JP2007093725A - Processing method for silver halide color photographic sensitive material - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a processing method for a silver halide color photographic sensitive material which suppresses occurrence of yellow stain after long-term storage due to contamination of a bleach-fixing solution and has improved abrasion resistance during transport for processing. <P>SOLUTION: In the processing method for the silver halide color photographic sensitive material, the silver halide color photographic sensitive material is processed through a color developing step, a bleach-fixing step, a rinsing, stabilizing or washing step and a drying step, wherein a bleach-fixing solution used in the bleach-fixing step has a surface tension at 20°C of ≤45 mN/m. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a method for processing a silver halide color photographic light-sensitive material having improved stain resistance on white background and scratch resistance during processing conveyance.

  In recent years, the London Convention has been concluded in order to protect the global environment. From January 1, 1996, the disposal of photographic processing wastewater into the ocean was substantially prohibited. For this reason, efforts have been made in the photographic industry to reduce photographic processing wastewater to the limit. As for the fixing solution used in the development processing, studies on the reduction of waste liquid and the reduction of replenishment have been made in JP-A-8-201997.

  In recent years, the number of prints ordered from mini-lab shops often found in photo shops and large-scale retail stores has decreased. In mini-lab development, the price of automatic processing equipment itself has been lowered, and low-replenishment processing agents are also available. Study to reduce running costs such as providing

  However, with the low replenishment in the development processing step, the proportion of the bleach-fixing solution component brought into the stabilization processing solution has increased, and this has caused the development-processed silver halide color photographic light-sensitive material to be preserved. However, the occurrence of stains has been a problem.

  Recently, the number of consumers who print photos at home using home printers such as inkjet printers is increasing rapidly. In such a trend, quick service for developing and receiving prints on the spot has been regarded as an important differentiation item. For this reason, there is an increasing demand for speeding up processing, and many studies on speeding up processing have been made.

  In order to achieve both low replenishment and rapid processing as described above, from the viewpoint of improving the quality of the silver halide color photographic light-sensitive material to be developed, increasing the number of stabilizing tanks or rinsing tanks is also a countermeasure. Although it is one, in addition to an increase in the price of the development processing apparatus itself, it is difficult to say that it is the best measure in terms of space saving.

  On the other hand, when processing a silver halide color photographic light-sensitive material using an automatic developing device comprising a continuous processing tank, for example, a silver halide color photograph is transferred from a bleach-fixing processing tank to a stabilizing processing tank which is the next step. A method of reducing the amount of the bleach-fixing solution brought into the stabilization processing tank, which is the cause of stain, as much as possible by increasing the pressure of a squeeze roller provided in the transfer portion that conveys the photosensitive material is also used. By applying this method, the occurrence of stains when storing the developed silver halide color photographic light-sensitive material is suppressed to some extent, but on the other hand, the bleach-fixing solution adheres to the squeeze roller and dries. The silver halide color photographic light-sensitive material to be transported thereafter causes new problems such as generation of scratches and transport failure (jam).

  In order to improve the occurrence of stains and deterioration of gloss when the developed silver halide color photographic light-sensitive material is stored for a long period of time under the conditions of rapid processing and low replenishment processing, A method has been proposed in which a compound having a specific structure is contained in a silver halide emulsion layer of a silver halide color photographic light-sensitive material (see, for example, Patent Document 1). However, the method disclosed in Patent Document 1 is a method in which an effect is manifested only in a silver halide color photographic light-sensitive material containing a compound having a specific structure, and various types of halogenation such as minilabs. When the silver color photographic light-sensitive material is processed with the same developing device, this is a partial effect, and it must be said that the versatility is extremely low as compared with the method improved by the processing composition or processing method.

In addition, a method for reducing stain as well as improving low temperature precipitation by adding a surfactant to a color development processing agent is disclosed (for example, see Patent Document 2). In the method disclosed in Patent Document 2, the occurrence of stain immediately after processing is certainly reduced to some extent, but there is no reduction in stain when the processed silver halide color photosensitive material is stored for a long period of time. There is no description or suggestion, and there is no mention of the problem of suppressing stains after long-term storage caused by contamination of the bleach-fixing solution.
JP 2005-215431 A JP-A-2005-107158

  The present invention has been made in view of the above problems, and its object is to reduce the occurrence of yellow stains after long-term storage due to contamination of the bleach-fixing solution, and to improve the scratch resistance during processing conveyance. It is an object of the present invention to provide a method for processing a silver halide color photographic light-sensitive material.

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

  (1) In a method for processing a silver halide color photographic light-sensitive material, wherein the silver halide color photographic light-sensitive material is processed through a color development processing step, a bleach-fixing processing step, a rinsing, a stabilization or washing step, and a drying step. A method for processing a silver halide color photographic light-sensitive material, wherein the bleach-fixing solution used in the bleach-fixing step has a surface tension at 20 ° C. of 45 mN / m or less.

  (2) The method for processing a silver halide color photographic light-sensitive material as described in (1) above, wherein the bleach-fixing solution has a surface tension at 20 ° C. of 35 mN / m or less.

  (3) In the item (1) or (2), the bleach-fixing solution contains at least one compound selected from compounds represented by the following general formulas (I) to (IV): A method for processing a silver halide color photographic light-sensitive material as described.

