JP2007017745A - Concentrated composition for stabilization of silver halide color photographic sensitive material - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a concentrated composition for stabilization of a silver halide color photographic sensitive material which proper in the improvement of the work environment and in environmental protection, excels in precipitation resistance during storage and in expansion preventing effect in a container, and excels also in continuous processing stability. <P>SOLUTION: The concentrated composition for stabilization of a silver halide color photographic sensitive material contains 0.05-8.0 mol/l of sodium ions or potassium ions, as well as contains alkylene oxides. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a concentrated composition for stabilizing a novel silver halide color photographic material.

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

  By the way, in the development processing of silver halide color photographic light-sensitive materials, a minilab that is installed at the store of a photo shop and processes the light-sensitive materials for quick printing services for general users and rationalization of collection and delivery between the photo shop and the development shop. An automatic developing processor referred to as "" is widely used. In addition, if the development processing composition used for processing for minilabs is in the form of a liquid composition in which constituent chemicals are previously dissolved in a solvent such as water, it can be processed by simple preparation operations such as mixing and dilution with water. This is often provided in this form because of the advantage that the liquid can be prepared. In addition, the liquid composition form is disadvantageous in terms of transportation cost, space, etc. because it involves a solvent such as water required for dissolution of the treatment composition component and a container for storing the composition. In general, it is supplied in the form of a liquid concentrated composition with reduced volume. On the other hand, in the process of supplying processing chemicals to a photo shop or the like where a minilab is installed, these processing compositions are stored in various environments. For example, in the summer season, the processing compositions are stored. The surrounding atmosphere becomes a high-temperature environment with an air temperature of 50 ° C or higher, and conversely, in winter, such as in a cold region, it may become a low-temperature environment during the transportation process, etc. Things are desired. Furthermore, these treatment compositions may be stored for several years at the longest until they are used in transportation and on the market, and improvement in storage stability during long-term storage is desired.

  On the other hand, from the viewpoint of improving the working environment and protecting the environment, attempts have been actively made to reduce the amount of ammonium salt used in the development processing composition. However, when potassium ions or sodium ions are used instead of ammonium salts, there is a problem that the solubility is lowered. In particular, in a concentrated composition (concentrated composition for stabilization treatment) used in a stabilization step having a high concentration rate, a concentrated composition is prepared using a compound containing a potassium salt or a sodium salt instead of an ammonium salt. If the product is stored for a long time under a low temperature condition or in a high temperature environment, the storage stability is poor, and problems such as precipitation of the concentrated composition and expansion of the container may occur. These problems not only reduce the commercial value, but also cause a problem that the component changes due to precipitation, the active ingredient loses its activity, and sufficient processing characteristics cannot be obtained. In addition, due to precipitation and the like, the environmental protection operation for recycling the waste container will be hindered.

  On the other hand, for a processing composition containing alkylene oxides, a stabilizer for silver halide color photographic light-sensitive materials characterized by containing a cyclic aldehyde compound and a glycol solvent is disclosed (for example, Patent Documents). 1). According to the method described in Patent Document 1, it is said that the dye fading is improved under low humidity, the storage stability of the concentrated composition is improved, and failures during processing of the photosensitive material can be reduced.

However, Patent Document 1 discloses nothing about the use of alkylene oxides for the improvement of precipitation resistance and storage expansion during storage at a specific concentration of potassium ion or sodium ion contained in the stabilization composition. It is neither mentioned nor suggested.
Japanese Patent No. 3146383

  The present invention has been made in view of the above problems, and its purpose is good in terms of improving the working environment and protecting the environment, and is excellent in precipitation resistance during storage and in the effect of preventing expansion in a container, and is continuous. An object of the present invention is to provide a concentrated composition for stabilizing processing of a silver halide color photographic material excellent in processing stability.

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

(Claim 1)
A concentrated composition for stabilizing processing of a silver halide color photographic material comprising sodium ion or potassium ion in an amount of 0.05 mol / L or more and 8.0 mol / L or less and an alkylene oxide. .

(Claim 2)
2. The concentrated composition for stabilizing processing of a silver halide color photographic material according to claim 1, wherein the concentration of the sodium ion or potassium ion is 0.25 mol / L or more and 6.0 mol / L or less. object.

(Claim 3)
The concentrated composition for stabilizing processing of a silver halide color photographic material according to claim 1 or 2, wherein the pH is 4.0 or more and 10.0 or less.

(Claim 4)
The concentrated composition for stabilizing processing of a silver halide color photographic material according to any one of claims 1 to 3, comprising a compound represented by the following general formula [I].

Formula [I]
RSO ₂ M
[Wherein, R represents an alkyl group, a cycloalkyl group, an alkenyl group, an alkynyl group, a heterocyclic group or an aryl group. M represents a hydrogen atom, an alkali metal atom, an ammonium group or a quaternary amine. ]
(Claim 5)
The silver halide color photographic photosensitive material according to any one of claims 1 to 4, wherein the silver halide color photographic photosensitive material is packaged with a packaging material, and the oxygen permeability coefficient of the packaging material is 50 ml / m ² · atm · day or less. Concentrated composition for material stabilization treatment.

  ADVANTAGE OF THE INVENTION According to this invention, the concentrated composition for the stabilization process of the silver halide color photographic photosensitive material excellent in the precipitation tolerance at the time of a preservation | save and the expansion | swelling prevention effect in a container can be provided.

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

  As a result of intensive studies in view of the above-mentioned problems, the present inventor contains sodium ions or potassium ions in an amount of 0.05 mol / L or more and 8.0 mol / L or less, and contains alkylene oxides. The concentrated composition for stabilizing processing of a silver halide color photographic light-sensitive material is excellent in resistance to precipitation during storage and the effect of preventing expansion in a container, and is a silver halide color photographic light-sensitive material excellent in continuous processing stability. As soon as the present inventors have found that a concentrated composition for stabilization treatment can be realized, the present invention has been achieved.

  That is, as described above, in the concentrated composition for stabilization treatment with a high concentration rate, an ammonium salt has been conventionally used as a counter cation of a constituent component or for pH adjustment, but this is replaced with a potassium salt or a sodium salt. Storage stability decreases, especially when stored for a long period of time in a low temperature environment or in a high temperature environment, the container may expand after storage due to gas generation due to precipitation of the concentrated composition or decomposition. As a result of the inventor's earnest study on the problem that comes, the concentrated composition for stabilization treatment containing potassium ions or sodium ions in a specific concentration range can be obtained by adding alkylene oxides. It has been found that the stability of materials can be improved, and it has been found that precipitation and generation of decomposition gas can be prevented.

  Details of the present invention will be described below.

  First, the concentrated composition for stabilization treatment of the present invention will be described.

  The concentrated composition for stabilization treatment of the present invention is a concentrated stabilized treatment composition for preparing a use liquid (tank liquid) or a replenisher used in a processing step after desilvering. In addition, a rinse solution or a washing solution which has been conventionally used is also included. Moreover, in this invention, unless there is a special meaning in distinguishing a stabilized use liquid (tank liquid) and a stabilization replenisher, both are expressed as a stabilization process composition.

  The concentration composition for stabilization treatment of the present invention (hereinafter also referred to as stabilization treatment composition) exhibits a target effect, so that the concentration of sodium ion or potassium ion is 0.05 mol / L or more, 8.0 mol. In addition, when the concentration of sodium ion or potassium ion is 0.25 mol / L or more and 6.0 mol / L or less, good container expansion resistance and low temperature precipitation resistance effect are exhibited. From the viewpoint of

  The sodium ion or potassium ion may be added in any state such as an alkaline agent such as sodium hydroxide (NaOH) or potassium hydroxide (KOH), or a sodium salt or potassium salt.

  Next, the alkylene oxides that are the characteristics of the concentrated composition for stabilization treatment of the present invention will be described.

  Examples of the alkylene oxides according to the present invention include alkylene glycols, polyalkylene glycols, polyalkylene oxides, and the like, and preferred examples include compounds represented by the following general formula [II].

General formula [II]
RO- (W-O) _p- R
In the general formula [II], R represents a hydrogen atom or an alkyl group. W is _{-CH 2 CH 2 -, - CH} 2 CH 2 CH 2 -, - CH 2 CH (CH 3) - or _{-CH 2 CH 2 CH 2 CH 2} - represents a. Moreover, p is an integer of 1-300, the integer of 1-160 is preferable and it is preferable from a soluble viewpoint that an average molecular weight is 10,000 or less.

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

II-1: Ethylene glycol
II-2: Propylene glycol
II-3: Diethylene glycol
II-4: Butylene glycol
II-5: Polyethylene glycol # 400 (average molecular weight 400)
II-6: Polyethylene glycol # 600 (average molecular weight 600)
II-7: Polyethylene glycol # 1000 (average molecular weight 1000)
II-8: Polyethylene glycol # 2000 (average molecular weight 2000)
II-9: Polyethylene glycol # 4000 (average molecular weight 4000)
II-10: Polyethylene glycol # 6000 (average molecular weight 6000)
II-11: Polyethylene glycol # 10000 (average molecular weight 10,000)
II-12: Polypropylene glycol # 400 (average molecular weight 400)
II-13: Polypropylene glycol # 700 (average molecular weight 700)
II-14: Polypropylene glycol # 1000 (average molecular weight 1000)
II-15: Polypropylene glycol # 2000 (average molecular weight 2000)
II-16: Polypropylene glycol # 4000 (average molecular weight 4000)
II-17: Polytetramethylene ether glycol (average molecular weight 700)
II-18: Polytetramethylene ether glycol (average molecular weight 1000)
Etc. Moreover, as addition amount of alkylene oxide, 0.1g-200g per 1L of concentration compositions for stabilization process are preferable from a soluble point.

