 1 part for color development replenisher for color photographic light-sensitive material according to 1 or 2 above, containing 0.01 to 0.2 mol / L of a sulfinic acid compound represented by the following general formula (II) Mold concentrate composition.
General formula (II) RSO ₂ M
In the formula, R represents an alkyl group, a cycloalkyl group, an alkenyl group, an alkynyl group, an aralkyl group or an aryl group. M represents a hydrogen atom or an alkali metal atom.
4). 4. The diaminostilbene derivative represented by the following general formula (III) and / or the following general formula (IV) is contained in an amount of 0.1 to 1.0 mol / L, A one-part concentrated composition for a color developer replenisher for a color photographic light-sensitive material.
General formula (III)

In the formula, R ₁₁ and R ₁₂ each independently represent a hydrogen atom or an alkyl group, R ₁₃ and R ₁₄ each independently represent a hydrogen atom, an alkyl group or an aryl group, and R ₁₅ represents at least one asymmetric carbon. An alkyl group having or a group represented by the following general formula (Ia), R ₁₆ represents an alkyl group having at least one asymmetric carbon or a group represented by the following general formula (Ib); M ₁ represents a hydrogen atom or an alkali metal atom. R ₁₃ and R ₁₅ , R ₁₄ and R ₁₆ may be bonded to each other to form a ring.
Formula (Ia)

In the formula, n ₁₁ represents an integer of 1 to 3.
Formula (Ib)

In the formula, n ₁₂ represents an integer of 2 to 4.
Formula (IV)

In the formula, Z ₁ and Z ₂ may be the same or different and each represents an amino group having 2 to 3 carbon atoms substituted with a hydroxy group or a sulfonic acid group. M represents a hydrogen atom or an alkali metal atom.

5). 5. A silver halide color photographic light-sensitive material characterized in that the one-part concentrated composition for color development replenisher according to any one of 1 to 4 above is diluted 3 to 6 times with water and used as a replenisher. Processing method.

  Regarding the first to fourth problems described above as problems to be solved by the one-part concentrated composition for color developer replenisher of the present invention, as described in the background art, means for solving each individual problem is disclosed. However, even if they are combined, it has generally not been possible to solve all of the above first to fourth. However, all can be solved within the scope of the special combination of the present invention.

The essential points of the color development replenishing concentrated composition of the present invention are a specific compound (ethylene glycol and a compound of the general formula (I)) that can satisfy any of the above-mentioned four requirements concerning processing quality, and That is, the present inventors have found specific composition conditions in which the concentration range, pH range, and color developing agent concentration are selected.
That is, the present invention uses ethylene glycols at a specific concentration in order to have rapid processing suitability without increasing the color developing agent at a high concentration, in particular diethylene glycol and a specific polyethylene glycol are used in combination, and an optimum pH is selected. Thus, the first to fourth problems have been achieved without sacrificing rapid processing suitability. In addition, by setting the upper limit of the concentration of the color developing agent and other components, there is no decrease in color developability due to diffusion inhibition due to high salt concentration, and the cost of the processing agent is not increased.

  The concentrated composition for color development replenishment for a silver halide photographic light-sensitive material of the present invention, comprising a specific developing agent concentration range, a specific concentration range of a specific compound and a specific pH range, is composed of one part. In addition, color development replenisher with sufficient color development activity and practical cost, which prevents precipitation and precipitation during storage, stains on the development tank and rack due to rising of the developer tank wall, and edge stains. Concentrated composition for use.

The present invention is described in further detail below.
The one-part color developer replenisher concentrated composition can be made into a color developer replenisher simply by diluting with a specified amount of water. Therefore, the composition contains all the components of the color developer replenisher in a concentrated state and constitutes a system that is stable against temperature fluctuations during storage over time. The processing chemicals dissolved in the color developer replenisher concentrated composition generally have (1) a color developing agent as an essential component, (2) an alkali agent component that activates the color developing agent, and (3) color development. Antioxidants (preservatives) that prevent the main agent from oxidative degradation due to air oxidation, etc. (4) Hard water softeners (metal chelates) that block metal impurities that cause turbidity in the developer and promote oxidation Agent), (5) a solubilizing agent that makes the processing composition concentration higher and compact, (6) the surface of the photosensitive material to be processed, and an interface for preventing the generation of bubbles on the development processing tank Activating agent, (7) Antifogging agent to prevent development fog and air fog, (8) Fluorescent whitening agent with effects such as improving whiteness of the white background of the finished photograph (in the case of reflection printing) and color image fastening (9) Appropriateness of other developing solutions It contains various treatment chemicals, such as compounds that fulfill the necessary functions depending on the subject. Among these groups, (1) to (3) are development processing agents, and (4) to (9) may not be included depending on the target photosensitive material and processing form. Moreover, even if one is selected from each group, several compounds may be used.

The color developer replenisher concentrated composition of the present invention satisfies the following requirements in the above-mentioned constitution.
(A) Contains 0.08 to 0.12 mol / L of p-phenylenediamine color developing agent.
(B) The substituted hydroxylamine derivative represented by the general formula (I) is contained in an amount of 0.06 to 0.16 mol / L.
(C) It contains 0.05 to 1.0 mol / L of ethylene glycol.
(D) The pH when diluted 3.84 times with water is 12.5 to 12.8.
(E) It contains substantially no alkanolamine.

The preferred range of requirements for the composition of the composition is as follows.
For (A), the preferred color developing agent concentration is 0.09 to 0.115 mol / L, more preferably 0.095 to 0.110 mol / L.
For (B), the preferred concentration of the substituted hydroxylamine derivative represented by the general formula (I) is 0.07 to 0.15 mol / L, more preferably 0.08 to 0.12 mol / L.
Regarding (C), the preferred ethylene glycol concentration is 0.08 to 0.80 mol / L, more preferably 0.10 to 0.50 mol / L.

About (D), preferable pH is 12.50-12.70, More preferably, it is 12.55-12.65.
Regarding (E), in the present invention, alkanolamines such as diethanolamine, triethanolamine, and triisopropanolamine are substantially not included. However, when alkanolamine is not substantially included, alkanolamine is intentionally added. Therefore, even if a trace amount of alkanolamine is mixed, it means that the influence is not recognized, and the concentration level is generally 1 g / L or less, preferably 0.1 g / L or less. Concentration.
When deviating from the above-described configuration, at least one of stability, concentration, rapid processability, low replenishment suitability and the like of the concentrated composition targeted by the present invention is not satisfied.

  Representative examples of the p-phenylenediamine type color developer contained in the color developer replenisher concentrated composition of the present invention are shown below, but are not limited thereto.

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-Methanesulfonamidoethylaniline 9) 4-amino-N, N-diethyl-3- (β-hydroxyethyl) aniline 10) 4-amino-3-methyl-N-ethyl-N- (β-methoxy ester) L) 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 15) N- (4-amino-3-methylphenyl) -3-hydroxypyrrolidine 16) N- (4 -Amino-3-methylphenyl) -3- (hydroxymethyl) pyrrolidine 17) N- (4-amino-3-methylphenyl) -3-pyrrolidinecarboxamide

  Of the above p-phenylenediamine derivatives, Exemplified Compounds 5) and 8) are particularly preferable, and Compound 8) is most preferable among them. Moreover, these p-phenylenediamine derivatives are usually in the form of a salt such as sulfate, hydrochloride, sulfite, naphthalene disulfonate, p-toluenesulfonate in the state of a solid material.

  The content of the aromatic primary amine developing agent in the processing composition is as described above, but the concentration of the color developing agent in the developing replenisher prepared by diluting the composition 3 to 6 times with water is It is prepared to be 10 to 40 mmol, preferably 12 to 35 mmol, more preferably 15 to 30 mmol per liter of liquid.

  Next, the compound of the general formula (I) according to the present invention will be described in detail. In the general formula (I), L represents a linear or branched alkylene group having 1 to 10 carbon atoms which may be substituted, and preferably 1 to 5 carbon atoms. Specifically, preferred examples include methylene, ethylene, trimethylene, and propylene. The substituent represents a carboxy group, a sulfo group, a phosphono group, a hydroxy group, or an amino group that may be alkyl-substituted, and preferred examples include a carboxy group, a sulfo group, and a hydroxy group. A represents a carboxy group, a sulfo group, a phosphono group, a hydroxy group, or an amino group that may be alkyl-substituted, and preferred examples include a carboxy group, a sulfo group, and a hydroxy group. These may be salts of sodium, potassium, lithium and the like. Preferred examples of -LA include a carboxymethyl group, a carboxyethyl group, a carboxypropyl group, a sulfoethyl group, a sulfopropyl group, and a hydroxyethyl group. R represents a hydrogen atom, a linear or branched alkyl group having 1 to 10 carbon atoms, and preferably having 1 to 5 carbon atoms. Examples of the substituent include a carboxy group, a sulfo group, a phosphono group, a hydroxy group, and an amino group that may be alkyl-substituted, and preferred examples include a carboxy group, a sulfo group, and a hydroxy group. These substituents may be salts of sodium, potassium, lithium and the like. Next, specific compounds of the general formula (I) will be described, but the compounds represented by the general formula (I) used in the present invention are not limited to these.

  Among the above specific compounds, exemplary compound (2), exemplary compound (6) and exemplary compound (16) are preferable, and exemplary compound (6) is particularly preferable. These compounds can be synthesized by the synthesis methods described in JP-A-3-56456 (US Pat. Nos. 5,262,563 and 5,248,811) and JP-A-3-157354.

  In the present invention, the compound of the general formula (I) is contained in an amount of 0.001 to 0.05 mol / liter in the liquid color development replenisher obtained by diluting the one-part concentrated composition for color developer replenisher. In particular, 0.005 to 0.04 mol / liter, more preferably 0.01 to 0.03 mol / liter is preferable. In the one-part concentrated composition for color development replenisher, only one kind of the above-mentioned compounds may be used, or two or more kinds may be used in combination. When used in combination, the total concentration of the compounds of general formula (I) in the color developer replenisher is preferably the above value.

  In the one-part concentrated composition for color developer replenisher of the present invention, hydroxylamine may be contained at a concentration of 0.02 mol / liter or less, but it is more preferable that hydroxylamine is not contained at all.

Next, the ethylene glycols used in the one-part concentrated composition for color developer replenisher of the present invention will be further described.
Preferred ethylene glycols are diethylene glycol, triethylene glycol, polyethylene glycol having a molecular weight of 200 to 600, and polyethylene glycol / propylene glycol block copolymer having a molecular weight of 200 to 600, and more preferably diethylene glycol and polyethylene glycol having a molecular weight of 200 to 600. is there.
In order to obtain the effects of the present invention, it is particularly preferable to use diethylene glycol and polyethylene glycol having a molecular weight of 200 to 600 in combination.

  The preferred molar ratio of diethylene glycol to polyethylene glycol having a molecular weight of 200 to 600 is 10: 1 to 1:10, preferably 5: 1 to 1: 1, particularly preferably 4: 1 to 2: 1.

  In the present invention, the sulfinic acid derivative represented by the general formula (II) preferably used in the one-part concentrated composition for color developer replenisher will be described.

General formula (II) RSO ₂ M
In the formula, R represents an alkyl group, a cycloalkyl group, an alkenyl group, an alkynyl group, an aralkyl group or an aryl group. M represents a hydrogen atom or an alkali metal atom.
In the general formula (II), R represents an alkyl group, a cycloalkyl group, an alkenyl group, an alkynyl group, an aralkyl group or an aryl group, and when R is an alkyl group, it has 1 to 10 carbon atoms, preferably 1 to 3 carbon atoms. It is an alkyl group. In the case of a cycloalkyl group, it has 6 to 10 carbon atoms, and the case of 6 is most preferred. In the case of an alkenyl group and an alkynyl group, it has 3 to 10 carbon atoms, preferably 3 to 6 carbon atoms. In the case of an aralkyl group, it has 7 to 10 carbon atoms. In the case of an aryl group, 6 to 10 carbon atoms are preferable, and the case of 6 is most preferable. These groups may be substituted with various substituents, and preferred substituents include hydroxyl group, amino group, sulfonic acid group, carboxylic acid group, nitro group, phosphoric acid group, halogen atom, alkoxy group, mercapto group. Cyano group, alkylthio group, sulfonyl group, carbamoyl group, carbonamido group, sulfonamido group, acyloxy group, sulfonyloxy group, ureido group and thioureido group. Moreover, when these substituents are acid groups, the case of the above salt with M is included.

  Among the above, preferred R is preferably an alkyl group having 1 to 3 carbon atoms or a phenyl group, and preferred substituents include an amino group, a carboxylic acid group, and a hydroxyl group. M in the general formula (II) represents a hydrogen atom, an alkali metal atom, ammonium or quaternary ammonium, and is preferably a hydrogen atom, a sodium atom or a potassium atom.

  Specific compounds of the general formula (II) are exemplified below, but the compounds of the general formula (II) are not limited to these. Moreover, although the sulfinic acid group and the carboxylic acid group are mainly shown in the form of an acid type or a Na, K metal salt, the following exemplary compounds may be other alkali metal salts.

By containing the benzenesulfinic acid compound among the compounds represented by the general formula (II) in the concentrated composition, the stability against air oxidation is improved, and at the same time, the phenomenon of scooping up the developer hardly occurs. Preferred benzenesulfinic acid compounds are m-carboxybenzenesulfinic acid, p-carboxybenzenesulfinic acid, 2,4-dicarboxybenzenesulfinic acid and 4-acetylcarboxybenzenesulfinic acid, among which m-carboxybenzenesulfinic acid is preferred. . These compounds may be used in the form of a free acid or in the form of an alkali metal salt such as a potassium salt, a sodium salt, or a lithium salt.
A preferable addition amount of the benzenesulfinic acid compound is 0.01 to 0.2 mol, more preferably 0.03 to 0.1 mol, per liter of the concentrated composition.