[Wherein, R ₁ represents an alkyl group or an alkenyl group, R ₂ represents a hydrogen atom, an alkyl group or a hydroxyalkyl group, and R ₃ and R ₄ independently represent a hydrogen atom, a hydroxyl group, an alkyl group or —COOM ₄ ( M ₄ represents a hydrogen atom or an alkali metal atom), X represents —CO— or —SO ₂ —, Y represents —O—, —S— or —CONR ₅ — (R ₅ represents a hydrogen atom, alkyl) M ₃ represents a hydrogen atom or an alkali metal atom, k represents 0 or 1, m1 represents an integer of 0 to 2, and n1 represents an integer of 1 to 3. ]
Formula (II)
R _6- (O) _x SO ₃ M ₆
[Wherein R ₆ represents an aliphatic group, alicyclic group, aromatic group or heterocyclic group, x represents 0 or 1, and M ₆ represents a cation. ]

[Wherein R ₇ represents an alkyl group having 1 to 2 carbon atoms, or a hydrogen atom, and R ₈ represents a substituted or unsubstituted alkyl group having 1 to 3 carbon atoms, a sulfonic acid group, a carboxyl group, a hydroxyl group, Alternatively, it represents a hydrogen atom, and R ₉ represents a hydrogen atom or a hydroxyl group. p represents an integer of 0 to 2, and r represents an integer of 1 to 3. A may be substituted with a hydrogen atom at any position of the benzene ring. Further, s represents 0 to 50, t represents an integer of 0 or 1, and u represents a number of 2 to 150. ]

[Wherein, R ¹ represents an alkyl group or alkenyl group having 8 to 21 carbon atoms in total. M represents a hydrogen atom or a metal cation. Z ¹ represents NH ₂ or OM ′, M ′ represents a hydrogen atom or a metal cation, and may be the same as or different from M. n represents 1 or 2. ]
(4) At least one of the modes of transporting the silver halide color photographic light-sensitive material between the bleach-fixing step and the final processing step is a submerged transport method, wherein (1) to (4) The method for processing a silver halide color photographic light-sensitive material according to any one of the above.

  According to the present invention, there is provided a method for processing a silver halide color photographic light-sensitive material that suppresses the occurrence of yellow stain after long-term storage, which is considered to be caused by contamination of the bleach-fixing solution, and has improved scratch resistance during processing conveyance. I was able to.

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

  As a result of intensive studies in view of the above problems, the present inventor has processed a silver halide color photographic light-sensitive material through a color development processing step, a bleach-fixing processing step, a rinse, a stabilization or a water washing processing step, and a drying processing step. In the processing method of silver halide color photographic light-sensitive material to be processed, the surface tension at 20 ° C. of the bleach-fixing solution used in the bleach-fixing step is 45 mN / m or less. This method can realize a method for processing a silver halide color photographic light-sensitive material that suppresses the occurrence of yellow stain after long-term storage, which is considered to be caused by contamination of the bleach-fixing solution, and has improved scratch resistance during processing conveyance. It is up to the headline and the present invention.

  That is, the present inventor made a bleach-fixing operation during the transfer from the bleach-fixing tank to the stabilizing tank (crossover part) in the color development processing step, the bleach-fixing processing step, the rinsing, the stabilization or the water-washing processing step, and the drying processing step. As a result of repeated studies on a method for preventing contamination of the bleach-fixing solution to the stabilizing solution due to entrainment with the silver halide color photographic light-sensitive material conveyed, the surface tension value of the bleach-fixing solution is 45 mN / m or less, More preferably, by setting to 35 mN / m or less, the amount of the bleach-fixing solution accompanying the silver halide color photographic light-sensitive material can be greatly reduced, and the pressure of the squeeze roller provided with the transition portion is increased. Even in this case, the removability of the bleach-fixing solution from the silver halide color photographic light-sensitive material was increased, and the amount of adhesion to the squeeze roller could be reduced. As a result, the amount of contamination in the stabilization tank, which is the next step, can be reduced, so that the occurrence of yellow stain after long-term storage can be suppressed, and continuous processing is performed as the amount of adhesion to the squeeze roller is reduced. It was possible to reduce the occurrence of scratches on the silver halide color photographic light-sensitive material.

  Details of the present invention will be described below.

  In the processing method of the silver halide color photographic light-sensitive material of the present invention (hereinafter also simply referred to as the processing method of the present invention), the processing steps are a color development processing step, a bleach-fixing processing step, a rinse, stabilization or water washing processing step, and The surface tension at 20 ° C. of the bleach-fixing solution used in the bleach-fixing processing step is 45 mN / m or less, preferably 20 mN / m or less, preferably 45 mN / m or less. More preferably, it is 35 mN / m or less, More preferably, it is 20 mN / m or less, 35 mN / m or less.

  The surface tension referred to in the present invention represents a static surface tension at 20 ° C., and a method for measuring the static surface tension is described in general interface chemistry, colloid chemistry reference books, etc. New Experimental Chemistry Lecture Volume 18 (Interface and Colloid), The Chemical Society of Japan, published by Maruzen Co., Ltd. 68-117. Specifically, it can be determined by using the ring method (Dunoi method) or the platinum plate method (Wilhelmy method). In the present invention, the bleach-fixing solution is made of platinum. The static surface tension value measured at 20 ° C. by the plate method is used.

  In the processing method of the present invention, as a method of adjusting the surface tension of the bleach-fixing solution at 20 ° C. within the range specified in the present invention, a method of adding a surfactant or the like to the bleach-fixing solution, or a silver halide color Examples thereof include a method in which a surfactant is added to a photographic light-sensitive material and eluted in a bleach-fixing solution. From the viewpoint of further achieving the object effects of the present invention, at least one compound selected from the compounds represented by the general formulas (I) to (IV) (anionic surfactants) is added to the bleach-fixing solution. It is preferable to adjust the surface tension as defined above.

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

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

In the general formula (I), R ₁ represents an alkyl group or an alkenyl group, R ₂ represents a hydrogen atom, an alkyl group or a hydroxyalkyl group, and R ₃ and R ₄ independently represent a hydrogen atom, a hydroxyl group, an alkyl group or —COOM ₄ (M ₄ represents a hydrogen atom or an alkali metal atom), X represents —CO— or —SO ₂ —, and the alkyl group represented by R _{1 to} R ₅ represents a substituent (for example, a hydroxyl group). And those having a carboxyl group). Y represents —O—, —S— or —CONR ₅ — (R ₅ represents a hydrogen atom, an alkyl group or a hydroxyalkyl group), M ₃ represents a hydrogen atom or an alkali metal atom, and k represents 0 or 1 , M1 represents an integer of 0 to 2, and n1 represents an integer of 1 to 3.