  In addition, the concentrated composition for stabilization treatment of the present invention is a sulfinic acid derivative represented by the above general formula [I], from the viewpoint that the objective effect of the present invention can be further exhibited under more severe storage conditions. It is preferable to contain.

  In the general formula [I], R represents an alkyl group, a cycloalkyl group, an alkenyl group, an alkynyl group, a heterocyclic group or an aryl group, and when R is an alkyl group, it preferably has 1 to 10 carbon atoms, more Preferably it is 1-3 alkyl groups. Moreover, in the case of a cycloalkyl group, C6-C10 is preferable and the case of C6-C is the most preferable. In the case of an alkenyl group and an alkynyl group, it preferably has 3 to 10 carbon atoms, more preferably 3 to 6 carbon atoms. In the case of an aryl group, 6 to 10 carbon atoms are preferable, and the case of 6 carbon atoms is most preferable. In the case of a heterocyclic group, C1-C6 is preferable. These groups include those having various substituents, and preferred substituents include a hydroxyl group, an alkyl group, an aryl group, an amino group, a sulfonic acid group, a carboxylic acid group, a nitro group, a phosphoric acid group, a halogen atom, and an 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 these, preferable R is preferably an alkyl group having 1 to 3 carbon atoms or a phenyl group, and preferable substituents include an amino group, a carboxylic acid group, and a hydroxyl group. M in the general formula [I] represents a hydrogen atom, an alkali metal atom, an ammonium group or a quaternary amine group, preferably a hydrogen atom, a sodium atom or a potassium atom.

  Of the sulfinic acid derivatives represented by the general formula [I], arylsulfinic acid derivatives in which R is an aryl group are preferable from the viewpoint of solubility.

  Specific examples of the sulfinic acid derivative represented by the general formula [I] according to the present invention are illustrated below, but the sulfinic acid derivative represented by the general formula [I] is not limited thereto. Moreover, although the sulfinic acid group and the carboxylic acid group are mainly shown in the form of a neutral salt in the exemplified compounds below, the salt shown in M above may be used.

  The sulfinic acid derivative represented by the general formula [I] according to the present invention is generally synthesized by reduction of a sulfonyl chloride compound. Examples of the reducing agent include zinc powder, sulfite ion, alkali metal sulfide, and the like. Used. Other methods are also known. The general synthesis method of the sulfinic acid derivative represented by the general formula [I] including the above is described in, for example, Chemical Review (Chem. Rev.), 4508, 69 (1951), Organic Synthesis (Organic Synthesis). ), Collective Vol. I. 492 (1941), Journal of American Chemical Society (J. Am. Chem. Soc.), 72, 1215 (1950), ibid, 50, 792, 274, (1928), etc. Yes.

  The addition concentration is preferably 0.01 to 0.5 mol, more preferably 0.04 to 0.4 mol, per liter of the stabilized composition for stabilization treatment of the present invention. Moreover, the addition amount per 1 L of the stabilization treatment composition is preferably 2.0 mmol or more and 30.0 mmol or less. In the concentration range, stable treatment liquid characteristics can be obtained.

  In addition to the above additives, the concentrated composition for stabilization treatment of the present invention contains a buffer (for example, potassium carbonate, borate, acetate, phosphate, etc.), an antifungal agent (for example, Diaside 702 ( Dearborn), Topside 2520 (Permachem), 1-bromo-3-chloro-5,5'-dimethylhydantoin, 1,3-bis (hydroxymethyl) bromo-3-5,5'-dimethylhydantoin 2-Bromo-2-nitropropane-1,3-diol, p-chloro-m-cresol, 1,2-benzisothiazolin-3-one, o-phenylphenol, sodium dichloroisocyanurate, trichloroisocyanuric acid, etc.) , Antioxidants (eg, ascorbate, etc.), water-soluble metal salts (eg, zinc salts, magnesium salts, etc.), alkyl sulfonic acids, allies Add surfactants such as sulfonic acids, aliphatic carboxylic acids, aromatic carboxylic acids, chelating agents, polymers or copolymers having a pyrrolidone nucleus in the molecular structure, fluorescent brighteners, triazine compounds, etc. Can do.

  Specific examples of the chelating agent include nitrilotriacetic acid, diethylenetriaminepentaacetic acid, ethylenediaminetetraacetic acid, N, N, N-trimethylenephosphonic acid, ethylenediamine-N, N, N ′, N′-tetramethylenesulfonic acid, trans Sirohexasidiaminetetraacetic acid, 1,2-diaminopropanetetraacetic acid, glycol etherdiaminetetraacetic acid, ethylenediamine orthohydroxyphenylacetic acid, ethylenediamine disuccinic acid (S, S form), N- (2-carboxylate ethyl) -L Aspartic acid, β-alanine diacetic acid, 2-phosphonobutane-1,2,4-tricarboxylic acid, 1-hydroxyethylidene-1,1-diphosphonic acid, N, N′-bis (2-hydroxybenzyl) ethylenediamine-N, N'-diacetic acid, 1,2-dihydroxybenzene- , A 6-disulfonic acid. Further, the addition concentration is preferably in the range of 1 g to 500 g per liter of the stabilizing composition for stabilization from the viewpoint of solubility.

  As the polymer or copolymer having a pyrrolidone nucleus in the molecular structure, those having an average molecular weight of 1,000 to 70,000 are preferable, and typical examples thereof are shown below.

[1] Poly-N-vinyl-2-pyrrolidone (* 1)
[2] Poly-N- (2-acryloyloxy) ethyl-1-pyrrolidone [3] Poly-N-glycidyl-2-pyrrolidone [4] Poly-N-allyl-2-pyrrolidone [5] Poly-N, N -Dimethyl-N- [3 (1-pyrrolidonyl) -2-hydroxy] propyl-amine-N'-acryloilymine [6] Copoly-N-vinyl-2-pyrrolidone / N-acryloylmorpholine (molar ratio 42:58)
[7] Copoly-N-vinyl-2-pyrrolidone / N-acryloylpiperidine (molar ratio 35:65)
[8] Poly-N-vinyl-2-pyrrolidone / N-methacryloyl-2-methylimidazole (molar ratio 55:45)
[9] Copoly-N- (2-acryloyloxy) -ethyl-2-pyrrolidone / acrylic acid diethylamide (molar ratio 60:40)
[10] Copoly-N- (2-methacryloyloxy) ethyl-2-pyrrolidone / sodium acrylate (molar ratio 75:25)
[11] Copoly-N- (3-acryloyloxy) propyl-2-pyrrolidone / methyl methacrylate (molar ratio 65:35)
[12] Copoly-N, N-dimethyl-N- [3- (1-pyrrolidonyl) -2-hydroxy] -propylamine-N'-acryloylmine / ethyl acrylate (molar ratio 70:30)
[13] Copoly-N-vinyl-2-pyrrolidone / vinyl acetate (molar ratio 70:30)
[14] Copoly-N-vinyl-2-pyrrolidone / methyl acrylate (molar ratio 70:30)
[15] Copoly-N-vinyl-2-pyrrolidone / styrene (molar ratio 80:20)
[16] Copoly-N-vinyl-2-pyrrolidone / acrylic amide / N-vinyl-2-methylimidazole (molar ratio 50:30:20)
[17] Copoly-N-vinyl-2-pyrrolidone / N- (1,1-dimethyl-3-oxo) -butyl-acrylamide (molar ratio 70:30)
[18] Copoly-N-allyl-2-pyrrolidone / vinyl acetate (molar ratio 64:36)
[19] Copoly-N-vinyl-2-pyrrolidone / 4-vinylpyridine (molar ratio 60:40)
[20] Copoly-N-vinyl-2-pyrrolidone / ethyl acrylate / acrylic acid monoethanolamic acid (molar ratio 50: 45: 5)
[21] Copoly-N-vinyl-2-pyrrolidone / piperidinomaleamic acid piperidine acid (molar ratio 53:47)
[22] Copoly-N-vinylpyrrolidone / 4-vinylpyridino-N-methyl iodide (molar ratio 42:58)
[23] Copoly-N-vinylpyrrolidone / thiourea half ammonium salt maleate (molar ratio 60:40)
* 1: Exemplified compound [1] is PVP K-15, PVP K-17, PVP K-30, PVP K-60, and PVP K-90 from General Aniline and Film Corp. As a trade name of BASF Aktiengesellschaft, Kollidon 12, Kollidon 17, Kollidon 25, Kollidon 30, Kollidon 90, Rubiscor K-17, Rubiscor K-30, Rubiscor K-90 It is commercially available under the trade name.