  The compound represented by the general formula (II) is generally synthesized by reduction of a sulfonyl chloride compound, and zinc powder, sulfite ion, alkali metal sulfide and the like are used as a reducing agent. Other methods are also known. Including the above, a general synthesis method of the compound of the general formula (II) is, for example, Chemical Review (Chem. Rev.), 4508, 69 (1951), Organic Synthesis, Collective Vol. 492 (1941), Journal of American Chemical Society (J. Am. Chem. Soc.), 72, 1215 (1950), ibid, 50, 792, 274, (1928), etc. Yes.

  The concentrated composition for color developer replenisher of the present invention preferably contains a fluorescent brightening agent. As a preferred optical brightener, a bis (triazinylamino) stilbene sulfonic acid compound is preferred. As the bis (triazinylamino) stilbene sulfonic acid compound, known or commercially available diaminostilbene-based brighteners 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. Examples of commercially available compounds are described in, for example, “Dyeing Note”, 9th edition (Colored dyeing), pages 165 to 168. Among the compounds described therein, Blankophor BSU liq. And Hakkol BRK and The following optical brighteners are preferred.

Of the bis (triazinylamino) stilbene sulfonic acid-based fluorescent brighteners, the compounds represented by the general formula (III) or the general formula (IV) are particularly preferable because they are effective for the stability of the composition.
General formula (III)

In the general formula (III), R ₁₁ and R ₁₂ each independently represent a hydrogen atom or an alkyl group, R ₁₃ and R ₁₄ each independently represent a hydrogen atom, an alkyl group or an aryl group, and R ₁₅ represents at least one An alkyl group having an asymmetric carbon or a group represented by the following general formula (Ia) is represented, and R ₁₆ is represented by an alkyl group having at least one asymmetric carbon or the following general formula (Ib). Represents a group, and M ₁ represents a hydrogen atom or an alkali metal atom. R ₁₃ and R ₁₅ , R ₁₄ and R ₁₆ may be bonded to each other to form a ring.
Formula (Ia)

In the general formula (I-a), n ₁₁ represents an integer of 1-3.
Formula (Ib)

In the general formula (Ib), n ₁₂ represents an integer of 2 to 4.
The general formula (III) will be described in detail. The alkyl group represented by R ₁₁ and R ₁₂ is preferably a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, more preferably 1 to 8 carbon atoms, and particularly preferably 1 to 4 carbon atoms. Examples of the substituent include a hydroxyl group, an alkoxy group (for example, methoxy, ethoxy and the like), a sulfonic acid group, an ethyleneoxy group and the like, and these may be further substituted with the above-described substituent. Specific examples of the alkyl group represented by R ₁₁ and R ₁₂ include, for example, methyl group, ethyl group, n-propyl group, i-propyl group, n-octyl group, 2-hydroxyethyl group, 3-hydroxypropyl group, 2 -Hydroxypropyl group, 2-sulfoethyl group, 2-methoxyethyl group, 2- (2-hydroxyethoxy) ethyl group, 2- [2- (2-hydroxyethoxy) ethoxy] ethyl group, 2- (2- [2 -(2-hydroxyethoxy) ethoxy] ethoxy) ethyl group. R ₁₁ and R ₁₂ are preferably a hydrogen atom, a methyl group, an ethyl group, an n-propyl group, an n-butyl group, or a 2-sulfoethyl group, and more preferably a hydrogen atom, a methyl group, an ethyl group, 2- A sulfoethyl group is particularly preferred, and a hydrogen atom and a methyl group are preferred.

Preferred carbon numbers, substituents, specific examples and the like of the alkyl group represented by R ₁₃ and R ₁₄ are the same as those shown for R ₁₁ and R ₁₂ , respectively. The aryl group represented by R ₁₃ and R ₁₄ is preferably a substituted or unsubstituted aryl group having 6 to 20 carbon atoms, more preferably 6 to 10 carbon atoms, and particularly preferably 6 to 8 carbon atoms. Examples of the substituent include a hydroxyl group, an alkoxy group (eg, methoxy, ethoxy, etc.), a carboxy group, an alkyl group (eg, methyl, ethyl, propyl, etc.), a sulfonic acid group, an amino group, a carbamoyl group, and the like. It may be further substituted with a group. Specific examples of the aryl group represented by R ₁₃ and R ₁₄ include a phenyl group, a naphthyl group, a 3,5-dicarboxyphenyl group, a 4-methoxyphenyl group, and a 3-isopropylphenyl group. R ₁₃ and R ₁₄ are each preferably a hydrogen atom, methyl group, ethyl group, n-propyl group, 2-hydroxyethyl group, 3-hydroxypropyl group, 2-hydroxypropyl group, 2-sulfoethyl group, 2- ( 2-hydroxyethoxy) ethyl group or 2- [2- (2-hydroxyethoxy) ethoxy] ethyl group, more preferably hydrogen atom, methyl group, ethyl group, 2-hydroxyethyl group, 2-hydroxypropyl group or A 2- (2-hydroxyethoxy) ethyl group, particularly preferably a hydrogen atom or a methyl group.

The alkyl group having at least one asymmetric carbon represented by R ₁₅ preferably has 1 to 20 carbon atoms, more preferably 1 to 8 carbon atoms, and particularly preferably 1 to 4 carbon atoms, and may be linear, branched or cyclic. There may be. Examples of the substituent include a hydroxyl group, an amino group, and a carboxyl group, and a hydroxyl group is preferable. Specific examples of the alkyl group having at least one asymmetric carbon represented by R ₁₅ include, for example, 1,2-dihydroxyethyl group, 2-ethyl-1-hydroxyethyl group, 1,2-dihydroxypropyl group, 1,2 -Hydroxyalkylalkyl groups such as dihydroxy-3-hydroxyethyl-propyl group.

  Specific examples of the compound represented by the general formula (III) are shown in the following table, but are not limited thereto.

  Among the compounds represented by the general formula (III), Exemplified Compound III-5 is particularly preferable.

Among the bis (triazinylamino) stilbene sulfonic acid-based fluorescent brighteners, the compound represented by the general formula (IV) that is effective and preferable for the stability of the composition of the present invention together with the compound represented by the general formula (III) The compound will be described.
Formula (IV)

In the compound represented by the general formula (IV), Z ₁ and Z ₂ may be the same or different and each represents an amino group having 2 to 3 carbon atoms substituted with a hydroxy group or a sulfonic acid group. M represents a hydrogen atom or an alkali metal atom such as sodium, potassium or lithium. Specific examples of the compound represented by the general formula (IV) are shown in the following table, but are not limited thereto.

  Among the compounds represented by the general formula (IV), compounds represented by IV-3, IV-4, IV-5, IV-8, IV-13, and IV-17 are preferable, and IV-13 is particularly preferable.

The concentration of these compounds in the concentrated composition is preferably 1 to 20 g / L, more preferably 2 to 15 g / L, and particularly preferably 5 to 15 g / L in the color developer replenisher prepared therefrom. L. Two or more compounds of the general formula (II) may be used, or may be used in combination with other triazinyl stilbene compounds. Also when used in combination, it is preferred that the compound of the general formula (II) is 30% or more, preferably 40% or more of the total fluorescent brightening agent. The compound of general formula (II) can be synthesized by known methods and is commercially available.
Further, the compound represented by the general formula (III) and the compound represented by the general formula (IV) are preferably used in combination, and the preferred molar ratio is 5: 1 to 1: 5, more preferably 3: 1 to 1: 3, particularly preferably 2: 1 to 1: 2.

  The total concentration of these compounds in 1 liter of the concentrated composition is preferably 1 to 50 mmol, more preferably 3 to 30 mmol.

The concentrated composition of the present invention can be further enhanced by adding a compound selected from alkylbenzene-substituted benzenesulfonic acids and lactams.
A preferable alkyl group substituted for benzenesulfonic acid is an alkyl group having 3 or less carbon atoms, more preferably a methyl group or an ethyl group. The substitution position is mono- or di-substitution. In the former case, 4-position substitution is preferred, and in the latter case, a 2,4-di substitution product is preferred.

  Preferred benzenesulfonic acids that may be alkyl-substituted are benzenesulfonic acid, p-toluenesulfonic acid, xylenesulfonic acid, 4-ethylsulfonic acid, and among them, benzenesulfonic acid and p-toluenesulfonic acid are preferable. Most preferred is p-toluenesulfonic acid. These compounds may be used in the form of a free acid or in the form of an alkali metal salt such as a potassium salt, a sodium salt, or a lithium salt.

The lactams that may be contained in the concentrated treatment composition of the present invention include β-propiolactam, γ-butyrolactam, δ-valerolactam, ε-caprolactam, N-methyl-β-propiolactam, N-methyl-γ -Butylactam, N-methyl-δ-valerolactam, and N-methyl-ε-caprolactam are preferable. Among them, δ-valerolactam and ε-caprolactam are preferable, and ε-caprolactam is most preferable.
The concentrated developer composition of the present invention may contain either benzenesulfonic acids or lactams, but the preferred concentration range in which the effect is particularly exerted is a liquid in use, that is, a developing replenisher or a mother liquid (tank liquid). ) Is 3 to 6 times. Therefore, the concentration in the concentrated composition is designed to be 0.01 to 200 g, preferably 1 to 100 g, more preferably 5 to 50 g per liter of the replenisher or mother liquor when diluted at the above magnification. .

  The concentrated composition for color development replenisher of the present invention can be applied to any color photographic light-sensitive material for photographing and printing, but the effect of the invention is exhibited particularly when applied to color paper.

  Constituent chemicals other than the above-mentioned characteristic constitution of the color development replenisher concentrated composition of the present invention will be described below, but each of the processing composition and the replenisher mixed with water at a predetermined ratio. Instead of explaining the above, both will be described together, and the component concentration will be described mainly with the concentration of the working solution.

  In addition to the substituted hydroxylamine derivative, an organic preservative may be added to the color developing composition as a preservative. The organic preservative refers to all organic compounds that reduce the deterioration rate of the aromatic primary amine color developing agent by being contained in the processing solution of the photosensitive material. That is, it is an organic compound having a function of preventing air oxidation of color developing agents, among others, hydroxylamine derivatives other than the general formula (I), hydroxamic acids, hydrazides, phenols, α-hydroxy ketones , Α-amino ketones, saccharides, monoamines, diamines, polyamines, quaternary ammonium salts, nitroxy radicals, alcohols, oximes, diamide compounds, and condensed amines are particularly effective. It is a constant agent. 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. You may contain the compound currently disclosed by each gazettes, such as No ..

  Other preservatives include various metals described in JP-A-57-44148 and 57-53749, salicylic acids described in JP-A-59-180588, and JP-A-56-94349. The polyethyleneimines described above, aromatic polyhydroxy compounds described in US Pat. No. 3,746,544 and the like may be contained as necessary.

  The content of the preservative in the processing agent varies depending on the type of the preservative, but generally the concentration in the working solution is 1 to 200 mmol, preferably 10 to 100 mmol per liter of the developer. Added.

In the color developing composition, for example, chlorine ion may be added to the developing composition for color paper, if necessary. Color developers (especially developers for color print materials) usually contain chlorine ions of 3.5 × 10 ^{−2 to} 1.5 × 10 ⁻¹ mol / liter, but chlorine ions are usually a by-product of development. In general, it is unnecessary to add to the replenishing developing composition. A developing composition for a light-sensitive material for photographing may not contain chlorine ions.

It regard bromine ion, bromine ion in the color developing solution, about 1～5X10 ^-3 mol / l in the processing of photographic materials, also, in the processing of the print material is less 1.0 × 10 ^-3 mol / liter Is preferred. However, the composition for color developer replenisher is often not necessary in the same manner as the above-mentioned chlorine ions, but when added, bromine ions are added to the processing agent as necessary so that the bromine ion concentration falls within the above range. Ions may be added.
When the photosensitive material to be obtained is obtained from a silver iodobromide emulsion such as a color negative film or a color reversal film, the situation is the same with respect to iodine ions, but usually iodine ions are released from the photosensitive material. Thus, the iodine ion concentration per liter of the developer is about 0.5 to 10 mg, and therefore it is usually not included in the replenishing processing composition.

In the present invention, the pH of the developer in the developing tank is 9.0 to 12.5, preferably 9.5 to 11.5, and more preferably 9.8 to 10.8. Accordingly, the pH of the replenisher is preferably set to 11.0 to 13.5, more preferably 11.5 to 13.2, particularly preferably 12.0 to 13.0, and most preferably 12. .5 to 12.8. On the other hand, in the present invention, the pH value is set to 12.5 to 12.8 when the pH value is measured by diluting the concentrated composition for developer replenisher solution 3.84 times, and the pH value is maintained. As possible, an alkali agent, a buffering agent and, if necessary, an acid agent can be included. The reason for measuring pH by diluting water 3.84 times is that the concentrated composition for developer replenisher according to the present invention has a very high pH, and the pH when directly measured without diluting with water is pH This is because the measurement electrode is close to the response limit and practical measurement accuracy cannot be obtained.
Various hydroxides can be added as the alkali. For example, potassium hydroxide, sodium hydroxide, lithium hydroxide, tripotassium hydrogen phosphate, trisodium hydrogen phosphate and their hydrates, triethanolamine, diethanolamine and the like can be mentioned. Moreover, as an acid agent added as needed, inorganic and organic water-soluble solid acid can be used. For example, succinic acid, tartaric acid, propionic acid, ascorbic acid can be mentioned.