In the general formula (I), R ₁ is preferably a linear or branched alkyl group or alkenyl group having 5 to 20 carbon atoms, and R ₂ is preferably a hydrogen atom or a linear or branched group having 1 to 5 carbon atoms. An alkyl group or a hydroxyalkyl group;

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

  In addition to the compounds exemplified above, exemplified compounds [II] -1 to [II] -55 described in JP-A No. 62-56961, pages 4 to 6 can also be used.

  The above exemplified compounds are known compounds or are commercially available and can be obtained by ordinary routes.

  Next, the anionic surfactant represented by the general formula (II) will be described.

In the general formula (II), R ₆ represents an aliphatic group, an alicyclic group, an aromatic group or a heterocyclic group, and includes those having a substituent. x represents 0 or 1, and M ₆ represents a cation.

In the general formula (II), examples of the aliphatic group represented by R ₆ include an alkyl group, an alkenyl group, and an alkynyl group. Examples of the alkyl group include methyl, ethyl, i-propyl, butyl, t- Examples thereof include butyl, pentyl, hexyl, octyl, dodecyl and the like. These alkyl groups are further halogen atoms (for example, halogen atoms such as chlorine, bromine and fluorine), alkoxy groups (for example, methoxy, ethoxy, 1,1-dimethylethoxy, hexyloxy, dodecyloxy and the like), Aryloxy groups (eg, phenoxy, naphthyloxy, etc.), alkoxycarbonyl groups (eg, methoxycarbonyl, ethoxycarbonyl, butoxycarbonyl, 2-ethylhexyloxycarbonyl, etc.), alkenyl groups (eg, vinyl, allyl) Each group such as 2-pyridyl, 3-pyridyl, 4-pyridyl, morpholyl, piperidyl, piperazyl, pyrimidinyl, pyrazolinyl, furyl, etc.], alkynyl group (for example, propargyl group, etc.) An amino group (for example, amino, N, N- Each group such as methylamino and anilino), cyano group, sulfoamido group (for example, each group such as methylsulfonylamino, ethylsulfonylamino, butylsulfonylamino, octylsulfonylamino, phenylsulfonylamino), acylamino group (for example, dodecanoyl) And those substituted with an amino group or the like.

  Examples of the alkenyl group include a vinyl group and an allyl group, and examples of the alkynyl group include a propargyl group.

Examples of the heterocyclic group represented by R ₆ include a pyridyl group (each group such as 2-pyridyl, 3-pyridyl, 4-pyridyl), thiazolyl group, oxazolyl group, imidazolyl group, furyl group, chenyl group, and pyrrolyl. Group, pyrazinyl group, pyrimidinyl group, pyridazinyl group, selenazolyl group, sulfolanyl group, piperidinyl group, pyrazolyl group, tetrazolyl group and the like.

Examples of the alicyclic group represented by R ₆ include a cycloalkyl group (for example, a cyclopentyl group, a cyclohexyl group, etc.).

Examples of the aromatic group represented by R ₆ include a phenyl group and a naphthyl group.

The above alkenyl group, alkynyl group, and heterocyclic group can all be substituted with an alkyl group represented by R ₆ and a substituent of the alkyl group, a group shown as a substituent atom, a group similar to the atom, or an atom. .

The cation represented by M ₆ is preferably a metal ion or an organic cation. Examples of metal ions include lithium ions, sodium ions, and potassium ions. Examples of organic cations include ammonium ions (for example, ammonium, tetramethylammonium, and tetrabutylammonium ions), phosphonium ions ( For example, a tetraphenylphosphonium ion etc.), a guanidyl ion, etc. are mentioned.

  Specific examples of the compound represented by the general formula (II) are listed below, but the present invention is not limited to these exemplified compounds.

II-1: CH ₃ (CH ₂ ) ₅ SO ₃ Na
II-2: CH ₃ (CH ₂ ) ₆ SO ₃ Na
II-3: CH ₃ (CH ₂ ) ₇ SO ₃ Na
II-4: CH ₃ (CH ₂ ) ₅ OSO ₃ Na
II-5: CH ₃ (CH ₂ ) ₆ OSO ₃ Na
II-6: CH ₃ (CH ₂ ) ₇ OSO ₃ Na
II-7: CH ₃ O (CH ₂ ) ₂ SO ₃ Na

II-11: CH ₃ (CH ₂ ) ₅ SO ₃ Na
Next, the anionic surfactant represented by the general formula (III) will be described.

In the general formula (III), R ₇ represents an alkyl group having 1 or 2 carbon atoms (for example, a methyl group or an ethyl group) or a hydrogen atom, and R ₈ is a linear or branched alkyl group having 1 to 3 carbon atoms. Group (the alkyl group includes those having a substituent, such as methyl group, ethyl group, propyl group, (i) propyl group, hydroxymethyl group, sulfomethyl group, hydroxyethyl group, sulfoethyl group, disulfoethyl group, dihydroxy group) Ethyl group, 1-hydroxypropyl group, 2-hydroxypropyl group, 1-sulfopropyl group, 2-sulfopropyl group, trihydroxy (i) propyl group, 1,2-disulfopropyl group, etc.), sulfonic acid group, A carboxyl group, a hydroxy group or a hydrogen atom is represented, and R ₉ represents a hydrogen atom or a hydroxy group.

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

  Specific compounds represented by the general formula (III) are shown below, but the present invention is not limited to these exemplified compounds.

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

  Next, the anionic surfactant represented by the general formula (IV) will be described.