  The addition amount of the polymer having a pyrrolidone nucleus in the molecular structure is preferably in the range of 0.1 g to 100 g per liter of the concentrated composition for stabilization treatment of the present invention from the viewpoint of solubility.

  As the optical brightener, a bis (triazinylamino) stilbene sulfonic acid compound is preferred. As the bis (triazinylamino) stilbene sulfonic acid compound, known or commercially available products can be used. As the known bis (triazinylamino) stilbene sulfonic acid compound, for example, compounds described in JP-A-6-329936, JP-A-7-140625, JP-A-10-14049 and the like are preferable. Commercially available compounds are described, for example, in “Dyeing Note”, 9th edition (Colored dyeing), pages 165 to 168, and among the compounds described therein, Tinopearl SFP, Blankophor BSU liq. , Hakkol BRK, Hakkol 508 and the like are preferable. Other bis (triazinylamino) stilbene sulfonic acid compounds include compounds I-1 to I-48 described in paragraphs [0038] to [0049] of JP-A No. 2001-281823 and JP-A No. 2001-2001. Examples include compounds II-1 to II-16 described in paragraph Nos. [0050] to [0052] of 281823. The addition amount of these optical brighteners to the stabilized composition for stabilization treatment so as to be 0.1 to 0.1 mol per liter of the treatment composition exhibits good white background. To preferred.

  Specific examples of the triazine compound include compounds A-1 to A-34 described in paragraph numbers [0023] to [0031] of JP-A No. 2002-139822 or paragraph numbers of JP-A No. 2002-196460. The compounds P-1 to P-20 described in [0022] to [0021] are listed. In addition, you may contain 1) -20) etc. of Paragraph Nos. [0017]-[0026] of Unexamined-Japanese-Patent No. 2003-255502. These triazine compounds or the compound addition amount described in JP-A-2003-255502 is from 0.1 to 0.1 mol per liter of the treatment composition from the viewpoint of solubility. It is preferable to add to.

The concentrated composition for stabilization treatment of the present invention preferably contains a sulfite from the viewpoint of liquid storage stability. The sulfite may be any organic or inorganic substance as long as it releases sulfite ions, but is preferably an inorganic salt. Specific examples of the compound include sodium sulfite, potassium sulfite, ammonium sulfite, ammonium bisulfite, potassium bisulfite, sodium bisulfite, sodium metabisulfite, potassium metabisulfite, and ammonium metabisulfite. These sulfites are added to the concentrated treatment composition so as to be 1 × 10 ⁻⁵ mol / L or more, further 5 × 10 ⁻⁵ mol / L to ⁵ × 10 ⁻² mol / L per liter of the treatment composition. Things are preferable.

  The pH of the stabilized composition for stabilization treatment of the present invention may be in any range, but is preferably in the range of 4.0 to 10.0 from the viewpoint of easily achieving the object effect of the present invention.

  Next, the concentration of the concentrated composition for stabilization treatment of the present invention will be described.

  Concentration of the concentrated composition for stabilization treatment of the present invention means that the concentrated composition is diluted with a solvent such as water to prepare a target treatment composition (replenisher or use liquid (tank liquid)). It is expressed as a volume ratio of the finished treatment composition to the original concentrated composition. The degree of the volume ratio is referred to as the concentration rate. In the present invention, the concentration ratio may be any number as long as there is no stability over time or inactivation of the treatment composition, but it is preferably 10 to 100 times from the viewpoint of storage space, transportation or handling properties.

The material of the packaging material (also referred to as a packaging container or simply a container) containing the concentrated composition for stabilization treatment of the present invention may be any material, but a plastic material is preferable, and the object effect of the present invention is From the viewpoint, the oxygen permeability coefficient is preferably 50 ml / m ² · atm · day or less, and more preferably 20 ml / m ² · atm · day or less. The oxygen permeability coefficient here is a value measured by the JIS K7126 B method (isobaric method) under the conditions of a temperature of 23 ° C. and a humidity of 40% RH.

  Specific packaging materials include polyolefin resins, polyethylene-vinyl acetate copolymer resins, ethylene-vinyl alcohol copolymer resins, polyamide resins, acrylonitrile resins, polyethylene terephthalate resins, poly (vinylidene halide) resins. Resin, polyhalogenated vinyl resin, polylactic acid, polycaprolactone, polybutylene succinate (including polybutylene succinate / adipate copolymer, polybutylene succinate / carbonate copolymer), polyethylene succinate , Polyvinyl alcohol, aliphatic polyester, terephthalic acid / 1,4-butanediol / adipic acid copolymer, β-hydroxybutyric acid / β-hydroxyvaleric acid copolymer, chito acid-cellulose-starch hybrid, cellulose acetate , Methyl A cellulose etc. can be mentioned.

  The resin used for the polyolefin resin layer is preferably polyethylene, and any of low density polyethylene (LDPE), medium density polyethylene (MDPE) and high density polyethylene (HDPE) can be used. HDPE has a density of 0.941 to 0.969. Further, LDPE is preferably synthesized by a high pressure polymerization method, and its density is 0.910 to 0.925. Also, plastic materials such as polylactic acid, polycaprolactone, polybutylene succinate, polyethylene succinate, and cellulose acetate can be used.

  Examples of commercially available products include, for polylactic acid, eco plastic (manufactured by Cargill Japan Co., Ltd., Cargill Dow Posimers Co., Ltd.), lacti (manufactured by Shimadzu Corporation), laceia (manufactured by Mitsui Chemicals, Inc.), polycaprolactone, PH (Daicel Chemical Industries, Ltd.), polybutylene succinate, Bionore (Showa Polymer Co., Ltd.), Ubeck (Mitsubishi Gas Chemical Co., Ltd.), polyethylene succinate, Lunare SE (Japan) Catalyst), polyvinyl alcohol, poval (made by Kuraray Co., Ltd., unitika), aliphatic polyester, green block (made by JSP), terephthalic acid / 1, For 4-butanediol / adipic acid copolymer, Ecoflex (manufactured by BASF Japan), β-hydroxybutyric acid / β-hydroxyvale As phosphoric acid copolymers, biofan (manufactured by Gunze Co., Ltd.), biopol (manufactured by ICI), chito acid-cellulose-starch reaction product, Delon CC (manufactured by Aicero Chemical Co., Ltd.), cellulose acetate, cell green PCA (Manufactured by Daicel Chemical Industries, Ltd.). These packaging materials can be blended with heat stabilizers, weather stabilizers, modifiers, lubricants, colorants, fillers, and the like. These ingredients are carbon black, titanium white, calcium silicate, silica, calcium carbonate, additives such as 2,6-di-t-butyl-4-methylphenol (BHT), dicetyl sulfide, tris (laurylthio) Phosphites, other known antioxidants such as amines, thioethers, and phenols, slipping agents such as stearic acid or its metal salts, plasticizers such as 2-hydroxy-4-n-octyloxybenzophenone, etc. Can be mentioned.

  The packaging container material may be molded and used alone, but two or more types of materials may be used as appropriate. Plastic materials with low air permeability and plastics with high mechanical strength are used as necessary. A combination of materials and the like, and a configuration in which a chemically stable plastic material having strong chemical resistance is arranged on the inner side and a plastic material having high mechanical strength on the outer surface side can be exemplified. The container can be molded by injection molding, blow molding (including injection blow molding, extrusion blow molding), extrusion molding, vacuum molding, or the like, and a molding method can be employed depending on the purpose. The container preferably has a container body having a certain degree of flexibility and shock absorption and a hard mouth projecting from the container body. Further, the mouth portion is preferably configured so that the upper opening portion is opened and closed by attaching and detaching a cap (lid member) that is screwed to the mouth portion. Wide-mouthed containers or round-shaped wide-mouthed containers. In addition, for example, containers that are mounted on an automatic processor disclosed in Japanese Patent Application Laid-Open Nos. 2000-2933 and 2000-3014, are automatically opened, and can be automatically prepared. . In the present invention, the packaging container may be a bag-like container in which films formed by an inflation molding method or an injection stretch molding method are laminated by a conventional method. A typical example is a bag-like container lined with a card board that is commonly used in the industry under the name of cubitena.

  Next, the development processing step including the stabilization step in which the concentrated composition for stabilization processing of the present invention is used will be described.