  In order to maintain the above pH when the concentrated composition is diluted with water to prepare a treatment liquid, it is preferable to use various buffers. 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-propanediol salt, valine salt, proline salt, trishydroxyaminomethane salt, lysine salt and the like can be used. In particular, carbonate, phosphate, tetraborate, and hydroxybenzoate have excellent buffering ability in the high pH range of pH 9.0 or higher, and adverse effects on photographic performance even when added to color developers (fogging, etc.) It is particularly preferable to use these buffering agents.

Specific examples of these buffering agents include sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, trisodium phosphate, tripotassium phosphate, disodium phosphate, dipotassium phosphate, sodium borate, boric acid. Potassium, sodium tetraborate (borax), potassium tetraborate, sodium o-hydroxybenzoate (sodium salicylate), potassium o-hydroxybenzoate, sodium 5-sulfo-2-hydroxybenzoate (sodium 5-sulfosalicylate) ), Potassium 5-sulfo-2-hydroxybenzoate (potassium 5-sulfosalicylate), and the like. However, the present invention is not limited to these compounds.
Since the buffer is not a component that is reacted and consumed, the concentration is 0.01 to 2 mol, preferably 0.1 to 0.5 mol, per liter of the development replenisher prepared from the processing agent. The addition amount in the composition is determined.

Various chelating agents which are precipitation inhibitors for other color developer components such as calcium and magnesium, or color developer stability improvers can also be added to the color developing composition. For example, nitrilotriacetic acid, diethylenetriaminepentaacetic acid, ethylenediaminetetraacetic acid, N, N, N-trimethylenephosphonic acid, ethylenediamine-N, N, N ′, N′-tetramethylenesulfonic acid, transsiloxanediaminetetraacetic acid, 1 , 2-diaminopropanetetraacetic 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- And dihydroxybenzene-4,6-disulfonic acid It is.
These chelating agents may be used in combination of two or more as required.
The amount of these chelating agents may be sufficient to sequester metal ions in the prepared color developer replenisher. For example, it is added so as to be about 0.1 to 10 g per liter.

  If necessary, an arbitrary development accelerator can be added to the color developing composition according to the present invention. As development accelerators, see 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. Thioether compounds represented, p-phenylenediamine compounds represented in JP-A-52-49829 and JP-A-50-15554, JP-A-50-137726, JP-B 44-30074, JP-A-56- Quaternary ammonium salts represented in 156826 and 52-43429, etc., U.S. Pat. 2,596,926 and 3,582,346, etc.Amine compounds described in each publication or specification, JP-B-37-16088, JP-A-42-25201, U.S. Pat.No. 3,128,183, JP-B-41-11431, JP-A-42-23883 And U.S. Pat.No. 3,532,501, etc. The 3-pyrazolidones or imidazoles may be added as needed. The added amount in the composition is determined so that the concentration of the developer and replenisher prepared from the processing agent is 0.001 to 0.2 mol, preferably 0.01 to 0.05 mol, per liter. It is done.

An optional antifoggant can be added to the color developing composition according to the present invention, if necessary, in addition to the halogen ion. Examples of organic antifoggants 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, various surfactants such as alkyl sulfonic acid, aryl sulfonic acid, aliphatic carboxylic acid, and aromatic carboxylic acid may be added to the color developer as necessary. The added amount in the composition is such that the concentration of the developer and replenisher prepared from the processing composition is 0.0001 to 0.2 mol, preferably 0.001 to 0.05 mol, per liter. It is decided.

  As the solvent of the concentrated composition, water is usually used, but an aqueous solvent may be used to increase the solubility. In that case, a developing agent such as diethylene glycol, triethylene glycol, or ethylene glycol, which is mainly composed of water, is preferable. A mixed solvent containing 1 to 20% by mass of a water-miscible organic solvent that increases solubility is selected.

  Next, in addition to the aminopolycarboxylic acid iron (III) complex salt, other known bleaching agents can be used as a bleaching agent used in combination with the color developing processing composition. Examples of bleaching agents that can be used in combination include iron (III) complex salts of organic acids such as citric acid, tartaric acid, malic acid, persulfates, and hydrogen peroxide.

  A preferable iron (III) complex salt of aminopolycarboxylic acid is an iron (III) complex salt of aminopolycarboxylic acid exemplified below. That is, biodegradable ethylenediamine disuccinic acid (SS form), N- (2-carboxylateethyl) -L-aspartic acid, betaalanine diacetic acid, methyliminodiacetic acid, ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, 1 , 3-diaminopropanetetraacetic acid, propylenediaminetetraacetic acid, nitrilotriacetic acid, cyclohexanediaminetetraacetic acid, iminodiacetic acid, glycol etherdiaminetetraacetic acid. These compounds may be any of sodium, potassium, thylium or ammonium salts. Among these compounds, ethylenediamine disuccinic acid (SS form), N- (2-carboxylateethyl) -L-aspartic acid, β-alanine diacetic acid, ethylenediaminetetraacetic acid, 1,3-diaminopropanetetraacetic acid, methyliminodioxy Acetic acid is preferable because its iron (III) complex salt has good photographic properties. These iron (III) 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 may be used to form an iron (III) complex salt in a solution. Further, the chelating agent is used in excess as compared with the formation of the iron (III) complex salt.

  The concentration of the bleaching agent in the bleaching agent part is 0.01 to 1.0 mol / L, preferably 0.03 to 0.80 mol / L, more preferably, in the processing solution prepared from the processing composition. Is determined to be 0.05 to 0.70 mol / L, more preferably 0.07 to 0.50 mol / L.

  The bleach part includes various known organic acids (eg acetic acid, lactic acid, glycolic acid, succinic acid, maleic acid, malonic acid, citric acid, sulfosuccinic acid, citric acid, tartaric acid, glutaric acid, lactic acid, etc.), organic A base (for example, imidazole, dimethylimidazole, etc.) or a compound represented by the general formula (Aa) described in JP-A-9-211819 including 2-picolinic acid and kojic acid. It is preferable to contain the compound represented by general formula (Bb) as described in above. The amount of these compounds added is determined so that the concentration of the prepared treatment liquid is preferably 0.005 to 3.0 mol, and more preferably 0.05 to 1.5 mol, per liter. The organic acid is preferably a monobasic acid or a dibasic acid, particularly preferably a dibasic acid because it is low in volatility, has little odor, and has a large buffer capacity at pH 2 to 3.5.

  The fixing agent part constituting the bleach-fixing solution processing composition in combination with the bleaching agent part is a known fixing chemical, that is, a thiosulfate such as sodium thiosulfate or ammonium thiosulfate, sodium thiocyanate, ammonium thiocyanate, etc. 1 or 2 selected from water-soluble silver halide solubilizers such as thioether compounds such as thiocyanate, ethylenebisthioglycolic acid, 3,6-dithia-1,8-octanediol, and thioureas The above can be mixed and contained. A special bleach-fixing solution comprising a combination of a fixing agent described in JP-A-55-155354 and a large amount of a halide such as potassium iodide can also be used. In the present invention, it is preferable to use thiosulfate, particularly ammonium thiosulfate. The concentration of the fixing chemical in the fixing agent part is preferably designed to be 0.3 to 3 mol per liter of the blended solution when the bleach-fixing solution is prepared, and more preferably 0.5 to 2.0. Designed in the molar range.

  Fixer parts include preservatives such as sulfites (eg, sodium sulfite, potassium sulfite, ammonium sulfite, etc.), bisulfites (eg, ammonium bisulfite, sodium bisulfite, potassium bisulfite, etc.), Sulphite ion releasing compounds such as sulfites (for example, potassium metabisulfite, sodium metabisulfite, ammonium metabisulfite, etc.), arylsulfinic acids such as p-toluenesulfinic acid, m-carboxybenzenesulfinic acid, etc. It is preferable to contain. These compounds are preferably contained in an amount of about 0.02 to 1.0 mol / L (as the concentration of the prepared treatment liquid) in terms of sulfite ions or sulfinate ions.

  As a preservative, ascorbic acid, a carbonyl bisulfite adduct, a carbonyl compound, or the like may be added in addition to the above.

  The following describes the bleach-fix solution prepared by mixing the bleach part and the fixer part, and adding a little water if necessary, but it can be contained in either the bleach part or the fixer part. A good bleach-fixing solution component is also described in this section.

The dissolution pH range of the bleach-fixing solution processing composition is preferably 3-8, more preferably 4-8. When the pH is lower than this, the desilvering property is improved, but the deterioration of the solution and the leuco conversion of the cyan dye are promoted. On the contrary, if the pH is higher than this, desilvering is delayed and stain is likely to occur.
In order to adjust the pH, potassium hydroxide, sodium hydroxide, lithium hydroxide, lithium carbonate, sodium carbonate, potassium carbonate, acidic or alkaline buffering agent, etc., which are alkaline are added to the fixing agent part side as necessary. be able to.

  In addition, one or both parts of the bleach-fixing solution processing composition may contain various other fluorescent brighteners, antifoaming agents, surfactants, polyvinylpyrrolidone, and the like.

Next, a color development processing step using the color developer replenisher concentrated composition of the present invention will be described.
The color development process to which the color development replenisher concentrated composition of the present invention is applied comprises a color development process, a desilvering process, a water washing or stabilizing bath process and a drying process, and a rinsing process, an intermediate water washing process, An auxiliary process such as a neutralization process may be inserted. The desilvering step is performed by a one-step process using a bleach-fixing solution. In addition to a water washing alternative stabilizing bath instead of the water washing step, an image stabilizing bath for the purpose of image stabilization can be provided between the water washing or stabilizing bath step and the drying step.

The development processing according to the present invention is designed to be applied to general-purpose processing of color light-sensitive materials, and the replenishing amount of the color development replenisher is preferably ^{20 to} 50 ml, more preferably 25 ml to 1 m ² of the light-sensitive material. 45 ml, most preferably 25-40 ml. The concentrated composition is designed to be diluted with water to the above concentration. The replenishing amount of the bleach-fixing solution is preferably 20 to 60 ml, more preferably 25 to 50 ml, and most preferably 25 to 45 ml per 1 m ² of the light-sensitive material. The replenishment amount of the bleach-fixing solution is preferably divided into a bleaching agent part and a fixing agent part. In this case, the replenishment amount of the bleach-fixing solution indicates the total replenishment amount of the bleaching agent part and the fixing agent part. is there. Moreover, it is preferable that the replenishment amount of the rinsing liquid (washing water and / or stabilizing liquid) is 50 ml to 200 ml as a whole.

  The color development time (that is, the time for performing the color development step) is preferably 45 seconds or less, more preferably 40 seconds or less, still more preferably 30 seconds or less, and particularly preferably 25 seconds or less and 6 seconds or more. Similarly, the bleach-fixing time (that is, the time for performing the bleach-fixing step) is preferably 45 seconds or less, more preferably 30 seconds or less, and even more preferably 25 seconds or less and 6 seconds or more. Further, the rinsing (washing or stabilizing) time (that is, the time for performing the rinsing step) is preferably 90 seconds or shorter, more preferably 30 seconds or shorter and 6 seconds or longer.

  The color development time refers to the time from when the photosensitive material enters the color developer until it enters the bleach-fixing solution in the next processing step. For example, when processed by an automatic developing machine, the time during which the photosensitive material is immersed in a color developer (so-called submerged time) and the photosensitive material leaves the color developer and is bleached and fixed in the next processing step. The sum of both the time during which air is conveyed toward the liquid (so-called air time) and the color development time. Similarly, the bleach-fixing time refers to the time from when the photosensitive material enters the bleach-fixing solution until the next washing or stabilizing bath. The rinsing (water washing or stabilization) time refers to the time (so-called liquid time) that the photosensitive material is in the liquid for the drying process after entering the rinse liquid (water washing or stabilization liquid).

  The processing solution temperature in the color development step, the bleach-fixing step, and the rinsing step is 30 to 60 ° C, preferably 38 to 50 ° C, more preferably 38 to 45 ° C.

The amount of rinsing solution can be set in a wide range depending on the characteristics of the photosensitive material (for example, depending on the material used such as coupler) and application, the temperature of the rinsing solution (washing water), the number of rinsing solutions (washing tank) (stage number), and various other conditions. Can do. Among these, the relationship between the number of rinse liquid tanks (water washing tanks) and the amount of water in the multi-stage countercurrent system is the Journal of the Society of Motion Picture and Motion of Picture Picture and Television Engineers) Vol. 64, p. It can be determined by the method described in 248-253 (May 1955).
Usually, the number of stages in the multistage countercurrent system is preferably from 3 to 15, particularly preferably from 3 to 10.

  According to the multi-stage counter-current system, the amount of the rinse liquid can be greatly reduced, and the increase of the residence time of water in the tank causes problems such as bacteria breeding and the generated suspended matter adhering to the photosensitive material. As a solution, a rinsing solution containing an antibacterial and antifungal agent described later is preferable.

  The developed silver halide color photographic material is subjected to post-processing such as a drying step. In the drying process, drying is performed by absorbing moisture with a squeeze roller or cloth immediately after the development process (rinsing process) from the viewpoint of reducing the amount of moisture carried into the image film of the silver halide color photographic light-sensitive material. It is also possible to expedite. Of course, drying can be accelerated by increasing the temperature or changing the shape of the spray nozzle to increase the drying air. Further, as described in JP-A-3-157650, drying can be accelerated by adjusting the blowing angle of the dry air to the photosensitive material or by the method of removing the exhaust air.