In the general formula (IV), R ² represents an alkyl group or an alkenyl group having 8 to 21 carbon atoms, including those having a substituent, preferably an alkyl having 10 to 18 carbon atoms in total. Group or alkenyl group. M represents a hydrogen atom or a metal cation such as Na ⁺ or K ⁺ . Z ¹ represents NH ₂ or OM ′, M ′ represents a hydrogen atom or a metal cation such as Na ⁺ or K ⁺ , and may be the same as or different from M. n represents 1 or 2.

  Although the example of a compound of the anionic surfactant represented by the said general formula (IV) concerning the present invention is shown below, the present invention is not limited to these.

  The addition amount of the anionic surfactants represented by the general formulas (I) to (IV) according to the present invention to the bleach-fixing solution is such that the surface tension of the bleach-fixing solution is 45 mN / m or less as defined in the present invention. Although there is no particular limitation as long as the conditions can be set, it is preferably contained in an amount of 0.002 mol or more and 0.1 mol or less per liter of the bleach-fixing solution. It is 0.004 mol or more and 0.05 mol or less per liter. It is preferable to contain 0.002 mol or more and 0.1 mol or less per liter of replenisher.

  Next, the silver halide color photographic light-sensitive material applied in the processing method of the silver halide color photographic light-sensitive material of the present invention is a color development processing step, a bleach-fixing processing step, a rinse, a stabilization or a water washing processing step, and a drying processing step. Details of each processing solution used in each step will be described.

  First, the bleach-fixing solution according to the present invention will be described.

  The bleach-fixing solution according to the present invention can contain any bleaching agent such as persulfate and hydrogen peroxide as a bleaching main agent, but preferably contains an aminopolycarboxylic acid ferric complex salt from the viewpoint of rapid processing suitability. Although there is no restriction | limiting in particular as aminopolycarboxylic acid ferric complex salt, The following aminopolycarboxylic acid and the iron complex salt complexed beforehand, or ferric salt and aminopolycarboxylic acid coexisted, and complex formation is carried out in a liquid. You may let them.

  Examples of the aminopolycarboxylic acid include ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, ethylenediamine-N- (β-oxyethyl) -N, N ′, N′-triacetic acid, ethylenediamine-N, N′-dioxalic acid (SS ), 1,2-diaminopropanetetraacetic acid, 1,3-diaminopropanetetraacetic acid, nitrilotriacetic acid, cyclohexanediaminetetraacetic acid, iminodiacetic acid, dihydroxyethylglycine, ethyletherdiaminetetraacetic acid, glycol etherdiaminetetraacetic acid, Ethylenediaminetetrapropionic acid, phenylenediaminetetraacetic acid, 1,3-diaminopropanol-N, N, N ′, N′-tetramethylenephosphonic acid, ethylenediamine-N, N, N ′, N′-tetramethylenephosphonic acid, 1 , 3-Propylenediamine-N, N, N ', N'-4 Tylene phosphonic acid, nitrilodiacetic acid monopropionic acid, nitrilomonoacetic acid dipropionic acid, 2- (bis-carboxymethyl-amino) -propionic acid, 2-hydroxy-3-aminopropionic acid-N, N-diacetic acid, serine-N, N-diacetic acid, 2-methyl-serine-N, N-diacetic acid, 2-hydroxymethyl-serine-N, N-diacetic acid, hydroxyethyliminodiacetic acid, methyliminodiacetic acid, N- (2-acetamido)- Examples include, but are not limited to, alkali metal salts (for example, lithium salt, sodium salt, potassium salt) and ammonium salts such as iminodiacetic acid, nitrilotripropionic acid, ethylenediaminediacetic acid, and ethylenediaminedipropionic acid.

  In addition, as the ferric salt, for example, ferric nitrate, ferric chloride, ferric bromide, iron (III) trisulfate (III) M1, iron sulfate (III) M1 (where M1 is ammonium, potassium) More specific compounds include ferric nitrate, ferric chloride, ferric bromide, ferric trisulfate (III) triammonium, ferric trisulfate ( III) Tripotassium, iron (III) trisulfate trisodium, iron (III) sulfate potassium, iron (III) sulfate sodium, iron (III) ammonium sulfate and the like. Moreover, aminopolycarboxylic acid ferrous complex may be included, and these bleaching agents may be used alone or in combination of two or more.

  The concentration of the aminopolycarboxylic acid ferric complex salt contained in the bleach-fixing solution and the replenisher according to the present invention is preferably in the range of 0.01 to 1.5 mol / liter, more preferably 0.02 to 0. .8 mol / liter, and when added in the above range, exhibits excellent processing performance under low replenishment and rapid processing conditions. The molar ratio of aminopolycarboxylic acid and iron ion is preferably aminopolycarboxylic acid: iron ion = 1.001 to 1.10: 1.00 from the viewpoint of the stability of the chelate structure. It is a range.

  Next, the fixing agent contained in the bleach-fixing solution and the replenisher according to the present invention will be described.

  As a fixing main agent of the bleach-fixing solution and the replenisher according to the present invention, a known silver halide solubilizer can be used. For example, alkali metal salts and ammonium salts of thiosulfates such as potassium thiosulfate, sodium thiosulfate and ammonium thiosulfate can be mentioned. Examples of other fixing agents include alkali metal salts and ammonium salts of thiocyanates such as sodium thiocyanate and ammonium thiocyanate.

  The concentration of the fixing agent is preferably from 0.3 to 5.0 mol, more preferably from 0.5 to 3.5 mol, per liter of the bleach-fixing solution and its replenisher. These may be used alone or in combination of two or more.