  In addition to the stabilization process (washing and rinsing process), the development process includes a color development process, a desilvering process (a bleaching process, a fixing process or a bleaching and fixing process in which bleaching and fixing processes are processed in the same process), and a drying process. In addition, auxiliary processes such as an intermediate water washing process and a neutralization process may be inserted between the processes. Further, it is preferable that the development process is performed in the order of a color development process and a desilvering process, followed by a stabilization process and then a drying process. In each processing step, continuous development processing is performed while replenishing a replenishing color developing solution, a replenishing bleaching solution, a replenishing fixing processing solution, a replenishing bleach-fixing processing solution, or a replenishing stabilizing treatment solution. You can also

The replenishment amount of each processing solution is preferably 15 to 200 ml, more preferably 15 to 120 ml, and particularly preferably 30 to 120 ml per 1 m ^{2 of} photosensitive material when the photosensitive material to be developed is color paper in the color development step. 60 ml. On the other hand, when the photosensitive material to be developed is a color negative film, the amount is preferably 100 to 800 ml, more preferably 200 to 500 ml, particularly preferably 250 to 400 ml per 1 m ² of the photosensitive material. The replenishment amount in the bleaching step is preferably 80 to 500 ml per 1 m ² of photosensitive material, and more preferably 80 to 200 ml. The replenishment amount in the bleach-fixing step is preferably 20 to 250 ml per 1 m ^{2 of} photosensitive material, more preferably 20 to 110 ml, and still more preferably 30 to 100 ml. The replenishing amount in the fixing step is preferably 3000 ml or less, more preferably 200 to 1000 ml or less per 1 m ² of the photosensitive material. The replenishment amount in the stabilization step is preferably 1000 ml or less as a whole. Further, the processing time of each step is preferably 45 seconds or less, more preferably 30 seconds or less, and more preferably 30 seconds or less, when the light-sensitive material is color paper, from the viewpoint of quickness of the color development time (time for performing the color development step). Preferably it is 26 seconds or less and 6 seconds or more. On the other hand, when the light-sensitive material is a color negative film, the time is preferably 20 seconds to 6 minutes, and more preferably 30 to 200 seconds. In the bleaching step, the time required for the treatment is preferably set within 2 minutes, more preferably within 60 seconds, and even more preferably within 45 seconds. The processing time of the bleach-fixing step is preferably set within 90 seconds, particularly preferably 45 seconds, and more preferably 26 seconds. The fixing time (time for performing the fixing step) is preferably within 3 minutes, and more preferably within 2 minutes. The stabilization time (time for performing the stabilization step) is preferably 90 seconds or less.

  The color development time refers to the time from when the photosensitive material is immersed in the first tank until it exits the final tank when the process has a plurality of tanks. It means the time from the start to the next processing step to the bleaching or bleach-fixing tank, including the crossover time (outside transport time). Similarly, the bleaching time is the time from when the photosensitive material is immersed in the first tank until it leaves the final tank when the process has a plurality of tanks. This refers to the time until the photosensitive material is immersed, and includes the crossover time. The time required for the bleach-fixing process is also the time from when the photosensitive material is immersed in the first tank until it leaves the final tank when the process has a plurality of tanks. This refers to the time until the photosensitive material is immersed, and includes the crossover time.

  Fixing time also refers to the time from when the photosensitive material is immersed in the first tank until it exits the final tank, and in the case of one tank, for example, it indicates the time until the photosensitive material is immersed in the subsequent stabilization tank. Including crossover time.

  Also, the stabilization time refers to the time from when the photosensitive material is immersed in the first tank until it exits the final tank, and in the case of one tank, it refers to the time from entering the stabilization tank to entering the drying process, Including the crossover time. The crossover time is preferably as short as possible from the viewpoint of stain and fog prevention, and is preferably 10 seconds or less, more preferably 5 seconds or less, and even more preferably 3 seconds or less.

  In the stabilization step, the crossover time is preferably 5 seconds or less and substantially 0 from the viewpoint of suppressing edge contamination. The edge contamination referred to here refers to the stain on the cut end surface (edge portion) of the paper support of the photosensitive material after processing. The means for making the crossover time substantially zero can be achieved by using a conveying system such as a submerged blade as described in FIGS. 2 to 5 of JP-A-5-66540.

  Moreover, although 1 tank may be sufficient as a stabilization process, it is preferable at the point which can reduce the replenishment amount by increasing the number of tanks about 2-10 tanks. The preferred number of tanks is about 2-6. In addition, when there are a plurality of stabilization steps, replenishment may be performed in several places. However, replenishment to the downstream side tank in the conveyance direction of the photosensitive material, and the overflow liquid (between the tanks below the liquid level). It is preferable to use a counter current method (multi-stage countercurrent method) in which the solution flows through the front tank of the tank when the pipes are connected by a pipe located at the front of the tank. Included in one. More preferably, the replenisher is replenished to the last tank in two or more stabilization tanks, and the overflow liquid is sequentially poured into the previous tank.

  The processing solution temperature in the color development step, desilvering step, and stabilization step is generally 30 to 40 ° C., but is preferably 38 to 60 ° C., more preferably 38 to 50 ° C. for rapid processing. The drying process is to absorb moisture with a squeeze roller or cloth immediately after the stabilization process of the development 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 speed up drying. Naturally, 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.

  Further, aeration may be performed in the bleaching step. Any means known in the art can be used for aeration. Regarding aeration, the items described in Eastman Kodak Co., Ltd., Z-121, Yuging Process C-41 3rd Edition (1982), BL-1 to BL-2 can be used. Further, in the bleaching step, it is preferable to enhance stirring, and the contents described in JP-A-3-33847, page 8, upper right column, line 6 to lower left column, line 2 are used as they are. it can. Among these, the jet stirring method in which the bleaching composition is sprayed on the emulsion surface of the light-sensitive material is preferable. Further, in the bleaching step and the bleach-fixing step, the overflow liquid after use can be recovered for processing, and the components can be added to correct the composition and then reused (regenerated).

  As a specific example, the method described in “Basics of Photographic Engineering—Silver Salt Photo Edition” (edited by the Japan Photography Society, published by Corona Inc., published in 1979) can be used. Specifically, in addition to electrolytic regeneration, bromic acid, chlorous acid, bromine, bromine precursor, persulfate, hydrogen peroxide, hydrogen peroxide using a catalyst, bromic acid, ozone, and the like can be given.

  Next, each processing composition used in the development processing step will be described.

  First, the color development processing composition will be described.

  Preferred examples of the color developing agent used in the color developing composition according to the present invention are known aromatic primary amine color developing agents, particularly p-phenylenediamine derivatives, and typical examples are shown below. It is not limited.

1) N, N-diethyl-p-phenylenediamine 2) 4-amino-3-methyl-N, N-diethylaniline 3) 4-amino-N- (β-hydroxyethyl) -N-methylaniline 4) 4 -Amino-N-ethyl-N- (β-hydroxyethyl) aniline 5) 4-amino-3-methyl-N-ethyl-N- (β-hydroxyethyl) aniline 6) 4-amino-3-methyl-N -Ethyl-N- (3-hydroxypropyl) aniline 7) 4-Amino-3-methyl-N-ethyl-N- (4-hydroxybutyl) aniline 8) 4-Amino-3-methyl-N-ethyl-N -(Β-Methanesulfonamidoethyl) aniline 9) 4-Amino-N, N-diethyl-3- (β-hydroxyethyl) aniline 10) 4-Amino-3-methyl-N-ethyl-N- (β- Me Xylethyl) aniline 11) 4-Amino-3-methyl-N- (β-ethoxyethyl) -N-ethylaniline 12) 4-Amino-3-methyl-N- (3-carbamoylpropyl-Nn-propyl- Aniline 13) 4-Amino-N- (4-carbamoylbutyl-Nn-propyl-3-methylaniline 14) N- (4-Amino-3-methylphenyl) -3-hydroxypyrrolidine 15) N- (4 -Amino-3-methylphenyl) -3- (hydroxymethyl) pyrrolidine 16) N- (4-Amino-3-methylphenyl) -3-pyrrolidinecarboxamide Among the above p-phenylenediamine derivatives, particularly preferred compounds 5), 6), 7), 8) and 12). Among them, exemplary compounds 5) and 8) are preferable. These p-phenylenediamine derivatives are in the form of a salt such as sulfate, hydrochloride, sulfite, naphthalene disulfonate, p-toluenesulfonate, or the free base type as described above. The concentration of the aromatic primary amine developing agent in the working solution is 2 to 200 mmol, preferably 6 to 100 mmol, more preferably 10 to 40 mmol per liter of color developer. It is done.

  An organic preservative may be added to the color development processing composition. 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, organic compounds having a function to prevent air oxidation of the color developing agent, such as hydroxamic acids, hydrazides, phenols, α-hydroxy ketones, α-amino ketones, saccharides, monoamines, diamines, polyamines , Quaternary ammonium salts, nitroxy radicals, alcohols, oximes, diamide compounds, condensed amines and the like are particularly effective organic preservatives. These are disclosed in JP-A 63-4235, 63-30845, 63-21647, 63-44655, 63-53551, 63-43140, 63-56654, 63- 58346, 63-43138, 63-146041, 63-44657, 63-44656, U.S. Pat.Nos. 3,615,503, 2,494,903, JP-A 52- No. 143,020, Japanese Patent Publication No. 4,830,496 and the like.

  Moreover, as another organic preservative, the compound represented by the following general formula (X) or (Y) can also be contained.

In the general formula (X), L represents an alkylene group that may be substituted, A represents a carboxyl group, a sulfo group, a phosphono group, a hydroxyl group, an amino group that may be alkyl-substituted, or an ammonio that may be alkyl-substituted. A carbamoyl group that may be alkyl-substituted, a sulfamoyl group that may be alkyl-substituted, a sulfonyl group that may be alkyl-substituted, a hydrogen atom, an alkoxyl group, or —O— (B—O) _n —R ′ , R and R ′ each represents a hydrogen atom or an optionally substituted alkyl group. B represents an alkylene group which may be substituted, and n represents an integer of 1 to 4.

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

  Although the representative compound example is shown below among the compounds represented by general formula (X), this invention is not limited to these compounds.