The development processing method according to the present invention is suitable for carrying out using an automatic developing machine.
The color paper automatic processor transports the color paper to the final size and then develops it (sheet type transport method), or develops the paper in a long roll and cuts it to the final size after processing (cine) However, the concentrated composition of the present invention can be preferably applied to a developing machine of any of those transport systems.

In the present invention, in order to perform processing quickly, the air time when the photosensitive material moves between the processing solutions, that is, the crossover time is preferably as short as possible, preferably 10 seconds or less, more preferably 7 seconds or less, More preferably, it is 5 seconds or less.
Further, in order to shorten the crossover time and prevent the mixing of the processing liquid, a crossover rack structure provided with a mixing prevention plate is preferable.

  The drying conditions of the photosensitive material also affect the evaporation of the processing solution. As a drying method, it is preferable to use a ceramic hot air heater.

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

Resin such as PVC (polyvinyl chloride), PP (polypropylene), PE (polyethylene), TPX (polymethylpentene) is suitable for the roller material of the processing section. These materials can also be used for other processing liquid contact portions. In addition, PE resin is preferable also for the material of the replenishment tank by blow formation.
Materials for processing parts, gears, sprockets, bearings, etc. include PA (polyamide), PBT (polybutylene terephthalate), UHMPE (ultra high molecular weight polyethylene), PPS (polyphenylene sulfide), LCP (fully aromatic polyester resin, liquid crystal polymer) ) Etc. are suitable.
PA resin is polyamide resin such as 66 nylon, 12 nylon, and 6 nylon, and those containing glass fiber or carbon fiber are strong against swelling by the treatment liquid and can be used.

High molecular weight products such as MC nylon and compression molded products can be used without fiber reinforcement. UHMPE resin is suitable for unreinforced products such as “Lubema” manufactured by Mitsui Petrochemical Co., Ltd., “Hi-X Million” Sakushin Kogyo Co., Ltd. “New Light”, Asahi Kasei Kogyo Co., Ltd. “Sun Fine”, etc. Are suitable. The molecular weight is preferably 1,000,000 or more, more preferably 1,000,000 to 5,000,000.
The PPS resin is preferably glass fiber or carbon fiber reinforced. Examples of the LCP resin include ICI Japan Co., Ltd. “Victrex”, Sumitomo Chemical Co., Ltd. “Econol”, Nippon Oil Co., Ltd. “Zyder”, Polyplastics Co., Ltd. “Vectra” and the like.
In particular, the material of the conveyor belt is preferably ultrahigh strength polyethylene fiber or polyvinylidene fluoride resin described in Japanese Patent Application No. 2-276886.
As a soft material such as a squeeze roller, a foamed vinyl chloride resin, a foamed silicon resin, and a foamed urethane resin are suitable. Examples of the urethane foam resin include “Rubicel” manufactured by Toyo Polymer Co., Ltd.
EPDM rubber, silicon rubber, Viton rubber and the like are preferable as rubber materials such as a pipe joint, an agitation jet pipe joint, and a sealing material.

  Moreover, it is also preferable to add a chemical | medical agent directly to a processing tank, and to add the water according to a dilution rate to a processing tank. Moreover, it is also preferable to use it as a replenishing solution by automatically dissolving and diluting it in a replenishing tank using an automatic preparation device.

The treatment agent used in the present invention is preferably used in the form of a kit in which treatment agents for each step are combined into a set, in addition to individually treating the treatment agents for each step. More preferably, the processing agents for the replenisher can be attached to or detached from the developing device all together in the form of a cartridge. The material of these treatment agent containers can be any material such as paper, plastic, metal, etc., but the oxygen permeation coefficient is 57 × 10 ⁻⁶ mL / Pa · m, apart from the treatment agent containing bleach agent. A plastic material of ² · s (50 ml / m ² · atm · day) or less is preferable. The oxygen permeability coefficient "O ₂ permeation of plastic Container, Modern Packing" _{(O 2 permeation of plastic container,} Modern Packing; NJCalyan, 1968) 12 January issue of, pp 143 to 145 It can be measured by the method.
Specific examples of preferable plastic materials include vinylidene chloride (PVDC), nylon (NY), polyethylene (PE), polypropylene (PP), polyester (PES), ethylene-vinyl acetate copolymer (EVA), and ethylene-vinyl. Examples include alcohol copolymer (EVAL), polyacrylonitrile (PAN), polyvinyl alcohol (PVA), polyethylene terephthalate (PET), and the like.
Apart from the bleach-containing treatment agent container, PVDC, NY, PE, EVA, EVAL and PET are preferably used for the purpose of reducing oxygen permeability.

  These materials may be used in a single composition or in a mixed configuration, may be used after being shaped, may be a film container or a bottle container, and are used by bonding a plurality of types (so-called composite film) ) May be used. As the shape of the container, various shapes such as a bottle type, a cubic type and a pillow type can be used. However, the present invention is a cubic type which is flexible and easy to handle and can be reduced in volume after use. A structure similar to is particularly preferred.

Moreover, when using as a composite film, although the thing of the structure shown below is especially preferable, it is not limited to these. That is, PE / EVAL / PE, PE / aluminum foil / PE, NY / PE / NY, NY / PE / EVAL, PE / NY / PE / WVAL / PE, PE / NY / PE / PE / PE / NY / PE PE / SiO ₂ film / PE, PE / PVDC / PE, PE / NY / aluminum foil / PE, PE / PP / aluminum foil / PE, NY / PE / PVDC / NY, NY / EVAL / PE / EVAL / NY NY / PE / EVAL / NY, NY / PE / PVDC / NY / EVAL / PE, PP / EVAL / PE, PP / EVAL / PP, NY / EVAL / PE, NY / aluminum foil / PE, paper / aluminum foil / PE, paper / PE / aluminum foil / PE, PE / PVDC / NY / PE, NY / PE / aluminum foil / PE, PET / EVAL / PE, ET / aluminum foil / PE, and the like PET / aluminum foil / PET / PE.

The thickness of the composite film is about 5 to 1500 microns, preferably about 10 to 1000 microns. The inner volume of the finished container is about 100 ml to 20 liters, preferably about 500 ml to 10 liters.
The container (cartridge) may have a cardboard or plastic outer box, or may be formed integrally with the outer box.
In the present invention, the cartridge can be filled with various processing solutions. For example, a color developer, black and white developer, bleach solution, adjustment solution, reversal solution, fixing solution, bleach-fix solution, stabilizer, and the like can be mentioned. It is preferable to use a developer, a fixing solution and a bleach-fixing solution.

Conventional containers for processing liquids include single layer materials such as high density polyethylene (HDPE), polyvinyl chloride resin (PVC), polyethylene terephthalate (PET), and multilayer materials such as nylon / polyethylene (NY / PE). The rigid container used can be used.
Further, after the contents are discharged and emptied, it is possible to use a liquid container having a flexibility that can easily reduce the volume of the container, that is, reduce the required space. As an example, it is preferable to use a container having the above flexibility. A specific example of the flexible container is a liquid container in which a hard mouth protruding upward from a flexible container body is opened and closed by a lid member engaged therewith, the container body and the mouth And a container having a bellows portion in at least a part in the height direction of the container body (FIGS. 1 and 2 described in JP-A-7-5670).

[Applicable photosensitive material]
Next, a silver halide color photographic light-sensitive material to which the color developer replenisher composition of the present invention is applied (hereinafter sometimes simply referred to as “photosensitive material”) will be described.
The light-sensitive material used in the present invention is a color photographic light-sensitive material for photographing and color printing paper for color printing, which are widely used in the photographic market as described above in relation to the object and background of the invention. At least one photosensitive layer is provided on the support. A typical example is a silver halide photographic light-sensitive material having at least one photosensitive layer comprising a plurality of silver halide emulsion layers having substantially the same color sensitivity but different sensitivity on a support. It is.

  In a multilayer silver halide color photographic light-sensitive material for photographing, the photosensitive layer is a unit photosensitive layer having a color sensitivity to any one of blue light, green light, and red light, and is generally an array of unit photosensitive layers. However, the red color-sensitive layer, the green color-sensitive layer, and the blue color-sensitive layer are installed in this order from the support side. However, depending on the purpose, the installation order may be reversed, or the installation order may be such that different photosensitive layers are sandwiched in the same color-sensitive layer. A non-photosensitive layer may be provided between the above-described silver halide photosensitive layers and as the uppermost layer and the lowermost layer. These may contain couplers, DIR compounds, color mixing inhibitors and the like described later. A plurality of silver halide emulsion layers constituting each unit photosensitive layer are sequentially exposed to a support, two layers of a high-sensitivity emulsion layer and a low-sensitivity emulsion layer as described in DE 1,121,470 or GB 923,045. It is preferable to arrange so that the degree is low. Further, as described in JP-A-57-112751, 62-200350, 62-206541, 62-206543, a low-sensitivity emulsion layer on the side away from the support, close to the support A high-sensitivity emulsion layer may be provided on the side.

  In addition, as described in JP-B-49-15495, the upper layer is a silver halide emulsion layer having the highest sensitivity, the middle layer is a silver halide emulsion layer having a lower sensitivity, and the lower layer is more sensitive than the middle layer. Examples include an arrangement composed of three layers having different sensitivities in which a low silver halide emulsion layer is arranged and the sensitivities are gradually lowered toward the support. Even in the case of being composed of three layers having different sensitivities, as described in JP-A-59-202464, the medium-sensitive emulsion layer / high They may be arranged in the order of sensitive emulsion layer / low sensitive emulsion layer.

  In order to improve color reproducibility, the main photosensitive layers such as BL, GL, and RL and spectral sensitivity distribution described in the specifications of US 4,663,271, 4,705,744, 4,707,436, and JP-A-62-160448 and 63-89850 are disclosed. It is preferable to dispose a donor layer (CL) having different multi-layer effects adjacent to or close to the main photosensitive layer.

  A photosensitive material for printing generally uses a reflective support, and is often installed in the order of a red color-sensitive layer, a green color-sensitive layer, and a blue color sensitivity in order from the side far from the support. As the silver halide emulsion, a cubic emulsion of silver chloride or silver chlorobromide grains of high silver chloride is used.

  Next, the photosensitive silver halide used in the present invention will be described. The silver halide of the present invention is substantially a cubic or tetradecahedral crystal grain having a {100} face (these grains may have rounded vertices and may have higher order faces), 8 It is preferable that the crystal lattice of the plane body and the main plane are composed of tabular grains having an aspect ratio of 2 or more and comprising {100} planes or {111} planes. The aspect ratio is a value obtained by dividing the diameter of a circle corresponding to the projected area by the thickness of the particle. For tabular grains having a main surface of {100} face or {111} face, reference can be made to columns 33 (P7) to P840 (P8) of JP-A No. 2000-352794. In the present invention, a cube is most preferable. The particle size is preferably 0.5 μm or less, more preferably 0.4 μm or less, in terms of cubic conversion side length.

  In this specification, the cube side length is represented by the length of one side when a volume equal to the volume of each particle is converted into a cube, and in this specification, the cube side length also indicates the same meaning. The emulsion of the present invention is preferably composed of grains having a monodispersed grain size distribution. The variation system number of the cubic conversion side length of all the particles of the present invention is preferably 20% or less, more preferably 15% or less, and still more preferably 10% or less. The coefficient of variation of the cubic conversion side length is expressed as a percentage of the average side length of the standard deviation of one side of the cubic conversion side length of each particle. At this time, for the purpose of obtaining a wide latitude, it is preferable to use the above monodispersed emulsion by blending it in the same layer or to carry out multilayer coating.

  The silver halide emulsion used in the present invention may contain silver halide grains other than the silver halide grains (that is, specific silver halide grains) contained in the silver halide emulsion defined in the present invention. However, the silver halide emulsion defined in the present invention requires that 50% or more of the total projected area of all grains be silver halide grains as defined in the present invention, and preferably 80% or more. More preferably, it is 90% or more.

  As the silver halide emulsion used in the present invention, an emulsion containing silver halide grains having a specific silver halide content is used, and the silver chloride content is 90 mol% or more from the viewpoint of rapid processability. The silver chloride content is preferably 93 mol% or more, more preferably 95 mol% or more. The silver bromide content is preferably 0.1 to 7 mol%, more preferably 0.5 to 5 mol%, since it is a high contrast and has excellent latent image stability. The silver iodide content is preferably 0.02-1 mol%, more preferably 0.05-0.50 mol%, and more preferably 0.07-0. 40 mol% is most preferred. The silver halide grains of the present invention are preferably silver iodobromochloride grains, and more preferably silver iodobromochloride grains having the above halogen composition.

  The silver halide grains in the silver halide emulsion used in the present invention preferably have a silver bromide-containing phase and / or a silver iodide-containing phase. Here, the silver bromide or silver iodide-containing phase means a portion where the concentration of silver bromide or silver iodide is higher than the surroundings. The halogen composition of the silver bromide-containing phase or silver iodide-containing phase and its surroundings may change continuously or may change sharply. Such a silver bromide or silver iodide-containing phase may form a layer having a substantially constant width at a certain portion in the grain, or may be a maximum point having no spread. The local silver bromide content of the silver bromide-containing phase is preferably 2 mol% or more, more preferably 3 to 50 mol%, and most preferably 4 to 20 mol%. The local silver iodide content of the silver iodide-containing phase is preferably 0.3 mol% or more, more preferably 0.5 to 8 mol%, and more preferably 1 to 5 mol%. Most preferred. Further, a plurality of such silver bromide or silver iodide-containing phases may be formed in layers in each grain, and the silver bromide or silver iodide content may be different, but at least one of each. It is necessary to have a contained phase of

  It is important that the silver bromide-containing phase or the silver iodide-containing phase of the silver halide emulsion used in the present invention is layered so as to surround each grain. In one preferred embodiment, the silver bromide-containing phase or the silver iodide-containing phase formed in layers so as to surround the grains has a uniform concentration distribution in the circumferential direction of the grains in each phase. However, in the silver bromide-containing phase or silver iodide-containing phase that are layered so as to surround the grain, the maximum or minimum point of the silver bromide or silver iodide concentration exists in the circumferential direction of the grain, and the concentration distribution You may have. For example, when a silver bromide-containing phase or silver iodide-containing phase is formed in a layer so as to surround the grain in the vicinity of the grain surface, the silver bromide or silver iodide concentration at the grain corner or edge is different from the main surface. There is a case. In addition to the silver bromide-containing phase and the silver iodide-containing phase that are layered so as to surround the grain, the silver bromide-containing phase that is completely isolated in a specific part of the surface of the grain and does not surround the grain Alternatively, there may be a silver iodide containing phase.