  In addition, other silver halide solubilizers may be added to the bleach-fixing solution and the replenisher according to the present invention as a secondary agent for the purpose of promoting fixing. Suitable silver halide solubilizers that can be added as secondary agents include, for example, ethylenebisthioglycolic acid, thioether compounds such as 3,6-dithia-1,8-octanediol, and thioureas such as thiourea and ethylenethiourea. These compounds can be added singly or in combination of two or more. Moreover, the compound which has desilvering acceleration | stimulation property can be added, and it can aim at the speeding-up of a process and the improvement of silver removal performance. Examples of compounds suitable for this purpose include 1,2,4-triazolium-3-sulfide type mesoionic compounds (representative examples) disclosed in JP-A-8-297356 and JP-A-8-137070. 1,4,5-trimethyl-1,2,4-triazolium-3-sulfide) and 3-mercapto-1,2,4-triazole type mercapto compounds disclosed in JP-A-9-005964 (Representative example: 3-mercapto-1,2,4-triazol-1-methylsulfonic acid) and the like. Preferred addition amounts of these compounds are 0 per liter of the bleach-fixing solution and its replenishing solution. 0.001 to 0.1 mol. Further, two or more kinds of these desilvering promoting compounds may be used in combination.

  In addition, a halogenating agent for promoting the oxidation of silver, such as chloride, bromide, or iodide, may be added to the bleach-fixing solution and the replenisher according to the present invention. The halogenating agent may be added as an alkali metal salt or ammonium salt, or a salt such as guanidine or amine, and specific examples include sodium bromide, potassium bromide, ammonium bromide, potassium chloride, and guanidine hydrochloride. . The concentration of the halogenating agent is preferably 1.8 mol or less, more preferably in the range of 0.1 to 1.6 mol, per liter of the bleach-fixing solution and the replenishing solution.

  The bleach-fixing solution and the replenisher according to the present invention preferably use ammonium ions when considering the speed of processing. On the other hand, when emphasizing work environment properties, they are substantially free of ammonium ions. Is preferred. The pH is preferably 2.0 to 8.0, more preferably 3.5 to 6.5. In the pH range, good processing performance can be obtained. Moreover, organic acid, an acid, an alkali agent, etc. can be used suitably for adjustment of the said pH. The organic acid preferably has a pKa of 2.0 to 5.5. Specific examples include the monocarboxylic acid, oxalic acid, malonic acid, succinic acid, tartaric acid, malic acid, maleic acid, fumaric acid, oxalo Aliphatic dibasic acids such as acetic acid, glutaric acid and adipic acid; amino acid dibasic acids such as aspartic acid, glutamic acid, cystine and ascorbic acid; aromatic dibasic acids such as phthalic acid and terephthalic acid; Examples thereof include polybasic acids such as citric acid. Among these, glycolic acid, succinic acid and maleic acid are preferable because they have a relatively small influence on the bleaching property.

  These organic acids can also be used in combination of two or more kinds or in combination with the monocarboxylic acid. The addition concentration is preferably 0.05 to 2.0 mol per liter of the bleach-fixing solution and the replenisher, and when used in the previous period, the processing solution and the replenisher have excellent temporal stability.

  The bleach-fixing solution and the replenisher according to the present invention preferably contain a preservative from the viewpoint of storage stability of the solution. Examples of preservatives include sulfites and sulfinic acid compounds. 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. The sulfinic acid compound is preferably an arylsulfinic acid compound, and specific examples include p-toluenesulfinic acid, m-carboxybenzenesulfinic acid, benzenesulfinic acid, sodium benzenesulfinate and the like. The concentration of the sulfite or sulfinic acid compound added is preferably 0.02 mol to 1.0 mol per liter of the bleach-fixing solution and its replenisher. In addition, various additives such as imidazole compounds, antifoaming agents, surfactants, optical brighteners, polyvinylpyrrolidone (PVP), phosphates or polyphosphate phosphates may be added as necessary. .

  Examples of the fluorescent brightening agent include bis (triazinylamino) stilbene sulfonic acid compounds, specifically, compounds described in paragraph numbers [0038] to [0049] of JP-A No. 2001-281823. Examples thereof include compounds II-1 to II-16 described in I-1 to I-48 and paragraph numbers [0050] to [0052] of JP-A No. 2001-281823. The addition amount of these optical brighteners is preferably from 0.1 mmol to 0.01 mol per liter of the bleach-fixing solution and the replenisher.

  Specific examples of the imidazole compound include 1-methylimidazole, 2-methylimidazole 4-methylimidazole, 4- (2-hydroxyethyl) imidazole, 4- (2-aminoethyl) imidazole, 2- (2-hydroxy Ethyl) imidazole, 2-ethylimidazole, 2-vinylimidazole, 4-propylimidazole, 2,4-dimethylimidazole, 2-chloroimidazole 4,5-di (2-hydroxyethyl) imidazole, and the like. It is not limited.

  These imidazole compounds may be used alone or in combination of two or more, and the addition concentration is preferably 0.01 mol to 3.0 mol, more preferably 0.05 mol to 1 liter of the bleach-fixing solution and its replenisher. 2.0 moles.

  Examples of the phosphate include, for example, 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. However, it is not limited to these. Specific examples of the polyphosphate include sodium hexametaphosphate, sodium tetraphosphate, hydroxyethanediphosphonic 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- Examples thereof include, but are not limited to, 1,2,4-tricarboxylic acid, 2-carboxyethane-phosphonic acid, and methylenediphosphonic acid. These phosphates or polyphosphates may be used alone or in combination of two or more, and the concentration is 0.01 mol to 2.5 mol per liter of the bleach-fixing composition.

  Next, development processing steps applied in the processing method of the present invention will be described.

  The development process according to the present invention comprises a color development process, a bleach-fixing process, a rinse, a washing or stabilization process, and a drying process, and auxiliary processes such as an intermediate washing process and a neutralization process are required between the processes. Depending on the situation, it can be inserted appropriately.

  Specific examples of the desilvering step including the bleach-fixing step according to the present invention will be given below, but are not limited thereto.

1) Bleaching and fixing 2) Bleaching and bleaching and fixing 3) Bleaching and washing and bleaching and fixing 4) Bleaching and bleaching and fixing and fixing Each of these steps may be divided into a plurality of tanks if necessary, and a cascade method may be adopted. Of these, the preferred step is 1).