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

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

  If s takes 1, A is

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

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

  Other organic preservatives include various metals described in JP-A-57-44148 and 57-53749, salicylic acids described in JP-A-59-180588, triethanolamine and triiamine. Alkanolamines described in JP-A No. 54-3532, such as sopanolamine, polyethyleneimines described in JP-A-56-94349, US Pat. No. 3,746,544, etc. An aromatic polyhydroxy compound or the like may be contained as necessary.

The addition amount of the organic preservative is preferably 1 × 10 ⁻³ mol or more and 1 × 10 ⁻¹ mol or less per liter of the color developing solution. Further, the color developing solution may contain a small amount of sulfite ions or may not substantially contain sulfite ions depending on the type of the photosensitive material, but in the present invention, it is preferable to contain a small amount of sulfite ions. Moreover, you may contain a small amount of hydroxylamine. Hydroxylamine (usually used in the form of hydrochloride or sulfate, but omits the salt form below) acts as a developer preservative like sulfite ion, but at the same time, hydroxylamine itself has silver developing activity. For this reason, the photographic characteristics may be affected. Therefore, it is necessary to keep this addition amount small. The color development processing composition may contain a sulfinic acid derivative represented by the general formula [I] according to the present invention.

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

  Examples of the buffer for maintaining the pH include carbonate, phosphate, borate, tetraborate, hydroxybenzoate, glycyl salt, N, N-dimethylglycine salt, leucine salt, norleucine salt, Guanine salt, 3,4-dihydroxyphenylalanine salt, alanine salt, aminobutyrate salt, 2-amino-2-methyl-1,3-provandiol salt, valine salt, proline salt, trishydroquinaminomethane salt, lysine salt, etc. Can be used. In particular, carbonate, phosphate, tetraborate, and hydroxybenzoate have excellent buffering ability in a high pH range of pH 9.0 or higher, and even when added to a color development processing composition, they adversely affect photographic performance. It is a particularly preferable buffer because it is free from fog (such as fogging) and is inexpensive.

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

  The addition amount of the buffering agent is preferably 0.01 to 2 mol, more preferably 0.1 to 0.5 mol, per liter of the color developing composition.

  As the other components, for example, calcium and magnesium precipitation inhibitors and various chelating agents that are also stability improvers can be added to the color development processing composition. Specific examples of various chelating agents include nitrilotriacetic acid, diethylenetriaminepentaacetic acid, ethylenediaminetetraacetic acid, N, N, N-trimethylenephosphonic acid, ethylenediamine-N, N, N ', N'-tetramethylenesulfonic acid. , Transsirohexadiaminediamineacetic acid, 1,2-diaminopropanetetraacetic acid, glycol etherdiaminetetraacetic acid, ethylenediamine orthohydroxyphenylacetic acid, ethylenediamine disuccinic acid (S, S form), N- (2-carboxylate ethyl) -L-aspartic acid, β-alanine diacetic acid, 2-phosphonobutane-1,2,4-tricarboxylic acid, 1-hydroxyethylidene-1,1-diphosphonic acid, N, N′-bis (2-hydroxybenzyl) ethylenediamine— N, N'-diacetic acid, 1,2-dihydroxybenzene Such as 4,6-disulfonic acid and the like. These chelating agents may be used in combination of two or more as required. The amount of these chelating agents may be an amount sufficient to sequester metal ions in the color development processing composition. For example, 0. It is added so as to be about 1 to 10 g.

  If necessary, an arbitrary development accelerator can be added to the color development processing composition. Examples of the development accelerator include JP-B-37-16088, JP-A-37-5987, JP-A-38-7826, JP-A-44-12380, JP-A-45-9019, and U.S. Pat. No. 3,813,247. Or neo ether compounds represented in the specification, p-phenylenediamine compounds represented in JP-A-52-49829 and JP-A-50-15554, JP-A-50-137726, JP-B 44-30074 Quaternary ammonium salts represented in JP-A-56-156826 and JP-A-52-43429, U.S. Pat. Nos. 2,494,903, 3,128,182 and 4,230,796. 3,253,919, Japanese Patent Publication No. 41-11431, U.S. Pat. Nos. 2,482,546, 2,596,926, and 3,582,346, etc. Japanese Patent Publication No. 37-16088, No. 42-25201, US Pat. No. 3,128,183, Japanese Patent Publication No. 41-11431, No. 42-23883, and US Pat. Polyalkylene oxide, other 1-phenyl-3-virazolitones or imidazoles represented in each publication or specification such as 3,532,501 can be added as necessary. The concentration thereof is 0.001 to 0.2 mol, preferably 0.01 to 0.05 mol, per liter for both the color developing composition and the replenisher thereof.

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

  A surfactant such as alkyl sulfonic acid, aryl sulfonic acid, aliphatic carboxylic acid or aromatic carboxylic acid may be added to the color development processing composition as necessary. Their concentration is preferably 0.0001 to 0.2 mol per liter for both the color developer and its replenisher, and more preferably 0.001 to 0.05 mol.

  If necessary, a fluorescent whitening agent or the triazine compound can be added to the color development processing composition. As the optical brightener, the bis (triazinylamino) stilbene sulfonic acid compound described above is preferable. Among these, Chino Pearl SFP, Blankophor BSU liq. Hakkol BRK and Hakkol 508 are preferable. Further, the amount of the fluorescent brightening agent or triazine compound added is preferably 0.1 mmol to 0.1 mol per liter of the color development processing composition.

In a color development processing composition for a color negative film, bromine ions are usually 0.2 × 10 ^{−2 to} 15.0 × 10 ⁻² mol / liter, preferably 0.5 × 10 ^{−2 to} 5.0 × 10. ^In many cases, it is contained at ^-2 mol / liter, but bromine ions are usually released as a by-product of development into the working solution, so it is often unnecessary to add to the replenisher. Further, iodine ions are often contained in an amount of 0.2 × 10 ^{−3 to} 15.0 × 10 ⁻³ mol / liter, preferably 0.5 × 10 ^{−3 to} 5.0 × 10 ⁻³ mol / liter. In general, iodine ions are also sometimes released into the working solution as a by-product of development, so that it is often unnecessary to add to the replenisher.

Color development processing compositions for color paper 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 many cases, it is unnecessary to add to the replenisher because it is released as a product into the working solution.

  Next, the bleaching composition or the bleach-fixing composition used in the bleaching process or the bleach-fixing process will be described.

  In the present invention, the bleaching composition or the bleach-fixing composition contains any bleaching agent such as ferric complex salts of organic acids such as citric acid, tartaric acid, malic acid, persulfate, and hydrogen peroxide as the bleaching agent. Among them, a ferric complex salt complexed from aminopolycarboxylic acid is preferable from the viewpoint of rapid suitability for treatment and environmental suitability. Examples of aminopolycarboxylic acid ferric complex salts include ethylenediamine disuccinic acid (S, S form), N- (2-carboxylateethyl) -L-aspartic acid, betaalanine diacetic acid, methyliminodiacetic acid, and ethylenediamine. Ferric iron with aminopolycarboxylic acids such as tetraacetic acid, diethylenetriaminepentaacetic acid, 1,3-diaminopropanetetraacetic acid, propylenediaminetetraacetic acid, nitrilotriacetic acid, cyclohexanediaminetetraacetic acid, iminodiacetic acid, glycol etherdiaminetetraacetic acid A complex salt etc. can be mentioned, The sodium salt, potassium salt, lithium salt, or ammonium salt of these compounds can be used arbitrarily. Among these, the second of ethylenediamine disuccinic acid (S, S form), N- (2-carboxylate ethyl) -L-aspartic acid, ethylenediaminetetraacetic acid, 1,3-diaminopropanetetraacetic acid, methyliminodiacetic acid. An iron complex salt is preferable from the viewpoint of good bleaching performance.

  These ferric complex salts may be used in the form of complex salts, for example, ferric sulfate, ferric chloride, ferric nitrate, ferric ammonium sulfate, ferric phosphate, and the amino acids described above. It may be complexed with a polycarboxylic acid in solution.

  The molar ratio between the aminopolycarboxylic acid and the iron ion is preferably in the range of aminopolycarboxylic acid: iron ion = 1.001: 1.00 to 1.10: 1.00 in view of the stability of the chelate structure. It is. The aforementioned bleaching agent may be used alone or in combination of two or more.

  The concentration of the bleaching agent is preferably in the range of 0.01 to 1.5 mol, more preferably 0.02 to 0.8 mol / liter, per liter of the bleaching processing composition or bleach-fixing processing composition. By setting it as this range, it is excellent in low replenishment suitability and processability under rapid conditions. Moreover, the preferable pH in a bleaching process composition is 3.0-7.0, and 3.5-6.5 are especially preferable. On the other hand, in the bleach-fixing processing solution, the preferred pH is 3.0 to 8.0, more preferably 4.0 to 7.5. In the above pH range, not only high bleaching ability can be obtained, but also stain and the like are not generated, and excellent processing performance can be obtained. To adjust to the above pH range, various organic acid salts (for example, acetic acid, lactic acid, glycolic acid, succinic acid, maleic acid, malonic acid, citric acid, sulfosuccinic acid, tartaric acid, glutaric acid, etc.), organic bases ( For example, imidazole, dimethylimidazole, etc.), 2-picolinic acid, kojic acid, or the like can be applied. Among these, imidazole, glycolic acid, succinic acid, and maleic acid are preferable because they have a relatively small influence on the bleaching ability. The addition amount is preferably 0.05 to 3.0 mol, more preferably 0.2 to 1.0 mol, per liter of the bleach-fixing treatment composition.