  When the silver halide emulsion used in the present invention contains a silver bromide-containing phase, the silver bromide-containing phase is preferably formed in a layered manner so as to have a silver bromide concentration maximum inside the grain. Further, when the silver halide emulsion of the present invention contains a silver iodide-containing phase, the silver iodide-containing phase is preferably formed in a layered manner so as to have a silver iodide concentration maximum on the surface of the grain. Such a silver bromide-containing phase or silver iodide-containing phase is composed of a silver amount of 3% to 30% of the grain volume in order to increase the local concentration with a smaller silver bromide or silver iodide content. It is preferable that the silver content is 3% or more and 15% or less.

  The silver halide emulsion used in the present invention preferably contains both a silver bromide-containing phase and a silver iodide-containing phase. In this case, the silver bromide-containing phase and the silver iodide-containing phase may be at the same place or different places in the grain, but it is preferable that the silver bromide-containing phase and the silver iodide-containing phase are in different places from the viewpoint of facilitating control of grain formation. Further, the silver bromide-containing phase may contain silver iodide, and conversely, the silver iodide-containing phase may contain silver bromide. In general, iodide added during the formation of high silver chloride grains tends to ooze out on the grain surface than bromide, so the silver iodide-containing phase tends to be formed near the grain surface. Therefore, when the silver bromide-containing phase and the silver iodide-containing phase are at different locations in the grain, the silver bromide-containing phase is preferably formed inside the silver iodide-containing phase. In such a case, another silver bromide-containing phase may be provided further outside the silver iodide-containing phase near the grain surface.

  The silver bromide content or silver iodide content necessary for exhibiting the effects of the present invention such as high sensitivity and high contrast is such that the silver bromide-containing phase or silver iodide-containing phase is formed inside the grain. There is a risk that the amount of silver chloride may be reduced more than necessary, and the rapid processability may be impaired. Therefore, in order to concentrate these functions for controlling the photographic action near the surface in the grain, the silver bromide-containing phase and the silver iodide-containing phase are preferably adjacent to each other. From these points, the silver bromide-containing phase is formed at any of the positions of 50% to 100% of the grain volume as measured from the inside, and the silver iodide-containing phase is any of the positions at 85% to 100% of the grain volume. It is preferable to form it. Further, the silver bromide-containing phase is formed at any position from 70% to 95% of the grain volume, and the silver iodide-containing phase is further formed at any position from 90% to 100% of the grain volume. preferable.

  In order to incorporate silver bromide or silver iodide into a silver halide emulsion, bromide or iodide ions can be introduced by adding a bromide salt or an iodide salt solution alone, or by adding a silver salt solution and a high chloride salt. Along with the addition of the solution, a bromide salt or iodide salt solution may be added. In the latter case, bromide salt or iodide salt solution and high chloride salt solution may be added separately or as a mixed solution of bromide salt or iodide salt and high chloride salt. The bromide salt or iodide salt is added in the form of a soluble salt such as an alkali or alkaline earth bromide salt or iodide salt. Alternatively, it can be introduced by cleaving bromide ions or iodide ions from organic molecules described in US Pat. No. 5,389,508. As another bromide or iodide ion source, fine silver bromide grains or fine silver iodide grains can also be used.

The addition of the bromide salt or iodide salt solution may be concentrated during a period of grain formation or may be performed over a certain period. The position of introduction of iodide ions into the high chloride emulsion is limited in obtaining a high sensitivity and low fog emulsion. Iodide ions are introduced more into the emulsion grains and the increase in sensitivity is smaller. Therefore, the iodide salt solution is preferably added outside 50% of the grain volume, more preferably outside 70%, and most preferably outside 85%. Further, the addition of the iodide salt solution is preferably completed within 98% of the grain volume, and most preferably within 96%. The addition of the iodide salt solution is completed slightly inside from the grain surface, whereby an emulsion with higher sensitivity and lower covering can be obtained.
On the other hand, the addition of the bromide salt solution is preferably performed outside 50% of the particle volume, more preferably outside 70%.

  Distribution of bromide or iodide ion concentration in the depth direction in the grain is measured by etching / TOF-SIMS (Time of Flight-Secondary Ion Mass Spectrometry) method, for example, using TRIFT II type TOF-SIMS manufactured by Phi Evans. it can. The TOF-SIMS method is specifically described in “Surface Analysis Technology Selection Secondary Ion Mass Spectrometry” Maruzen Co., Ltd. (1999), edited by the Surface Science Society of Japan. When the emulsion grains are analyzed by the etching / TOF-SIMS method, it is possible to analyze that iodide ions ooze out toward the grain surface even when the addition of the iodide salt solution is finished inside the grains. The emulsion of the present invention is analyzed by etching / TOF-SIMS method, and it is preferable that iodide ions have a maximum concentration on the grain surface, and the iodide ion concentration is attenuated toward the inside. It is preferable to have a concentration maximum inside. The local concentration of silver bromide can also be measured by X-ray diffraction if the silver bromide content is somewhat high.

  The silver halide emulsion used in the present invention preferably contains iridium. As the iridium compound, a 6-coordination complex having 6 ligands and having iridium as a central metal is preferable because it can be uniformly incorporated into a silver halide crystal. As one preferred embodiment of the iridium used in the present invention, a hexacoordinate complex having Ir as a central metal having Cl, Br or I as a ligand is preferred, and Ir comprising all six ligands consisting of Cl, Br or I is preferred. A hexacoordinate complex as a central metal is more preferable. In this case, Cl, Br, or I may be mixed in the hexacoordinate complex. It is particularly preferable that a hexacoordinate complex having Ir as a central metal having Cl, Br, or I as a ligand is contained in a silver bromide-containing phase in order to obtain a high gradation at high illumination exposure.

Specific examples of the 6-coordination complex in which all six ligands are composed of Cl, Br or I and having Ir as a central metal are given below, but iridium in the present invention is not limited to these.
[IrCl ₆ ] ^2-
[IrCl ₆ ] ^3-
[IrBr ₆ ] ^2-
[IrBr ₆ ] ^3-
[IrI ₆ ] ^3-

As a different preferred embodiment of iridium used in the present invention, a hexacoordination complex having at least one ligand other than halogen or cyan as a central metal is preferable, and H ₂ O, OH, O, OCN, thiazole or substituted thiazole is preferable. Preferred is a hexacoordination complex having Ir as a central metal and having at least one H ₂ O, OH, O, OCN, thiazole or substituted thiazole as a ligand and the remaining ligands from Cl, Br or I A hexacoordinate complex having Ir as a central metal is more preferable.

Specific examples of 6-coordination complexes having at least one H ₂ O, OH, O, OCN, thiazole or substituted thiazole as a ligand and the remaining ligand consisting of Cl, Br or I as a central metal The iridium in the present invention is not limited to these.

[IrCl ₅ (H ₂ O)] ^2-
[IrCl ₄ (H ₂ O) ₂ ] ^-
[IrCl ₅ (H ₂ O)] ^-
[IrCl ₄ (H ₂ O) ₂ ] ⁰
[IrCl ₅ (OH)] ^3-
[IrCl ₄ (OH) ₂ ] ^2-
[IrCl ₅ (OH)] ^2-
[IrCl ₄ (OH) ₂ ] ^2-
[IrCl ₅ (O)] ^4-
[IrCl ₄ (O) ₂ ] ^5-
[IrCl ₅ (O)] ^3-
[IrCl ₄ (O) ₂ ] ^4-
[IrBr ₅ (H ₂ O)] ^2-
[IrBr ₄ (H ₂ O) ₂ ] ^-
[IrBr ₅ (H ₂ O)] ^-
[IrBr ₄ (H ₂ O) ₂ ] ⁰
[IrBr ₅ (OH)] ^3-
[IrBr ₄ (OH) ₂ ] ^2-
[IrBr ₅ (OH)] ^2-
[IrBr ₄ (OH) ₂ ] ^2-
[IrBr ₅ (O)] ^4-
[IrBr ₄ (O) ₂ ] ^5-
[IrBr ₅ (O)] ^3-
[IrBr ₄ (O) ₂ ] ^4-
[IrCl ₅ (OCN)] ^3-
[IrBr ₅ (OCN)] ^3-
[IrCl ₅ (thiazole)] ^2-
[IrCl ₄ (thiazole) ₂ ] ^-
[IrCl ₃ (thiazole) ₃ ] ⁰
[IrBr ₅ (thiazole)] ^2-
[IrBr ₄ (thiazole) ₂ ] ^-
[IrBr ₃ (thiazole) ₃ ] ⁰
[IrCl ₅ (5-methylthiazole)] ^2-
[IrCl ₄ (5-methylthiazole) ₂ ] ^-
[IrBr ₅ (5-methylthiazole)] ^2-
[IrBr ₄ (5-methylthiazole) ₂ ] ^-
[IrCl ₅ (5-chlorothiazole)] ^2-
[IrCl ₄ (5-chlorothiazole) ₂ ] ^-
[IrBr ₅ (5-chlorothiazole)] ^2-
[IrBr ₄ (5-chlorothiazole) ₂ ] ^-

The metal complex mentioned above is an anion, and when a salt is formed with a cation, the metal complex that is easily dissolved in water as the counter cation is preferable. Specifically, alkali metal ions such as sodium ion, potassium ion, rubidium ion, cesium ion and lithium ion, ammonium ion and alkylammonium ion are preferable. In addition to water, these metal complexes should be dissolved in a mixed solvent with an appropriate organic solvent (for example, alcohols, ethers, glycols, ketones, esters, amides, etc.) that can be mixed with water. Can do. These iridium complexes are preferably added in an amount of 1 × 10 ⁻¹⁰ mol to 1 × 10 ⁻³ mol per mol of silver during grain formation, and 1 × 10 ⁻⁸ mol to 1 × 10 ⁻⁵ mol is preferably added. Most preferred.

  In the present invention, the above-mentioned iridium complex is added directly to the reaction solution at the time of silver halide grain formation, added to an aqueous halide solution for forming silver halide grains, or to other solutions to form grains. It is preferably incorporated into the silver halide grains by adding to the reaction solution. It is also preferable to physically ripen the fine particles in which the iridium complex is previously incorporated in the grains and to incorporate them in the silver halide grains. Further, these methods can be combined and contained in the silver halide grains.

  When these complexes are incorporated into silver halide grains, they can be uniformly present inside the grains, but they are disclosed in JP-A-4-208936, JP-A-2-125245, and JP-A-3-188437. As described above, it is also preferable to be present only in the particle surface layer, and it is also preferable to add a layer containing only the complex inside the particle and not containing the complex on the particle surface. Further, as disclosed in US Pat. Nos. 5,252,451 and 5,256,530, physical ripening is performed with fine particles in which the complex is incorporated in the particles to modify the particle surface phase. It is also preferable. Further, these methods can be used in combination, and a plurality of types of complexes may be incorporated in one silver halide grain. The halogen composition at the position where the above complex is contained is not particularly limited, but the hexacoordinate complex having Ir as the central metal, in which all six ligands are Cl, Br or I, has a silver bromide concentration maximum. It is preferable to contain.

  In the present invention, it is preferable to contain a rhodium compound. More preferably, a compound represented by the following general formula (VI) is used.

Formula (VI)
[RhQnL ^I _(6-n) ] ^m
In the general formula (VI), Q represents a halogen atom of chlorine, bromine or iodine, preferably a bromine atom. L ^I represents any ligand different from Br, n represents 3, 4, 5 or 6 and m preferably represents 3-, 2-, 1-, 0 or 1+. L ^I may be an organic compound be an inorganic compound, or may be even without electricity have an electric charge, but is preferably an inorganic compound. L ^I is preferably Cl, H ₂ O, NO or NS, more preferably H ₂ O. n is preferably 5 or 6, and 6 is more preferable. m is preferably 3- or 2-, and 3- is preferred.

Although the preferable specific example of a metal complex represented with general formula (VI) below is given, this invention is not limited to these.
[RhBr ₅ Cl] ^3-
[RhBr ₆ ] ^3-
[RhBr ₅ (H ₂ O)] ^2-
[RhBr ₄ (H ₂ O) ₂ ] ⁻

  When the metal complex represented by the general formula (VI) is an anion, it is preferable that when a salt is formed with a cation, it is easily dissolved in water as a counter cation. Specifically, alkali metal ions such as sodium ion, potassium ion, rubidium ion, cesium ion and ruthenium ion, ammonium ion and alkylammonium ion are preferable. These metal complexes are used by being dissolved in a mixed solvent with water or an appropriate organic solvent (for example, alcohols, ethers, glycols, ketones, esters, amides, etc.) that can be mixed with water. be able to.