The replenishment amount of the bleach-fixing step according to the present invention (the replenisher amount replenished in the processing tank according to the processing amount of the silver halide color photographic light-sensitive material) is ^{20 to} 200 ml per 1 m ^{2 of the} silver halide color photographic light-sensitive material. Is more preferable, and 35 ml to 100 ml is more preferable.

The replenishing amount in the color development step is preferably 15 to 200 ml, more preferably 15 per 1 m ^{2 of the} silver halide color photographic light-sensitive material when the silver halide color photographic light-sensitive material to be developed is color paper. -120 ml, particularly preferably 30-60 ml. On the other hand, when the silver halide color photographic light-sensitive material to be developed is a color negative film, the amount is preferably from 100 to 800 ml, more preferably from 200 to 500 ml, particularly preferably from 250 to 1 m ^{2 of} silver halide color photographic light-sensitive material. 400 ml.

The replenishing amount in the rinsing step, washing step or stabilizing step is preferably 300 ml or less, more preferably 200 ml or less, per 1 m ^{2 of the} silver halide color photographic light-sensitive material as a whole.

  The color development time (that is, the processing time in the color development process) is preferably 45 seconds or less, more preferably 30 seconds or less, more preferably 30 seconds or less, when the silver halide color photographic light-sensitive material is color paper, from the viewpoint of rapidity. Preferably, it is 30 seconds or less and 6 seconds or more. On the other hand, when the silver halide color photographic light-sensitive material is a color negative film, the time is preferably 20 seconds to 6 minutes, and more preferably 30 to 200 seconds. The color development time referred to in the present invention means the time from when the silver halide color photographic light-sensitive material enters the color development processing step to the next processing step, for example, the bleach-fixing processing step. The time during which the color photographic light-sensitive material is immersed in the color development process (so-called submerged time) and the air transport time until the silver halide color photographic light-sensitive material leaves the color development processing process and enters the next bleach-fixing process. The total of both (so-called air time) is called color development time.

  The bleach-fixing time (that is, the time for performing the bleach-fixing process) is preferably 1 minute or less, more preferably 45 seconds or less, still more preferably 30 seconds or less, and 6 seconds or more from the viewpoint of rapidity. In the present invention, the bleach-fixing time refers to the time from when the silver halide color photographic light-sensitive material enters the bleach-fixing solution until it enters the next step of rinsing, washing or stabilizing processing solution. The air time is preferably as short as possible from the viewpoint of quickness, and is 5 seconds or less, more preferably 3 seconds or less.

  The rinsing, stabilization or washing time (that is, the time for rinsing, stabilization or washing treatment) is preferably 90 seconds or less, more preferably 30 seconds or less, and even more preferably 30 seconds or less. The rinsing, stabilization or washing time refers to the time (so-called in-solution time) that the silver halide color photographic light-sensitive material is in the liquid for the drying process after entering the rinsing, stabilization or washing process. In addition, when the rinsing, stabilization or washing treatment process is composed of a plurality of treatment tanks, the air time between the treatment tanks is preferably as short as possible from the viewpoint of rapidity, and is preferably 5 seconds or less, more preferably 3 seconds or less. .

  In the method for processing a silver halide color photographic light-sensitive material of the present invention, at least one processing step of a bleach-fixing processing step, a rinsing, a stabilization or a water-washing processing step is performed from the viewpoint that the object and effects of the present invention can be exhibited more. It is preferable that the transport mode of the silver halide color photographic light-sensitive material is a submerged transport system.

  The submerged conveyance method referred to in the present invention is a method in which when the silver halide color photographic light-sensitive material moves between the processing tanks, it is once in the air as described above and then moved to the processing tank of the next process. In this method, the movement between the treatment tanks is moved from the treatment tank of the previous bath to the liquid in the treatment tank of the next step, that is, without moving to the air. Therefore, in such a submerged conveyance method, the air time becomes zero.

  In the processing method of the present invention, it is preferable that this submerged transport system is transported by providing at least one submerged transport means between the bleach-fixing step and the final processing tank, more preferably the bleach-fixing step. It is preferable to apply the submerged conveyance method when moving from the step to the rinse, stabilization or washing process.

  When the bleach-fixing process, or the rinsing, stabilization or washing process is composed of a plurality of processing tanks, the low surface tension bleaching according to the present invention is applied by applying such a submerged conveyance system. When the fixer is used, the carryover amount of the bleach-fixer when the silver halide color photographic light-sensitive material is transported from the bleach-fixing bath to the rinse, stabilization or washing bath is greatly reduced, and the transport section is By not contacting the air at all, no precipitation at the conveying section of the bleach-fixing solution occurs, so that it is possible to completely prevent the occurrence of scratches due to foreign matters.

  Examples of the submerged conveyance method applicable to the present invention include, for example, the methods described in FIGS. 2 and 3 described in JP-A-2005-99262 and paragraphs [0014] to [0020] of the same publication, Examples thereof include a submerged blade conveying means (mechanism) using a single or double blade described in Japanese Unexamined Patent Application Publication No. 2002-55422.

  Hereinafter, examples in which the submerged conveyance method is applied to the processing method of the present invention will be described with reference to the drawings. However, the present invention is not limited to these exemplified methods.

  FIG. 1 is a schematic cross-sectional view showing an example of an automatic developer using an out-of-liquid conveyance method.

  In FIG. 1, the processing tank is a processing apparatus for color paper comprising a color development processing tank 1, a bleach-fixing processing tank 2 and a stabilizing processing tank 3-1, 3-2, 3-3 consisting of three tanks. The processing is performed in each processing tank while conveying the silver halide color photographic light-sensitive material P. At this time, the movement from the color development processing tank 1 to the bleach-fixing processing tank 2, the movement from the bleach-fixing processing tank 2 to the stabilization processing tank 3-1, or the movement between the respective stabilization processing tanks is all out of the liquid. It moves in the air over a predetermined period of time via an out-of-liquid transport unit A (also referred to as a crossing rack) composed of the provided transport rollers. The outside liquid transport unit A is provided with a squeeze roller 6 in order to prevent the pre-bath processing liquid from being carried over by the processing liquid for the next process. In the out-of-liquid conveyance method, the pre-bath processing solution adhering to the squeeze roller is air-dried, causing crystallization of the silver halide color photographic light-sensitive material to be conveyed after crystallization.