  Further, in the bleaching processing composition or the bleach-fixing processing composition, the sulfinic acid compound represented by the general formula [I] according to the present invention is about 0.01 to 3.0 mol per liter of each processing composition. It may be contained.

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

  In addition, a phosphate or polyphosphate phosphate may be added. Examples of the phosphate include ammonium dihydrogen phosphate, diammonium hydrogen phosphate, triammonium phosphate, potassium dihydrogen phosphate, dipotassium hydrogen phosphate, tripotassium phosphate, sodium dihydrogen phosphate, disodium hydrogen phosphate, and trisodium phosphate. be able to. Specific compounds of the polyphosphate include sodium hexametaphosphate, sodium tetraphosphate, hydroxyethane diphosphonic acid, N (-2-carboxyethyl) -1-aminoethane-1,1-diphosphonic acid, N, N-bis -(Carboxymethylene) -1-aminoethane-1,1-diphosphonic acid, morpholinomethane-diphosphonic acid, nitrilotrismethylene-phosphonic acid, ethylenediamine-tetramethylenephosphonic acid, hexamethylenediaminetetramethylenephosphonic acid, 2-phosphonobutane-1 2,2-tricarboxylic acid, 2-carboxyethane-phosphonic acid, methylenediphosphonic acid and the like. These phosphates or polyphosphates may be used alone or in combination of two or more, and the addition concentration is preferably 0.01 mol to 2.5 mol per liter of the bleaching or bleach-fixing treatment composition.

  Further, it may contain a fluorescent brightening agent such as bis (triazinylamino) stilbene sulfonic acid. These concentrations are preferably from 0.1 mmol to 0.01 mol per liter of bleaching or bleach-fixing processing solution.

  You may contain the said triazine type compound. These addition concentrations are 0.02 to 20 mmol, more preferably 0.05 to 10 mmol, particularly preferably 0.1 to 5 mmol, per liter of the bleaching processing composition or the bleach-fixing processing composition.

  A nitrate such as ammonium nitrate, sodium nitrate or potassium nitrate can be added, and the addition concentration is preferably 0.5 to 7.0 mol per liter of the bleaching or bleach-fixing treatment composition. Moreover, organic solvents, such as various antifoamers or surfactant, the said poly-N-vinyl-2- pyrrolidone, and methanol, can also be contained.

  In the bleaching processing composition or the bleach-fixing processing composition, it is preferable to use ammonium ions when considering rapid processing suitability. On the other hand, when the emphasis is placed on work environment, it substantially contains ammonium ions. Preferably not.

  The bleach-fixing composition preferably contains a preservative from the viewpoint of the temporal stability of the fixing agent described below. Preservatives include sulfites (for example, sodium sulfite, potassium sulfite, ammonium sulfite, ammonium bisulfite, sodium bisulfite, potassium bisulfite, potassium metabisulfite, sodium metabisulfite, ammonium metabisulfite, etc.) or sulfite An ion releasing compound or the like is preferable. The concentration is preferably 0.02 mol to 1.0 mol in terms of sulfite ion per liter.

  Next, the fixing main agent contained in the bleach-fixing processing composition will be described.

  As the fixing main agent, a known silver halide solvent can be used, and examples thereof include alkali metal salts and ammonium salts of thiosulfates such as potassium thiosulfate, sodium thiosulfate or ammonium thiosulfate. Other examples include alkali metal salts and ammonium salts of thiocyanate such as sodium thiocyanate and ammonium thiocyanate. The concentration of the fixing agent is preferably from 0.3 to 5 mol, more preferably from 0.5 to 3.5 mol, per liter of the bleach-fixing processing composition. These may be used alone or in combination of two or more. Other secondary fixing agents include one or more thioether compounds such as ethylenebisthioglycolic acid and 3,6-dithia-1,8-octanediol, and thioureas such as thiourea and ethylenethiourea. It may be included in combination. The concentration of these secondary fixing main agents is preferably 1.8 mol / L or less, more preferably 0.1 to 1.6 mol / L.

  Next, the fixing treatment composition will be described.

  The fixing processing composition contains the fixing main agent (for example, potassium thiosulfate, sodium thiosulfate, or ammonium thiosulfate) that is a known silver halide solubilizer, and if necessary, a secondary fixing main agent (for example, Thioether compounds such as ethylenebisthioglycolic acid and 3,6-dithia-1,8-octanediol, and thiourea and ethylenethiourea). The concentration of the fixing main agent is preferably 0.3 to 5 mol, more preferably 0.5 to 3.5 mol, per liter of the fixing processing composition. Further, the pH of the fixing treatment composition is preferably 4 to 9, and more preferably 5.5 to 8. When the pH is in the above range, not only excellent fixing ability is obtained, but also no odor or the like is generated, and good processing performance is obtained. In order to adjust to the said pH range, the said organic base (For example, imidazole, dimethylimidazole etc.) etc. are mentioned. The fixing processing composition preferably contains a sulfite or a sulfinic acid compound from the viewpoint of stability over time of the processing solution, and the concentration is 0 in terms of sulfite ions or sulfinic acid ions per liter of the fixing processing solution. 0.02 mol to 1.0 mol is preferred.

  Next, the silver halide color photosensitive material used in the development processing step will be described.

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

  For example, a color negative film, a color reversal film, a color paper, a color movie film, etc. can be mentioned. A color negative film or color paper is preferred.

  As typical constituent elements of the silver halide color photographic light-sensitive material, the details are described in, for example, the following Research Disclosure (hereinafter abbreviated as RD) and can be referred to.

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

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

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

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

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

  Next, a processing apparatus (automatic developing machine) when the development processing is performed by a machine will be described.

In the present invention, the automatic processor preferably has a linear velocity of conveyance of 100 mm / second or less, more preferably 27.8 mm / second to 80 mm / second, and particularly preferably 27.8 mm / second to 50 mm / second. . In the automatic paper color developer transport system, the color paper is cut to the final size before development processing (sheet-type transport method), and the paper is developed with a long roll and cut to the final size after processing (cine). Mold conveyance system). The cine type conveyance method is preferably a sheet type conveyance method because a photosensitive material of about 2 mm is wasted between images. The treatment composition according to the present invention is preferably as small as possible in the treatment tank and the replenisher tank. For example, when the opening ratio is a value obtained by dividing the opening area (cm ² ) by the liquid tank (cm ³ ) in the tank, the opening ratio is preferably 0.08 (cm ⁻¹ ) or less. In order to reduce the area in contact with air, it is preferable to provide solid or liquid air non-contact means that floats on the liquid surface in the treatment tank and the replenishment tank.

Specifically, it is preferable to cover a plastic float or the like on a liquid surface or a liquid that does not mix with the processing liquid and does not cause a chemical reaction. Examples of the liquid include liquid paraffin and liquid saturated hydrocarbons. Etc. In order to perform processing rapidly with an automatic developing machine, it is preferable to set the air time during which the photosensitive material moves between the processing solutions, that is, the crossover time, to be equal to or less than the above-described time. 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. Further, as a method for eliminating the crossover time, it is preferable to use a submerged conveyance structure using a blade described in JP-A-2002-55422. The submerged conveying structure using this blade is preferably a liquid circulation structure in which the liquid circulation direction flows downward as described in JP-A No. 2002-339383, and a porous material pleated filter is installed in the circulation system. Moreover, it is preferable to perform so-called evaporation correction in which water corresponding to the amount of evaporation of the processing liquid is supplied to each processing liquid according to the present invention. In particular, it is preferable in a color developing tank solution and a bleach-fixing tank solution. A specific method for performing such water replenishment is not particularly limited, but a monitor water tank different from the bleach-fixing tank described in JP-A-1-254959 and 1-254960 is installed, and the monitor Calculate the amount of water evaporation in the tank, calculate the amount of water evaporation in the bleach-fixing tank from this amount of water evaporation, replenish the water to the bleach-fixing tank in proportion to this amount of evaporation, liquid level sensor, and overflow An evaporation correction method using a sensor is preferred. The most preferable evaporation correction method is to predict and add water corresponding to the amount of evaporation, and is described in the Japanese Institute of Invention and Technology Publication No. 94-49925, page 1, right column, line 26 to page 3, left column, line 28. As described above, the amount of water calculated by a coefficient determined in advance based on the information on the operation time, stop time, and temperature control time of the automatic processor is added. Further, a device for reducing the evaporation amount is also required, and it is required to reduce the opening area and adjust the air volume of the exhaust fan. As means for reducing the evaporation amount, it is particularly preferable to “keep the humidity of the upper space of the treatment tank at 80% RH or more” described in JP-A-6-110171, and the evaporation prevention rack described in FIGS. A structure having a roller automatic cleaning mechanism is particularly preferable. Although the exhaust fan is mounted normal to prevent dew condensation at the temperature control, a preferable exhaust amount per minute 0.1 m ³ to 1 m ^3, particularly preferably at 0.2m ³ ~0.4m ³ is there. The drying conditions of the photosensitive material also affect the evaporation of the processing solution. The drying method is preferably a ceramic hot air heater is preferably min 4m ³ to 20 m ³ as feed air volume, particularly 6 m ³ through 10m ³ preferred. The thermostat for preventing the heating of the ceramic warm air heater is preferably operated by heat transfer, and the mounting position is preferably leeward or upwind through the radiating fins and the heat transfer section. The drying temperature is preferably adjusted according to the water content of the photosensitive material to be processed. The optimum temperature is 50 to 70 ° C. for color paper, 45 to 55 ° C. for APS format and 35 mm wide film, and 55 to 65 ° C. for Brownie film. is there. The drying time is preferably 5 seconds to 2 minutes, more preferably 5 seconds to 60 seconds. A replenishment pump is used for replenishing the working solution, but a bellows type replenishment pump is preferred. In addition, as a replenishment method, the concentrated treatment composition may be added directly to the treatment tank, and water corresponding to the dilution ratio may be added directly to the treatment tank, and the concentrated treatment composition is dissolved and diluted in the replenishment tank. It may be replenished as a replenisher, or it may be replenished as a replenisher by automatically dissolving and diluting the concentrated treatment composition using an automatic preparation device in a replenishment tank. As a method for improving the replenishment accuracy, it is effective to reduce the diameter of the liquid feeding tube to the replenishing nozzle in order to prevent backflow when the pump is stopped. A preferable inner diameter is 1 to 8 mm, and a particularly preferable inner diameter is 2 to 5 mm. Next, various component materials used in the automatic processor will be described below.