The optimum amount of these metal complexes may vary depending on the size of the silver halide grains to be contained, but it is preferable to use 5 × 10 ⁻¹⁰ moles to 1 × 10 ⁻⁷ moles per mole of silver during grain formation. More preferably, 2 × 10 ⁻¹⁰ mol to 8 × 10 ⁻⁸ mol, particularly preferably 5 × 10 ⁻¹⁰ mol to 5 × 10 ⁻⁸ mol are used.

  In the present invention, in addition to iridium and rhodium, other metal ions can be doped inside and / or on the surface of silver halide grains. As a metal ion to be used, a transition metal ion is preferable, and iron, ruthenium, osmium, lead, cadmium, or zinc is particularly preferable. Further, these metal ions are more preferably used as a hexacoordinate octahedral complex with a ligand. When an inorganic compound is used as a ligand, cyanide ion, halide ion, thiocyan, hydroxide ion, peroxide ion, azide ion, nitrite ion, water, ammonia, nitrosyl ion, or thiol It is preferable to use a nitrosyl ion, and it is also preferable to use it in coordination with any of the above metal ions of iron, ruthenium, osmium, lead, cadmium, or zinc, and a plurality of kinds of ligands are contained in one complex molecule. It is also preferable to use it. An organic compound can also be used as the ligand, and preferred organic compounds include a chain compound having 5 or less carbon atoms in the main chain and / or a 5-membered or 6-membered heterocyclic compound. . More preferable organic compounds are compounds having a nitrogen atom, a phosphorus atom, an oxygen atom or a sulfur atom in the molecule as a coordination atom to the metal, particularly preferably furan, thiophene, oxazole, isoxazole, thiazole, isothiazole. , Imidazole, pyrazole, triazole, furazane, pyran, pyridine, pyridazine, pyrimidine, and pyrazine, and compounds in which these compounds are used as a basic skeleton and substituents are introduced into them are also preferable.

A combination of metal ions and ligands is preferably a combination of iron ions, ruthenium ions and cyanide ions. In the present invention, it is preferable to use iridium and these compounds in combination. In these compounds, the cyanide ion preferably accounts for a majority of the coordination number to iron or ruthenium as the central metal, and the remaining coordination sites are thiocyanate, ammonia, water, nitrosyl ion, dimethyl sulfoxide, pyridine, It is preferably occupied by pyrazine or 4,4′-bipyridine. Most preferably, all six coordination sites of the central metal are occupied by cyanide ions to form a hexacyanoiron complex or a hexacyanoruthenium complex. These complexes containing cyanide ions as ligands are preferably added in an amount of 1 × 10 ⁻⁸ mol to 1 × 10 ⁻² mol per mol of silver during grain formation, and 1 × 10 ⁻⁶ mol to 5 × 10 5 mol. It is most preferable to add ^-4 mol. When ruthenium and osmium are used as the central metals, it is also preferable to use nitrosyl ions, thionitrosyl ions, or water molecules and chloride ions together as ligands. More preferably, a pentachloronitrosyl complex, a pentachlorothionitrosyl complex, or a pentachloroaqua complex is formed, and a hexachloro complex is also preferably formed. These complexes are preferably added in an amount of 1 × 10 ⁻¹⁰ mol to 1 × 10 ⁻⁶ mol, more preferably 1 × 10 ⁻⁹ mol to 1 × 10 ⁻⁶ mol, per mol of silver during grain formation. That is.

  In the photosensitive silver halide emulsion used in the present invention, examples of spectral sensitizing dyes used for spectral sensitization in the green and red regions include, for example, Heterocyclic compounds-Cyanine dyes and related compounds (John Wiley & Sons [New] York, London] (published in 1964). As specific examples of compounds and spectral sensitization, those described in JP-A-62-215272, page 22, right upper column to page 38 are preferably used. In particular, as a red-sensitive spectral sensitizing dye for silver halide emulsion grains having a high silver chloride content, the spectral sensitizing dye described in JP-A-3-123340 is stable, the strength of adsorption, and the exposure temperature. This is very preferable from the viewpoint of dependency and the like.

  The silver halide emulsion used in the present invention is preferably subjected to gold sensitization known in the art. For gold sensitization, various inorganic gold compounds, gold (I) complexes having inorganic ligands, and gold (I) compounds having organic ligands can be used. Examples of the inorganic gold compound include chloroauric acid or a salt thereof, and a gold (I) complex having an inorganic ligand, for example, a gold dithiocyanate such as gold (I) potassium dithiocyanate or gold (I) 3 dithiosulfate. Compounds such as gold dithiosulfate compounds such as sodium can be used.

In addition to gold sensitization, chalcogen sensitization can be performed with the same molecule, and molecules capable of releasing AuCh ⁻ can be used. Here, Au represents Au (I), and Ch represents a sulfur atom, a selenium atom, or a tellurium atom. Examples of the molecule capable of releasing AuCh ⁻ include a gold compound represented by AuCh-L. Here, L represents an atomic group constituting a molecule by bonding with AuCh. Further, one or more ligands may be coordinated with Au together with Ch-L. In addition, the gold compound represented by AuCh-L, when reacted in a solvent in the presence of silver ions, easily produces AgAuS when Ch is S, AgAuSe when Ch is Se, and AgAuTe when Ch is Te It is what has. Examples of such a compound include those in which L is an acyl group, and other examples include compounds represented by the following formula (AuCh1), formula (AuCh2), and formula (AuCh3).

Formula (AuCh1) R ₁ -X-M-ChAu
Here, Au represents Au (I), Ch represents a sulfur atom, selenium atom, tellurium atom, M represents a substituted or unsubstituted methylene group, X represents an oxygen atom, sulfur atom, selenium atom, NR ₂ R ₁ represents an atomic group (for example, an organic group such as an alkyl group, an aryl group, and a heterocyclic group) that forms a molecule by binding to X, and R ₂ represents a hydrogen atom and a substituent (for example, Represents an organic group such as an alkyl group, an aryl group, and a heterocyclic group. R ₁ and M may be bonded to each other to form a ring.
In the compound represented by the formula (AuCh1), those in which Ch is a sulfur atom and a selenium atom are preferable, X is preferably an oxygen atom and a sulfur atom, and R ₁ is preferably an alkyl group or an aryl group. Examples of more specific compounds include Au (I) salts of thiosugars (gold thioglucose such as α-gold thioglucose, gold peracetylthioglucose, gold thiomannose, gold thiogalactose, and gold thioarabinose), seleno Au (I) salts of sugars (gold peracetylselenoglucose, gold peracetylselenomannose, etc.), Au (I) salts of tellurosugar, and the like. Here, thio sugar, seleno sugar, and telluro sugar represent compounds in which the anomeric hydroxyl group of the sugar is replaced with an SH group, a SeH group, and a TeH group, respectively.

Formula (AuCh2) W ₁ W ₂ C = CR ₃ ChAu
Here, Au represents Au (I), Ch represents a sulfur atom, a selenium atom, or a tellurium atom, and R ₃ and W ₂ are substituents (for example, a hydrogen atom, a halogen atom, an alkyl group, an aryl group) W ₁ represents an electron-withdrawing group having a positive Hammett's substituent constant σp value. R ₃ and W ₁ , R ₃ and W ₂ , W ₁ and W ₂ may be bonded to each other to form a ring.
In the compound represented by the formula (AuCh2), those in which Ch is a sulfur atom and a selenium atom are preferable, R ₃ is preferably a hydrogen atom and an alkyl group, and W ₁ and W ₂ are Hammett's substituent constants σp value Is preferably an electron withdrawing group. More specific examples of the compound include (NC) ₂ C═CHSAu, (CH ₃ OCO) ₂ C═CHSAu, CH ₃ CO (CH ₃ OCO) C═CHSAu, and the like.

Formula (AuCh3) W ₃ -E-ChAu
Here, Au represents Au (I), Ch represents a sulfur atom, a selenium atom, and a tellurium atom, E represents a substituted or unsubstituted ethylene group, and W ₃ represents a positive Hammett substituent constant σp value. The value represents an electron-withdrawing group.
In the compound represented by the formula (AuCh3), Ch is preferably a sulfur atom and a selenium atom, and E is an ethylene group having an electron-withdrawing group having a positive Hammett's substituent constant σp value. W ₃ is preferably an electron-withdrawing group having a Hammett's substituent constant σp value of 0.2 or more. The amount of these compounds added may vary widely depending on the case, but is 5 × 10 ^{−7 to} 5 × 10 ⁻³ mol, preferably 3 × 10 ^{−6 to} 3 × 10 ⁻⁴ mol, per mol of silver halide. is there.

  Colloidal gold sulfide can also be used, and the manufacturing method thereof is Research Disclosure (37154), Solid State Ionics 79, 60-66, 1995, Compt. Rend.Hebt.Seances Acad.Sci.Sect.B, 263, 1328, published in 1966. The Research Disclosure describes a method using a thiocyanate ion in the production of colloidal gold sulfide, but a thioether compound such as methionine or thiodiethanol can be used instead.

Various sizes of colloidal gold sulfide can be used, those having an average particle size of 50 nm or less are preferred, average particle size of 10 nm or less is more preferred, and average particle size of 3 nm or less is even more preferred. This particle size can be measured from a TEM photograph. The composition of the colloidal gold sulfide may also Au ₂ S _1, may be of Au ₂ S ₁ ~Au ₂ S ₂ in such sulfur excess composition, sulfur excess composition is preferred. Au ₂ S _1.1 ~Au ₂ S _1.8 is more preferred.

The composition analysis of the colloidal gold sulfide can be obtained, for example, by taking out gold sulfide particles and determining the gold content and sulfur content by using an analysis method such as ICP or iodometry, respectively. If gold ions and sulfur ions (including hydrogen sulfide and its salts) dissolved in the liquid phase are present in the gold sulfide colloid, the composition analysis of the gold sulfide colloid particles will be affected. The analysis is performed after separation. The amount of colloidal gold sulfide may vary widely depending on the case, but 5 × 10 ^{−7 to} 5 × 10 ⁻³ mol, preferably 5 × 10 ^{−6 to} 5 × 10 ⁻ as gold atoms per mol of silver halide. ⁴ moles.

  In the present invention, the above gold sensitization may be combined with other sensitization methods such as sulfur sensitization, selenium sensitization, tellurium sensitization, reduction sensitization or noble metal sensitization using other than gold compounds. . It is particularly preferable to combine with sulfur sensitization and selenium sensitization.

In the present invention, a surfactant can be added to the photosensitive material from the viewpoints of improving the coating stability of the photosensitive material, preventing the generation of static electricity, and adjusting the charge amount. Examples of the surfactant include an anionic surfactant, a cationic surfactant, a betaine surfactant, and a nonionic surfactant, and examples thereof include those described in JP-A-5-333492. The surfactant used in the present invention is preferably a fluorine atom-containing surfactant. In particular, a fluorine atom-containing surfactant can be preferably used. These fluorine atom-containing surfactants may be used alone or in combination with other conventionally known surfactants, but are preferably used in combination with other conventionally known surfactants. The amount of these surfactants added to the light-sensitive material is not particularly limited, but is generally 1 × 10 ^{−5 to} 1 g / m ² , preferably 1 × 10 ⁻⁴ to 1 × 10 ^{−. 1} g / m ² , more preferably 1 × 10 ⁻³ to 1 × 10 ⁻² g / m ² .

  In addition, the photosensitive material used in the present invention includes various color couplers, polymer couplers, photographically useful group releasing couplers described in the table of paragraph 0100 of JP-A No. 2001-183778 or paragraphs 0101 to 0119, Known additives such as an oxidized developer scavenger, an anti-stain agent, an anti-fading agent, dyes, and an ultraviolet absorber can be contained.

  The photosensitive material used in the present invention can form an image by an exposure process in which light is irradiated according to image information and a development process in which the photosensitive material irradiated with light is developed.

  Photosensitive materials are monochromatic high-density light such as gas lasers, light-emitting diodes, semiconductor lasers, semiconductor lasers, or second harmonic light-emitting light sources (SHG) that combine nonlinear optical crystals with solid-state lasers that use semiconductor lasers as excitation light sources. The digital scanning exposure method used is preferably used. In order to make the system compact and inexpensive, it is preferable to use a second harmonic generation light source (SHG) that combines a semiconductor laser, a semiconductor laser, or a solid-state laser and a nonlinear optical crystal. In particular, in order to design a compact, inexpensive, long-life and high-stability device, it is preferable to use a semiconductor laser, and at least one of the exposure light sources is preferably a semiconductor laser.

  The photosensitive material is preferably imagewise exposed with coherent light of a blue laser having an emission wavelength of 420 nm to 460 nm. Among blue lasers, it is particularly preferable to use a blue semiconductor laser.

Specifically, as a laser light source, a blue semiconductor laser having a wavelength of 430 to 450 nm (announced by Nichia Chemical Co., Ltd. at the 48th Applied Physics Related Conference in March 2001), a semiconductor laser (oscillation wavelength: About 470 nm of blue laser and semiconductor laser (oscillation wavelength: about 1060 nm) extracted by wavelength conversion of LiNbO ₃ SHG crystal having a waveguide inversion domain structure and having a waveguide inversion domain structure A green laser with a wavelength of about 530 nm, a red semiconductor laser with a wavelength of about 685 nm (Hitachi type No. HL6738MG), a red semiconductor laser with a wavelength of about 650 nm (Hitachi type No. HL6501MG), etc., extracted by converting the wavelength with an SHG crystal of LiNbO ₃ is preferable. Used.