  FIG. 2 is a schematic cross-sectional view showing an example of an automatic developing machine in which a submerged conveyance system is incorporated in a part between processing tanks.

  FIG. 2 shows a specification in which the movement from the bleach-fixing processing tank 2 to the stabilization processing tank 3-1 is performed by a submerged conveyance method. A slit portion (not shown) for transferring the silver halide color photographic light-sensitive material is provided in the liquid portion of the separation wall of the bleach-fixing processing tank 2 and the stabilization processing tank 3-1, and a pair of blade transport mechanisms 7 are provided at the upper and lower portions thereof. And a support roller 8 group for holding the transport of the silver halide color photographic light-sensitive material, and a blade conveying mechanism for contamination of the bleach-fixing bath 2 to the stabilization bath 3-1. 7 to prevent.

  Further, in this submerged transport method, the air time of the bleach-fixing step (between the bleach-fixing processing tank 2 and the stabilization processing tank 3-1) is substantially 0 seconds because it is transported in the liquid. Further, since it does not come into contact with air during this period, there is no generation of a crystal of the bleach-fixing solution, and it is possible to prevent scratches during conveyance.

  3 and 4 are schematic cross-sectional views showing another example of an automatic developing machine in which a submerged conveyance system is incorporated in a part between processing tanks.

  FIG. 3 shows an example in which the submerged conveyance method is applied to all the isolation walls from the bleach-fixing processing tanks 2 to 3 to the stabilization processing tanks 3-1, 3-2 and 3-3.

  In FIG. 4, the conveying method from the bleach-fixing treatment tank 2 to the stabilization treatment tank 3-1 is a conventional extra-liquid conveyance, and the stabilization treatment tanks 3-1, 3-2, 3-3 comprising three tanks. This is an example in which the in-liquid transfer method is applied to all the isolation walls up to.

  A drying step for drying the liquid-processed silver halide color light-sensitive material is provided as a step subsequent to the color development processing step, bleach-fixing processing step, rinsing, stabilization or washing step described above.

  The drying process absorbs moisture with a squeeze roller or cloth immediately after rinsing, stabilization, or washing with water, in order to reduce the amount of moisture brought into the image forming 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, changing the shape of the spray nozzle, and increasing the drying air. Furthermore, as described in JP-A-3-157650, drying can be accelerated by adjusting the blowing angle of the dry air to the silver halide color photographic light-sensitive material and by the method of removing the exhaust air.

  Next, each processing composition excluding the bleach-fixing solution used in each development processing step will be described.

  First, the details of the color development processing composition used in the color development step 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 Of the above p-phenylenediamine derivatives, particularly preferred compound 5 ), 6), 7), 8) and 12), and among them, exemplary compounds 5) and 8) are preferred.

  These p-phenylenediamine derivatives may be in the form of a salt such as sulfate, hydrochloride, sulfite, naphthalene disulfonate, p-toluenesulfonate, or the free base type as described above.

  The concentration of the aromatic primary amine developing agent is 2 to 200 millimoles, preferably 6 to 100 millimoles, more preferably 10 to 40 millimoles per liter of the color developing composition. .

  An organic preservative may be added to the color development processing composition. Organic preservatives refer to all organic compounds that reduce the degradation rate of an aromatic primary amine color developing agent when added to a color developing solution. That is, organic compounds having a function to prevent air oxidation of color developing agents, 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, and condensed amines are particularly effective organic preservatives. These are disclosed in JP-A 63-4235, 63-30845, 63-21647, 63-44655, 63-53551, 63-43140, 63-56654, 63- 58346, 63-43138, 63-146041, 63-44657, 63-44656, U.S. Pat.Nos. 3,615,503, 2,494,903, JP-A 52- No. 143,020, Japanese Patent Publication No. 4,830,496 and the like.

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

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

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

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

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

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

Represents. R ″ represents an alkylene group having 2 to 8 carbon atoms or an alkanetriyl group which may be substituted with a hydroxyl group. In the case of an alkylene group, q is 0, and in the case of an alkanetriyl group, q is 1. In the case of 1, B represents a polymer represented by the general formula (Y), 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 organic preservative is preferably contained in an amount of 1 × 10 ⁻³ mol or more and 1 × 10 ⁻¹ mol or less per liter of the color developing composition. In addition, a small amount of sulfite ion and / or hydroxylamine (usually used in the form of hydrochloride or sulfate, but hereinafter abbreviated in the form of salt) can be included as a preservative depending on the type of the photosensitive material to be processed. In addition, from the viewpoint of the temporal stability of the treatment composition, sulfinic acid compounds, particularly arylsulfinic acid compounds such as benzenesulfinic acid, p-toluenesulfinic acid, and m-carboxybenzenesulfinic acid may be included. The addition concentration is preferably 0.02 mol to 1.0 mol per liter of the treatment composition treatment.

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

  Examples of the buffer include carbonate, bicarbonate, phosphate, borate, tetraborate, hydroxybenzoate, glycyl salt, N, N-dimethylglycine salt, leucine salt, norleucine salt, guanine salt, Use 3,4-dihydroxyphenylalanine salt, alanine salt, aminobutyrate, 2-amino-2-methyl-1,3-propanediol salt, valine salt, proline salt, trishydroquinaminomethane salt, lysine salt, etc. Can do. In particular, carbonates, bicarbonates, phosphates, tetraborate and hydroxybenzoates are excellent in buffering ability in a high pH range of pH 9.0 or higher, and have photographic performance even when added to a color developing composition. This is a particularly preferred buffering agent because it does not adversely affect (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) , Potassium 5-sulfo-2-hydroxybenzoate (potassium 5-sulfosalicylate) and the like, but are not limited to these compounds.