  The tank material such as the treatment tank and the temperature control tank is preferably modified PPO (modified polyphenylene oxide) or modified PPE (modified polyphenylene ether) resin. Examples of the modified PPO include “Noryl” manufactured by GE Plastics Japan, and the modified PPE includes “Zylon” manufactured by Asahi Kasei Kogyo, “Iupiace” manufactured by Mitsubishi Gas Chemical, and the like. Moreover, these materials are suitable for parts that may come into contact with the processing liquid such as processing racks and crossovers. Resin such as PVC (polyvinyl chloride), PP (polypropylene), PE (polyethylene), TPX (polymethylpentene) is suitable for the roller material of the processing section. These materials can also be used for other processing liquid contact portions. In addition, PE resin is preferable also for the material of the replenishment tank by blow formation. PA (polyamide), PBT (polybutylene terephthalate), UHMPE (ultra high molecular weight polyethylene), PPS (polyphenylene sulfide), LCP (fully aromatic polyester resin, liquid crystal polymer) ) Etc. are suitable. PA resin is polyamide resin such as 66 nylon, 12 nylon, and 6 nylon, and those containing glass fiber or carbon fiber are strong against swelling by the treatment liquid and can be used. 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”, “Hi-Zex Million” manufactured by Mitsui Petrochemical Co., Ltd., “New Light” manufactured by Sakushin Kogyo Co., Ltd. “Sunfine” is suitable. The molecular weight is preferably 1,000,000 or more, more preferably 1,000,000 to 5,000,000. The PPS resin is preferably glass fiber or carbon fiber reinforced. The LCP resin includes “Victrex” manufactured by ICI Japan, “Econol” manufactured by Sumitomo Chemical, “Zider” manufactured by Nippon Oil Co., Ltd., “Vectra” manufactured by Polyplastics Co., Ltd., etc. included. In particular, the material of the conveyor belt is preferably an ultrahigh strength polyethylene fiber or polyvinylidene fluoride resin described in JP-A-4-151656. As a soft material such as a squeeze roller, a foamed vinyl chloride resin, a foamed silicon resin, and a foamed urethane resin are suitable. Examples of the urethane foam resin include “Rubicel” manufactured by Toyo Polymer Co., Ltd. EPDM rubber, silicon rubber, Viton rubber and the like are preferable as rubber materials such as a pipe joint, an agitation jet pipe joint, and a sealing material. In addition, the replenisher used in the automatic developing machine may be in the form of a cartridge in which the replenisher for each process is individually made into a product form. It is preferable that the automatic processor has.

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

Example 1
<< Preparation of the stabilization composition for stabilization treatment >>
Concentrated compositions for stabilization treatment 1-1 to 1-53 having the following composition were prepared.

Ethylenediaminetetraacetic acid 50.0g
1-hydroxyethylidene-1,1-diphosphonic acid 40.0 g
Benzoisothiazolin-3-one 5.0 g
Triazine compound (T-1) 20.0g
Alkylene oxides: Compounds represented by general formula [II] (compounds described in Tables 1 and 2) Addition amounts described in Tables 1 and 2 Sulfinic acid derivatives: Compounds represented by general formula [I] (Table 1) 2)
Addition amounts listed in Tables 1 and 2 Alkaline agent ^{* 1)} (Compounds listed in Tables 1 and 2) Addition amounts listed in Tables 1 and 2 Using pure water, finish to 1 L and adjust pH to 7.3 did.

  * 1) Alkaline agent is a supply material of a counter cation necessary for adjusting to a predetermined pH (pH 7.3), and a concentrated composition whose pH does not become 7.3 with the addition amount shown in Table 1 Then, ammonium hydroxide or 50% sulfuric acid was appropriately added for adjustment. Moreover, pH of the concentrated composition 1-1 for stabilization treatment was adjusted with ammonium hydroxide.

《Storage in packaging container》
Each of the prepared concentrated compositions for stabilization treatment has a porosity of 20% in a packaging container in which the thickness and material of the plastic are appropriately selected and adjusted so that the oxygen permeability coefficient is 50 ml / m ² · day · atm. It was loaded and stored for 2 months in a constant temperature bath at 50 ° C. Subsequently, the precipitation resistance and the container expansion resistance of the concentrated composition for stabilization treatment after storage were evaluated. The obtained results are shown in Tables 1 and 2.

[Evaluation of precipitation resistance]
The concentrated composition for stabilization treatment after the storage and the soiled state of the container were visually observed, and precipitation resistance was evaluated according to the following criteria.

◎: No precipitate was observed in the concentrated composition for stabilization after storage, and no deposits or dirt adhered to the inner wall of the container. ○: In the concentrated composition for stabilization after storage Although no generation of precipitates is observed, slight deposits or dirt are observed on the inner wall of the container. Δ: Generation of precipitates is observed in the concentrated composition for stabilization after storage, and the inner wall of the container is Slight deposits or dirt adherence is observed, and this is a quality that is a problem in practical use. ×: The occurrence of obvious precipitates is observed in the concentrated composition for stabilization after storage, and the precipitate is deposited on the inner wall of the container. Adherence to objects or dirt is recognized, and this is a quality that is problematic in practice. [Evaluation of container expansion resistance]
The container state of the concentrated composition for stabilization treatment after storage was visually observed, and the container expansion resistance was evaluated according to the following criteria.

◎: Deformation and breakage of the container are not observed. ○: Although slight expansion is observed in the container, there is no problem in practical use. △: Expansion of the container is observed, and the quality is problematic in practical use and product image. Strong expansion of the container occurs, damage, cracks and liquid leakage are observed in a part of the container, and this is a quality that is practically problematic.

  As apparent from the results shown in Tables 1 and 2, ammonium ions have been conventionally used for pH adjustment, but as a result of replacing them with sodium ions or potassium ions as shown in Tables 1 and 2, sodium ions were obtained. Alternatively, when the potassium ion is in the concentration range of 0.05 mol / L or more and 8.0 mol / L or less of the present invention, by adding alkylene oxides represented by the general formula [II], It can be seen that it is excellent in resistance and container expansion resistance, and exhibits an effect of excellent long-term storage stability in a high temperature environment.

  Further, among the configurations of the present invention, sodium ion or potassium ion exhibits particularly good container expansion resistance when the concentration range of the present invention is 0.25 mol / L or more and 6.0 mol / L or less. Among the constitutions, it can be seen that the above effect is more exerted by including the sulfinic acid derivative represented by the general formula [I].

Example 2
<< Preparation of Stabilized Concentration Compositions 2-1 to 2-12 >>
In the preparation of the concentration compositions for stabilization treatment 1-4 and 1-12 described in Example 1, the addition amount of the alkaline agent (mol / L) was changed in the same manner as described in Table 3, Concentrated compositions for stabilization treatment 2-1 to 2-12 were prepared.

<< Evaluation of low-temperature precipitation resistance of concentrated composition for stabilization treatment >>
90 ml of each of the above-prepared stabilized compositions 2-1 to 2-12 and the stabilized compositions 1-4 and 1-12 prepared in Example 1 were stored in a 100 ml glass bottle. Then, low temperature precipitation tolerance was evaluated according to the following method.

[Evaluation of low temperature precipitation resistance]
10 mg of a mixed crystal (1: 1) of ethylenediaminetetraacetic acid and 1-hydroxyethylidene-1,1-diphosphonic acid was added as a crystal nucleus to each concentrated composition for stabilization treatment placed in a glass bottle, and then sealed. Then, after storing these for 2 weeks in an environment of −8 ° C., the state of the concentrated composition for stabilization treatment was visually observed, and low temperature precipitation resistance was evaluated according to the following criteria.