When such a scanning exposure light source is used, the spectral sensitivity maximum wavelength of the photosensitive material of the present invention can be arbitrarily set according to the wavelength of the scanning exposure light source to be used. In a solid laser using a semiconductor laser as an excitation light source or an SHG light source obtained by combining a semiconductor laser and a nonlinear optical crystal, the oscillation wavelength of the laser can be halved, so that blue light and green light can be obtained. Therefore, the spectral sensitivity maximum of the photosensitive material can be given to the usual three wavelength regions of blue, green, and red. When the exposure time in such scanning exposure is defined as the time for exposing the pixel size when the pixel density is 300 dpi, the preferable exposure time is 1 × 10 ⁻⁴ seconds or less, more preferably 1 × 10 ⁻⁶ seconds. It is as follows.

  The silver halide color photographic light-sensitive material used in the present invention can be preferably used in combination with the exposure and development systems described in the following known documents. Examples of the developing system include an automatic printing and developing system described in JP-A-10-333253, a photosensitive material conveying apparatus described in JP-A-2000-10206, and an image reading apparatus described in JP-A-11-215312. , An exposure system comprising a color image recording system described in JP-A-11-88619 and JP-A-10-202950, and a digital photo print including a remote diagnosis system described in JP-A-10-210206 And a photo print system including an image recording apparatus described in JP 2000-310822 A.

  Preferred scanning exposure methods applicable to the present invention are described in detail in the patents listed in the table above.

EXAMPLES Hereinafter, although an Example demonstrates this invention more concretely, these do not limit the scope of the present invention at all.
(Preparation of color developer replenisher concentrated composition)
Color development replenisher concentrated composition samples # 1 to # 6 having the compositions shown in Table 3 were prepared. In addition, the quantity in a table | surface is a prescription value per 1L of compositions. Also, CBS, DSHA, PTS. Na, TIPA, DEG, PEG300 are m-carboxybenzenesulfinic acid, disodium-N, N-bis (sulfonate ethyl) hydroxylamine, sodium p-toluenesulfonate, triisopropanolamine, diethylene glycol, polyethylene glycol average molecular weight, respectively. 300, and the developing agent is 4-amino-3-methyl-N-ethyl-N- (β-methanesulfonamidoethyl) aniline, 3/2 sulfate, monohydrate.

(Evaluation of concentrated composition)
The prepared concentrated composition samples # 1 to # 6 were subjected to the following evaluation tests on the stability of the concentrated composition, the creep-suppressing property of the development replenisher, photographic properties, and edge penetration.

<Precipitation of concentrated composition>
400 mL of each sample was prepared, put into 200 mL of a 200 mL transparent PVC bottle, capped, and stored at 0 ° C. and −5 ° C. for 2 weeks. The sample was taken out after 2 weeks, and the presence or absence of precipitates and the liquid turbidity were visually observed. The results are shown in Table 4.

<Development replenisher creep-up deterrence>
260 mL of each of the above concentrated composition samples # 1 to # 6 was diluted with water to make 1 L (3.84 times dilution) developer replenisher. 1L of each replenisher solution is placed in a rigid vinyl chloride resin container with a 10cm x 10cm inner bottom and 15cm height, and 9.7mm x 9.7mm and 3mm thick foam vinyl chloride on the liquid surface. Floating lid made of resin to reduce the opening area. This is a simulation of a development replenishment tank. After storing in this state at room temperature (about 20 to 25 ° C.) for 2 weeks, the presence or absence of precipitate around the floating lid after storage was visually observed. The results are also shown in Table 4.

<Photogenicity>
1. Preparation of photosensitive material sample The photosensitive material used for the continuous processing test was prepared as follows.
(Preparation of blue-sensitive layer emulsion BH-1)
High silver chloride cubic particles were prepared by a method in which silver nitrate and sodium chloride were simultaneously added to and mixed with deionized distilled water containing stirred deionized gelatin. In the course of this preparation, Cs ₂ [OsCl ₅ (NO)] was added from 60% to 80% addition of silver nitrate. Potassium bromide (1.5 mole percent per mole of finished silver halide) and K ₄ [Fe (CN) ₆ ] were added from the 80% to 90% addition of silver nitrate. K ₂ [IrCl ₆ ] was added from 83% to 88% addition of silver nitrate. K ₂ [IrCl ₅ (H ₂ O)] and K [IrCl ₄ (H ₂ O) ₂ ] were added from 92% to 98% addition of silver nitrate. When 94% of the addition of silver nitrate was completed, potassium iodide (0.27 mol% per mol of the finished silver halide) was added with vigorous stirring. The obtained emulsion grains were monodispersed cubic silver iodobromochloride grains having a side length of 0.54 μm and a coefficient of variation of 8.5%. This emulsion was subjected to precipitation desalting treatment, and gelatin, compounds Ab-1, Ab-2, Ab-3, and calcium nitrate were added thereto and redispersed.

The redispersed emulsion was dissolved at 40 ° C., and sensitizing dye S-1, sensitizing dye S-2, and sensitizing dye S-3 of the present invention were added so as to optimize spectral sensitization. Next, sodium benzenethiosulfate, triethylthiourea as a sulfur sensitizer, and compound-1 as a gold sensitizer were added and ripened so as to optimize chemical sensitization. Thereafter, 1- (5-methylureidophenyl) -5-mercaptotetrazole, compound-2, compound having repeating unit 2 or 3 represented by compound-3 as a main component (terminal X ₁ and X ₂ are hydroxyl groups), Compound -4 and potassium bromide were added to complete the chemical sensitization. The emulsion thus obtained was designated as Emulsion BH-1.

(Preparation of blue-sensitive layer emulsion BL-1)
In preparation of emulsion BH-1, the temperature and the addition speed of the step of adding and mixing silver nitrate and sodium chloride at the same time were changed, and the amounts of various metal complexes added during the addition of silver nitrate and sodium chloride were changed. Thus, emulsion grains were obtained. The emulsion grains were monodispersed cubic silver iodobromochloride grains having a side length of 0.44 μm and a coefficient of variation of 9.5%. After redispersing this emulsion, Emulsion BL-1 was prepared in the same manner except that the amount of various compounds added was changed from that of BH-1.

(Preparation of green sensitive layer emulsion GH-1)
High silver chloride cubic particles were prepared by a method in which silver nitrate and sodium chloride were simultaneously added to and mixed with deionized distilled water containing stirred deionized gelatin. In the course of this preparation, K ₄ [Ru (CN) ₆ ] was added from 80% to 90% addition of silver nitrate. Potassium bromide (2 mol% per mole of finished silver halide) was added from the point where the addition of silver nitrate was 80% to 100%. K ₂ [IrCl ₆ ] and K ₂ [RhBr ₅ (H ₂ O)] were added from 83% to 88% addition of silver nitrate. When 90% of the addition of silver nitrate was completed, potassium iodide (0.1 mol% per mol of the finished silver halide) was added with vigorous stirring. Further, K ₂ [IrCl ₅ (H ₂ O)] and K [IrCl ₄ (H ₂ O) ₂ ] were added when the addition of silver nitrate was 92% to 98%. The obtained emulsion grains were monodispersed cubic silver iodobromochloride grains having a side length of 0.42 μm and a coefficient of variation of 8.0%. This emulsion was subjected to precipitation desalting and redispersion in the same manner as described above.

  This emulsion was dissolved at 40 ° C. and sodium benzenethiosulfate, p-glutaramide phenyl disulfide, sodium thiosulfate pentahydrate as a sulfur sensitizer and (bis (1,4,5-trimethyl-1) as a gold sensitizer. , 2,4-triazolium-3-thiolate) orate (I) tetrafluoroborate) and ripened to optimize chemical sensitization. Thereafter, 1- (3-acetamidophenyl) -5-mercaptotetrazole, 1- (5-methylureidophenyl) -5-mercaptotetrazole, compound-2, compound-4 and potassium bromide were added. Furthermore, spectral sensitization was performed by adding sensitizing dyes S-4, S-5, S-6 and S-7 as sensitizing dyes during the emulsion preparation process. The emulsion thus obtained was designated as Emulsion GH-1.

(Preparation of green-sensitive layer emulsion GL-1)
In preparation of Emulsion GH-1, the temperature and rate of addition of silver nitrate and sodium chloride are added and mixed, and the amount of various metal complexes added during the addition of silver nitrate and sodium chloride is changed. Thus, emulsion grains were obtained. The emulsion grains were monodispersed cubic silver iodobromochloride grains having a side length of 0.35 μm and a coefficient of variation of 9.8%. After redispersing this emulsion, Emulsion GL-1 was similarly prepared except that the amount of various compounds added was changed from that of Emulsion GH-1.

(Preparation of emulsion RH-1 for red-sensitive layer)
High silver chloride cubic particles were prepared by a method in which silver nitrate and sodium chloride were simultaneously added to and mixed with deionized distilled water containing stirred deionized gelatin. In the course of this preparation, Cs ₂ [OsCl ₅ (NO)] was added from 60% to 80% addition of silver nitrate. K ₄ [Ru (CN) ₆ ] was added from the time when the addition of silver nitrate was 80% to 90%. Potassium bromide (1.3 mol% per mol of finished silver halide) was added from the 80% to 100% addition of silver nitrate. K ₂ [IrCl ₅ (5-methylthiazole)] was added from 83% to 88% when silver nitrate was added. When the addition of silver nitrate was completed 88%, potassium iodide (amount of silver iodide to be 0.05 mol% per mol of finished silver halide) was added with vigorous stirring. Further, K ₂ [IrCl ₅ (H ₂ O)] and K [IrCl ₄ (H ₂ O) ₂ ] were added when the addition of silver nitrate was 92% to 98%. The obtained emulsion grains were monodispersed cubic silver iodobromochloride emulsion grains having a cube side length of 0.39 μm and a coefficient of variation of 10%. The obtained emulsion was subjected to precipitation desalting and redispersion in the same manner as described above.

  This emulsion is dissolved at 40 ° C., and sensitizing dye S-8, compound-5, triethylthiourea as sulfur sensitizer and compound-1 as gold sensitizer are added to optimize chemical sensitization. Aged. Thereafter, 1- (3-acetamidophenyl) -5-mercaptotetrazole, 1- (5-methylureidophenyl) -5-mercaptotetrazole, compound-2, compound-4, and potassium bromide were added. The emulsion thus obtained was designated as Emulsion RH-1.

(Preparation of emulsion RL-1 for red-sensitive layer)
In preparation of emulsion RH-1, the temperature and rate of addition of silver nitrate and sodium chloride are added and mixed, and the amounts of various metal complexes added during the addition of silver nitrate and sodium chloride are changed. Thus, emulsion grains were obtained. The emulsion grains were monodispersed cubic silver iodobromochloride grains having a side length of 0.29 μm and a coefficient of variation of 9.9%. Emulsion RL-1 was prepared in the same manner except that the amount of various compounds added was changed from that of Emulsion RH-1 after precipitation desalting treatment and maximum dispersion.

Preparation of first layer coating solution 34 g of yellow coupler (Ex-Y), 1 g of color image stabilizer (Cpd-1), 1 g of color image stabilizer (Cpd-2), 8 g of color image stabilizer (Cpd-8), color image 1 g of stabilizer (Cpd-18), 2 g of color image stabilizer (Cpd-19), 15 g of color image stabilizer (Cpd-20), 1 g of color image stabilizer (Cpd-21), color image stabilizer (Cpd-23) 15 g, 0.1 g of additive (ExC-1), 1 g of color image stabilizer (UV-A) 23 g of solvent (Solv-4), 4 g of solvent (Solv-6), 23 g of solvent (Solv-9) and acetic acid Dissolve in 60 ml of ethyl, and emulsify and disperse this liquid in 270 g of a 20% by weight gelatin aqueous solution containing 4 g of sodium dodecylbenzenesulfonate using a high-speed stirring emulsifier (dissolver), and add 900 g of emulsion dispersion A by adding water. did.
On the other hand, the emulsified dispersion A and the emulsions BH-1 and BL-1 were mixed and dissolved to prepare a first layer coating solution having a composition described later. The emulsion coating amount indicates the silver coating amount.

Preparation of coating solution for second layer to seventh layer The coating solution for second layer to seventh layer was prepared in the same manner as the coating solution for first layer. (H-1), (H-2), and (H-3) were used as gelatin hardeners for each layer. Also, Ab-1 to each layer, Ab-2, Ab-3 , and Ab-4 the total amount respectively ^{14.0mg / m 2, 62.0mg / m} 2, 5.0mg / m 2 and 10.0 mg / m It added so that it might become ² .

1- (3-methyl) -5-mercaptotetrazole, the second layer, the fourth layer, and the sixth layer, respectively ^{0.2mg / m 2, 0.2mg / m} 2, 0.6mg / m 2 It added so that it might become. 4-Hydroxy-6-methyl-1,3,3a, 7-tetrazaindene is added to the blue-sensitive emulsion layer and the green-sensitive emulsion layer in an amount of 1 × 10 ⁻⁴ mol and 2 ×, respectively, per mol of silver halide. 10 ^-4 mol was added. 0.05 g / m ² of copolymer latex of methacrylic acid and butyl acrylate (mass ratio 1: 1, average molecular weight 200,000 to 400,000) was added to the red sensitive emulsion layer. The second layer, was added the fourth layer and the sixth layer in disodium catechol-3,5-disulfonate as respectively a ^{6mg / m 2, 6mg / m} 2, 18mg / m 2. Sodium polystyrene sulfonate was added to each layer as necessary to adjust the viscosity of the coating solution. In order to prevent irradiation, the following dyes were added (the amount in parentheses represents the coating amount).

(Layer structure)
The structure of each layer is shown below. The numbers represent the coating amount (g / m ² ). The silver halide emulsion represents a coating amount in terms of silver.
Support Polyethylene resin-laminated paper [White pigment (TiO ₂ ; content: 16% by mass, ZnO; content: 4% by mass), polyethylene brightening agent (4,4′-bis (5- Methylbenzoxazolyl) stilbene (content 0.03% by mass) and bluish dye (ultraviolet, content 0.33% by mass) .The amount of polyethylene resin is 29.2 g / m ² ]
First layer (blue photosensitive emulsion layer)
Emulsion (5: 5 mixture of BH-1 and BL-1 (silver molar ratio 0.16
Gelatin 1.35
Yellow coupler (Ex-Y) 0.36
Color image stabilizer (Cpd-1) 0.01
Color image stabilizer (Cpd-2) 0.01
Color image stabilizer (Cpd-8) 0.08
Color image stabilizer (Cpd-18) 0.01
Color image stabilizer (Cpd-19) 0.02
Color image stabilizer (Cpd-20) 0.15
Color image stabilizer (Cpd-21) 0.01
Color image stabilizer (Cpd-23) 0.15
Additive (ExC-1) 0.002
Color image stabilizer (UV-A) 0.01
Solvent (Solv-4) 0.23
Solvent (Solv-6) 0.04
Solvent (Solv-9) 0.23

Second layer (color mixing prevention layer)
Gelatin 0.80
Color mixing inhibitor (Cpd-4) 0.05
Color mixing inhibitor (Cpd-12) 0.01
Color image stabilizer (Cpd-3) 0.01
Color image stabilizer (Cpd-5) 0.006
Color image stabilizer (Cpd-6) 0.05
Color image stabilizer (UV-A) 0.06
Color image stabilizer (Cpd-7) 0.006
Solvent (Solv-1) 0.06
Solvent (Solv-2) 0.06
Solvent (Solv-5) 0.07
Solvent (Solv-8) 0.07

Third layer (green photosensitive emulsion layer)
Emulsion (1: 3 mixture of GH-1 and GL-1 (silver molar ratio)) 0.10
Gelatin 0.93
Magenta coupler (ExM) 0.12
UV absorber (UV-A) 0.03
Color image stabilizer (Cpd-2) 0.01
Color image stabilizer (Cpd-6) 0.08
Color image stabilizer (Cpd-7) 0.005
Color image stabilizer (Cpd-8) 0.01
Color image stabilizer (Cpd-9) 0.01
Color image stabilizer (Cpd-10) 0.005
Color image stabilizer (Cpd-11) 0.0001
Color image stabilizer (Cpd-20) 0.01
Solvent (Solv-3) 0.06
Solvent (Solv-4) 0.12
Solvent (Solv-6) 0.05
Solvent (Solv-9) 0.16

Fourth layer (color mixing prevention layer)
Gelatin 0.63
Color mixing inhibitor (Cpd-4) 0.04
Color mixing inhibitor (Cpd-12) 0.01
Color image stabilizer (Cpd-3) 0.01
Color image stabilizer (Cpd-5) 0.005
Color image stabilizer (Cpd-6) 0.04
Color image stabilizer (UV-A) 0.05
Color image stabilizer (Cpd-7) 0.005
Solvent (Solv-1) 0.05
Solvent (Solv-2) 0.05
Solvent (Solv-5) 0.06
Solvent (Solv-8) 0.06

5th layer (red photosensitive emulsion layer)
Emulsion (4: 6 mixture of RH-1 and RL-1 (silver molar ratio)) 0.10
Gelatin 1.12
Cyan coupler (ExC-1) 0.10
Cyan coupler (ExC-2) 0.02
Cyan coupler (ExC-3) 0.02
Color image stabilizer (Cpd-1) 0.03
Color image stabilizer (Cpd-7) 0.01
Color image stabilizer (Cpd-9) 0.04
Color image stabilizer (Cpd-10) 0.001
Color image stabilizer (Cpd-14) 0.001
Color image stabilizer (Cpd-15) 0.18
Color image stabilizer (Cpd-16) 0.002
Color image stabilizer (Cpd-17) 0.001
Color image stabilizer (Cpd-18) 0.05
Color image stabilizer (Cpd-19) 0.04
Color image stabilizer (UV-5) 0.10
Solvent (Solv-5) 0.19

Sixth layer (UV absorbing layer)
Gelatin 0.34
Ultraviolet absorber (UV-B) 0.24
Compound (S1-4) 0.0015
Solvent (Solv-7) 0.11

Seventh layer (protective layer)
Gelatin 0.80
Additive (Cpd-22) 0.03
Liquid paraffin 0.02
Surfactant (Cpd-13) 0.02

The sample prepared as described above was used.
2. Development processing Using the Fuji Photo Film minilab printer processor Frontier 330, the above samples were continuously processed until 3 times the amount of color developing tank solution was replenished (3 rounds) in the following processing steps and processing composition. It was. The above photosensitive material was printed with a standard negative so that the average visual density of the print would be 0.6, and was run with a processing amount of one round processing per week.

<Development processing conditions>
Processing process Temperature Time Replenishment amount Color development 38.5 ° C 45 seconds 45 ml / m ²
Bleach fixing 38.0 ° C. 25 seconds A agent 17.5 ml / m ²
Agent B 17.5 ml / m ²
Rinse (1) 38.0 ° C. 20 seconds −
Rinse (2) 38.0 ° C. 20 seconds −
Rinse (3) 38.0 ° C. 20 seconds −
Rinse (4) 38.0 ° C., 20 seconds, 175 ml / m ²
Drying 80 ° C 20 seconds * Replenishment amount per 1 m ^{2 of} photosensitive material ** Mount the rinse screening system RC50D manufactured by Fuji Photo Film Co., Ltd. on the rinse 3, take out the rinse solution from the rinse 3, and reverse osmosis module (RC50D) with a pump Send to. The permeated water sent in the tank is supplied to the rinse 4 and the concentrated solution is returned to the rinse 3. The pump pressure was adjusted so that the amount of permeated water to the reverse osmosis module was maintained at 50 to 300 mL / min, and the temperature was circulated for 10 hours per day. The rinsing was a 4-tank counterflow system from 1 to 4.

<Color developer>
Replenisher:
Separately, each of the color development concentrated compositions of Samples # 1 to # 6 prepared was diluted 3.84 times with water to prepare a color development replenisher. Tank liquid:
A developing tank solution was prepared by mixing 300 mL of each developer replenisher solution with 100 mL of CP-47L P1-S solution manufactured by Fuji Photo Film Co., Ltd. and 600 mL of water.

<Bleaching Fixer> Tank Solution Replenisher A Replenisher B
Water 650ml 300ml 300ml
Ammonium thiosulfate (750 g / l) 97.0 ml-376.0 ml
Ammonium bisulfite solution (65%) 50.0g-185.5g
Ethylenediaminetetraacetic acid iron (III) 30.0 g 94.0 g −
Ammonium ethylenediaminetetraacetic acid 3.0 g 2.0 g 10.0 g
m-carboxybenzenesulfinic acid 5.0 g 15.0 g −
Nitric acid 5.2g 25.0g-
Succinic acid-20.0 g-
Ammonia water (27%) 8.0 g 15.0 g 36.0 g
Add water 1000ml 1000ml 1000ml
pH (25 ° C./ammonia, nitric acid adjustment) 5.9 2.5 5.75

<Rinse> Tank solution and replenisher common chlorinated sodium isocyanurate 0.02g
Deionized water (conductivity 5μs / cm or less) 1000ml

The replenishers A and B for bleach-fixing were used by diluting parts A and B of the bleach-fixing concentrated composition 1.5 times each with water.
Moreover, in the frontier 330 used this time, when the color developing concentrated composition and the bleach-fixed concentrated composition parts A and B are set in a container for 1.3 liters each, the concentrated composition enters the replenishing tank fully automatically. It can be processed by diluting with water to the above dilution factor.

(Photographic evaluation: GL sensitivity)
Using the above-described color development concentrated compositions # 1 to # 6, three round running processes were performed in accordance with the above processing methods. Thereafter, the sample was subjected to a gray imagewise exposure, and the magenta density at the exposure amount at which the magenta density at # 1 was 0.6 was obtained, and the difference (ΔD (GL)) was calculated. Indicated. If this value is negative, it means that the sensitivity has decreased, and if it is positive, it means that the sensitivity has increased. A larger value is preferable because there is no decrease in sensitivity.
(Evaluation of edge dirt)
After evaluating the photographic properties of the above-described color development concentrated compositions # 1 to # 6, 20 unexposed samples were processed in L size, and the stains on the edges (the stains on the ridges on the four sides of the support) were visually observed. Table 3 shows the degree of occurrence of contamination.

  From this result, according to the present invention, the precipitation of the concentrated solution (especially the precipitation of the optical brightener) is improved, the crystal precipitation due to the replenishing solution is not deteriorated, and the sensitivity is lowered even if the concentration of the color developing agent is reduced. In addition, it is possible to provide a processing agent with improved photographic properties and no edge stains. Also, reducing the color developing agent concentration, PTS. By not using Na and TIPA, an inexpensive treatment agent can be supplied. Furthermore, when DEG and PEG300 were used in combination, the most preferable effect was obtained.

  A colored coloring composition was prepared in the same manner as in Example 1 except that PEG300 of # 6 was replaced with equimolar amounts of PEG200, PEG600, and PEG1000, and the precipitation property and creeping property were evaluated. The results were all good, but PEG 300 was most preferred, followed by PEG 200 and 600, and PEG 1000 was not very effective.

  For # 6 of Example 1, the pH was adjusted by changing the addition amount of KOH, and the evaluation was performed in the same manner as in Example 1 by changing the addition amount of the color developing agent and the addition amount of DSHA. As a result, it was confirmed that the above-described preferable addition amount of the present invention is more preferable. Further, when a concentrated solution was prepared in the same manner except that # 6 DSHA was replaced by equimolar amount with diethylhydroxylamine, precipitation occurred.

[Comparative example]
As for # 6 of Example 1, it was found that when TIPA was added at 30 g / L, the precipitation of the concentrated solution and the edge contamination were remarkably deteriorated, and the effects of the present invention could not be obtained.

About # 6 of Example 1, it processed similarly to Example 1 except having changed into the following process conditions using the frontier 340E by Fuji Photo Film Co., Ltd.
<Development processing conditions>
Processing process Temperature Time Replenishment amount Color development 45.0 ° C 25 seconds 45 ml / m ²
Bleach fixing 40.0 ° C 25 seconds A agent 17.5ml / m ²
Agent B 17.5 ml / m ²
Rinse (1) 40.0 ° C 7 seconds-
Rinse (2) 40.0 ° C 4 seconds-
Rinse (3) 40.0 ° C 4 seconds-
Rinse (4) 40.0 ° C. 7 seconds 175 ml / m ²
Drying at 80 ° C. for 20 seconds As a result, it was confirmed that good photographic performance was obtained and no edge smearing occurred.

Claims (5)

A one-part concentrated composition for a color development replenisher for a color photographic light-sensitive material, which satisfies the following compositional requirements.
(A) Contains 0.08 to 0.12 mol / L of p-phenylenediamine color developing agent.
(B) The substituted hydroxylamine derivative represented by the following general formula (I) is contained in an amount of 0.06 to 0.16 mol / L.

In the formula, L represents an alkylene group which may be substituted, A represents a carboxy group, a sulfo group, a phosphono group, a hydroxy group, an amino group which may be alkyl-substituted, and R represents a hydrogen atom or may be substituted. Represents an alkyl group.
(C) It contains 0.05 to 1.0 mol / L of ethylene glycol.
(D) The pH when diluted 3.84 times with water is 12.5 to 12.8.
(E) It contains substantially no alkanolamine.   2. The one-part concentrated composition for color development replenisher for a color photographic light-sensitive material according to claim 1, wherein the ethylene glycol is a combination of at least diethylene glycol and polyethylene glycol having a molecular weight of 200 to 600. The color developing replenisher 1 for a color photographic light-sensitive material according to claim 1, comprising 0.01 to 0.2 mol / L of a sulfinic acid compound represented by the following general formula (II): Part-type concentrated composition.
General formula (II) RSO ₂ M
In the formula, R represents an alkyl group, a cycloalkyl group, an alkenyl group, an alkynyl group, an aralkyl group or an aryl group. M represents a hydrogen atom or an alkali metal atom. The color photographic light-sensitive material according to any one of claims 1 to 3, which contains 1 to 50 mmol / L of a diaminostilbene derivative represented by the following general formula (III) and / or the following general formula (IV). A one-part concentrated composition for a color developer replenisher of the material.
General formula (III)

In the formula, R ₁₁ and R ₁₂ each independently represent a hydrogen atom or an alkyl group, R ₁₃ and R ₁₄ each independently represent a hydrogen atom, an alkyl group or an aryl group, and R ₁₅ represents at least one asymmetric carbon. An alkyl group having or a group represented by the following general formula (Ia), R ₁₆ represents an alkyl group having at least one asymmetric carbon or a group represented by the following general formula (Ib); M ₁ represents a hydrogen atom or an alkali metal atom. R ₁₃ and R ₁₅ , R ₁₄ and R ₁₆ may be bonded to each other to form a ring.
Formula (Ia)

In the formula, n ₁₁ represents an integer of 1 to 3.
Formula (Ib)

In the formula, n ₁₂ represents an integer of 2 to 4.

In the formula, Z ₁ and Z ₂ may be the same or different and each represents an amino group having 2 to 3 carbon atoms substituted with a hydroxy group or a sulfonic acid group. M represents a hydrogen atom or an alkali metal atom.   A halogenated composition comprising the one-part concentrated composition for a color development replenisher for a color photographic light-sensitive material according to any one of claims 1 to 4 diluted 3 to 6 times with water and used as a replenisher. Processing method for silver color photographic light-sensitive material.