A: No increase in crystals is observed. O: Almost no increase in crystals is observed. Δ: A slight increase in crystals is observed. X: A large amount of precipitated crystals is observed. Table 3 shows the results obtained as described above. Shown in

  As is clear from the results shown in Table 3, the sodium ion is contained in an amount of 0.05 mol / L or more and 8.0 mol / L or less, and the alkylene oxides represented by the general formula [II] are contained. It can be seen that the concentrated composition for stabilization treatment is superior to the comparative example in low-temperature precipitation resistance when stored in an extremely low temperature environment of -8 ° C. Furthermore, among the concentrated compositions for stabilization treatment of the present invention, the sodium ion is in the range of 0.25 mol / L or more and 6.0 mol / L or less, compared with a comparative example containing the same concentration of sodium ions at low temperature. It turns out that the improvement effect of tolerance is remarkable.

Example 3
<< Preparation of Stabilized Concentration Compositions 3-1 to 3-7 >>
In the preparation of the stabilizing composition 1-12 described in Example 1, the same procedure except that the pH was changed as shown in Table 4 was followed. 7 was prepared.

<< Evaluation of Concentrated Composition for Stabilization >>
Each of the prepared concentrated compositions for stabilization treatment has a porosity of 20% in a packaging container in which the thickness and material of the plastic are appropriately selected and adjusted so that the oxygen permeability coefficient is 50 ml / m ² · day · atm. It was loaded and stored in a constant temperature bath at 65 ° C. for 2 months. Next, the precipitation resistance and the container expansion resistance were evaluated for the concentrated composition for stabilization treatment in the same manner as in the method described in Example 1. Table 4 shows the obtained results.

  As is clear from the results shown in Table 4, under more severe high-temperature storage conditions, the pH of the concentrated composition for stabilization treatment of the present invention was in the range of 4.0 to 10.0, which was particularly excellent. It can be seen that it exhibits precipitation resistance and container expansion resistance.

Example 4
A plastic container having an oxygen permeability coefficient shown in Table 5 was produced by appropriately adjusting the thickness and material of the plastic.

  Each of the produced plastic containers was filled with the stabilization composition 1-12 described in Example 1 at a porosity of 20%, and then stored in a thermostatic bath at 65 ° C. for 4 months. 4-1 to 4-6.

  Subsequently, the preservation | save samples 4-1 to 4-6 were evaluated in the same manner as in Example 1 for deposition resistance and container expansion resistance. Table 5 shows the obtained results.

As is clear from the results shown in Table 5, under a more severe storage environment, particularly excellent precipitation resistance and container expansion resistance are obtained if the oxygen permeability coefficient of the container to be stored is 50 ml / m ² · atm · day or less. If it is 20 ml / m ₂ · atm · day or less, it can be seen that it is even better.

Example 5
<< Preparation of silver halide color photographic material >>
In accordance with the following method, a color paper which is a silver halide color photographic material for reflection viewing was prepared.

High-density polyethylene was laminated on both sides of a paper pulp having a basis weight of 180 g / m ² to prepare a paper support. However, the reflective support A was prepared by laminating a melted polyethylene containing a dispersion of anatase-type titanium oxide (content: 15% by mass) on the side on which each emulsion layer was applied. After the reflective support A was subjected to corona discharge treatment, a gelatin subbing layer was provided, and each constituent layer having the following constitution was further applied to prepare a sample 101 which was a color paper. However, in Tables 6 and 7, the addition amount of the silver halide emulsion is described in terms of silver.

In the preparation of the sample 101, (H-1) and (H-2) were added as hardeners. As coating aids, surfactants (SU-2) and (SU-3) were added to adjust the surface tension. Further, F-1 was added to each layer so that the total amount was 0.04 g / m ² .

  The details of each additive listed in Tables 6 and 7 are as follows.

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

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

  The following compounds were used for the above EMP-1, and chemical sensitization was performed so that the sensitivity-fogging relationship was optimized. Similarly, after chemical sensitization to optimize the sensitivity-fogging relationship for EMP-1B, the sensitized EMP-1 and EMP-1B are each in a silver ratio of 1: 1. By mixing, a blue-sensitive silver halide emulsion (Em-B) was prepared.

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

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

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

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

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

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

<< Exposure and development process >>
After performing imagewise exposure from a color negative film on which a live-action scene was photographed using sample 101, which was the color paper produced as described above, the processing amount of sample 101 per day was 10 m ² , and the following until it reached 2R: Continuous processing (running processing) was performed under the development processing conditions. Note that 2R means that a stabilizing replenisher twice as much as the capacity of the stabilizing tank liquid is replenished. Further, as a developing processor, a processing machine modified from an automatic developing machine NPS-808GOLD manufactured by Konica Minolta Photo Imaging Co., Ltd. so as to satisfy the following processing conditions was used.

[Development processing conditions]
(Processing process) (Processing temperature) (Time) (Replenishment amount) (Tank capacity)
Color development 40.0 ° C 25 seconds 80ml / m ² 125L
Bleaching fixing 38.0 ° C 25 seconds 100ml / m ² 12.3L
Stabilization-1 38.0 ℃ 25 seconds 11.8L
Stabilization-2 38.0 ℃ 25 seconds 11.8L
Stabilization-3 38.0 ° C 25 seconds 200ml / m ² 11.8L
Drying 60 to 80 ° C. 30 seconds In addition, the stabilization process is a multi-stage countercurrent system of stabilization-3 → stabilization-2 → stabilization-1.

[Preparation of each treatment solution]
(Color developing composition: per liter)
Tank liquid Replenisher Diethylene glycol 20.0 g 20.0 g
Sodium p-toluenesulfonate 12.0 g 12.0 g
Potassium chloride 3.0g −
4-Amino-3-methyl-N-ethyl-N- (β- (methanesulfonamido) ethyl) aniline sulfate 6.0 g 12.0 g
N, N-bis (sulfoethyl) hydroxylamine disodium salt
5.0g 10.0g
Potassium carbonate 30.0g 30.0g
Sodium diethylenetriaminepentaacetate 6.0g 6.0g
pH 10.3 12.0
Both the tank liquid and the replenisher were adjusted to 1 L by adding water, and the pH was adjusted using potassium hydroxide or 50% sulfuric acid.

(Bleaching and fixing composition: per liter)
Tank liquid Replenisher Ammonium ferric ammonium tetraacetate 0.2 mol 0.25 mol Ammonium thiosulfate 0.54 mol 0.70 mol Ammonium sulfite 0.15 mol 0.30 mol Succinic acid 16.0 g 20.0 g
Imidazole 8.0 g 10.0 g
pH 6.0 5.5
Both the tank liquid and the replenisher were adjusted to 1 L by adding water, and the pH was adjusted using 25% ammonium hydroxide or 50% sulfuric acid.

(Preparation of stabilization treatment composition)
Concentrated composition for stabilization 1-12 of the present invention and the concentrated composition for stabilization 1-12 of Example 1 described in Example 1 were stored in a thermostat at 50 ° C. for 2 months with water, 25 each. Diluted twice, 0.5 g / L of Tinopearl SFP (Ciba Geigy Corp., fluorescent whitening agent) was added thereto to prepare a stabilizing replenisher and a stabilizing tank.

  The pH of the stabilizing replenisher and the stabilizing tank solution was adjusted to 7.5 using 50% sulfuric acid.

《Characteristic evaluation after continuous processing》
Next, each of the stabilization treatment compositions was used to perform a 2R running process, and then the unexposed sample 101 was processed. The reflection density of the white background was measured using a reflection densitometer (Spectroscan) manufactured by Gretag Machbeth. The white background characteristics were evaluated by measuring using As a result, both the stabilization treatment composition subjected to the high-temperature storage treatment and the stabilization treatment composition not subjected to the high-temperature storage treatment had the same white background characteristics.

Claims (5)

A concentrated composition for stabilizing processing of a silver halide color photographic material comprising sodium ion or potassium ion in an amount of 0.05 mol / L or more and 8.0 mol / L or less and an alkylene oxide. . 2. The concentrated composition for stabilizing processing of a silver halide color photographic material according to claim 1, wherein the concentration of the sodium ion or potassium ion is 0.25 mol / L or more and 6.0 mol / L or less. object. The concentrated composition for stabilizing processing of a silver halide color photographic material according to claim 1 or 2, wherein the pH is 4.0 or more and 10.0 or less. The concentrated composition for stabilizing processing of a silver halide color photographic material according to any one of claims 1 to 3, comprising a compound represented by the following general formula [I].
Formula [I]
RSO ₂ M
[Wherein, R represents an alkyl group, a cycloalkyl group, an alkenyl group, an alkynyl group, a heterocyclic group or an aryl group. M represents a hydrogen atom, an alkali metal atom, an ammonium group or a quaternary amine. ] The silver halide color photographic photosensitive material according to any one of claims 1 to 4, wherein the silver halide color photographic photosensitive material is packaged with a packaging material, and the oxygen permeability coefficient of the packaging material is 50 ml / m ² · atm · day or less. Concentrated composition for material stabilization treatment.