  The amount of the buffer added is preferably 0.01 to 2 mol, more preferably 0.1 to 0.5 mol, per liter of the color development processing composition.

  Specific examples of the alkali agent include sodium hydroxide, potassium hydroxide, lithium hydroxide and the like.

  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. For example, nitrilotriacetic acid, diethylenetriaminepentaacetic acid, ethylenediaminetetraacetic acid, N, N, N-trimethylenephosphonic acid, ethylenediamine-N, N, N ′, N′-tetramethylenesulfonic acid, transsirohexasidiaminetetraacetic acid, 1,2-diaminopropanetetraacetic acid, glycol ether diamine tetraacetic acid, ethylenediamine orthohydroxyphenylacetic acid, ethylenediamine-N, N′-disuccinic acid (SS form), N- (2-carboxylateethyl) -L-aspartic acid , Β-alanine diacetate, 2-phosphonobutane-1,2,4-tricarboxylic acid, 1-hydroxyethylidene-1,1-diphosphonic acid, N, N′-bis (2-hydroxybenzyl) ethylenediamine-N, N′- Diacetic acid, 1,2-dihydroxybenzene-4,6-disulfo 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 sufficient to sequester the metal ions in the color developing 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 addition amount thereof is 0.001 to 0.2 mol, preferably 0.01 to 0.05 mol, per liter of the color development processing composition.

  An optional antifoggant can be added to the color development processing composition as required. For example, benzotriazole, 6-nitrobenzimidazole, 5-nitroisoindazole, 5-methylbenzotriazole, 5-nitrobenzotriazole, 5-chloro-benzotriazole, 2-thiazolyl-benzimidazole, 2-thiazolylmethyl-benzimidazole, And nitrogen-containing heterocyclic compounds such as indazole, hydroxyazaindolizine, and adenine.

  Moreover, you may add various surfactants, such as alkyl sulfonic acid, aryl sulfonic acid, aliphatic carboxylic acid, and aromatic carboxylic acid, as needed. The addition amount thereof is preferably 0.0001 to 0.2 mol, more preferably 0.001 to 0.05 mol, per liter of the treatment composition. In addition, a fluorescent whitening agent can be used in the color development processing composition as necessary. As the optical brightener, a bis (triazinylamino) stilbene sulfonic acid compound is preferred. As the bis (triazinylamino) stetilbenesulfonic acid compound, a known or commercially available product 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, Tinopearl MSP, Blankophor BSU liq. , Hakkol 508 and Hakkol BRK are preferred. Examples of the other bis (triazinylamino) stilbene sulfonic acid compounds include the compounds described above. The addition amount is preferably from 0.1 mmol to 0.1 mol per liter of the color development processing composition.

  Moreover, the compound represented by the said general formula (I) based on this invention can also be included. The addition amount is preferably from 0.1 mmol to 0.1 mol per liter of the color development processing composition.

The color development processing composition for color paper usually contains 3.5 × 10 ^{−2 to} 1.5 × 10 ⁻¹ mol / liter of chlorine ions, but chlorine ions are usually a by-product of development. In many cases, the replenisher does not need to be added to the replenisher. On the other hand, 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 ×. In many cases, it is contained at 10 ⁻² mol / liter, but bromine ions are usually released into the processing composition as a by-product of development, and therefore often need not be added 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 processing composition as a by-product of development, so that it is often unnecessary to add them to the replenisher.

  Next, each treatment liquid for rinsing, stabilization or washing with water will be described.

  The rinse or stabilizing solution used in the present invention includes a chelating agent (for example, ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, 1-hydroxyethylidene-1,1-diphosphonic acid, etc.), a buffering agent (for example, potassium carbonate, borate, Acetate, phosphate, etc.), antifungal agents (eg, Dearside 702 (made by Dearborn, USA), p-chloro-m-cresol, benzoisothiazolin-3-one, etc.), optical brighteners (eg, A triazinyl stilbene compound, etc.), an antioxidant (eg, ascorbate, etc.), a water-soluble metal salt (eg, zinc salt, magnesium salt, etc.) or the general formula (I) according to the present invention. A compound etc. can be added suitably.

Further, it is preferable to add the sulfite and / or sulfinic acid compound to the rinsing or stabilizing solution from the viewpoint of liquid storage stability. The amount of these sulfites and / or sulfine compounds added is preferably at least 1 × 10 ⁻⁵ mol / L or more, more preferably 5 × 10 ⁻⁵ mol / L to the rinsing or stabilizing solution. 5 × 10 ⁻² mol / L. Further, the pH of the treatment liquid for rinsing stabilization or washing is preferably in the range of 4.0 to 10.0. Moreover, in order to adjust to the said pH, a pH adjuster can also be contained. The pH adjuster may be any of commonly known alkali agents or acid agents.

  Next, the silver halide color photographic light-sensitive material processed by the processing method of the present invention will be described.

  The silver halide color photographic light-sensitive material according to the present invention is usually a light-sensitive silver halide emulsion layer containing a yellow dye-forming coupler on a support, a light-sensitive silver halide emulsion layer containing a magenta dye-forming coupler, and cyan. Each is composed of a layer containing one or more photosensitive silver halide emulsion layers containing a dye-forming coupler and a non-photosensitive hydrophilic colloid layer as required.

  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. The silver halide color photographic light-sensitive material may be included in a non-photosensitive hydrophilic colloid layer, an antihalation layer, an intermediate layer, and a colored layer in addition to the yellow coloring layer, the magenta coloring layer, and the cyan coloring layer. .

  In the processing method of the present invention, the applied silver halide color photographic light-sensitive material has a hydrophilic colloid constituent layer on the exposed surface side, for example, each of the above-described photosensitive silver halide emulsion layers, non-photosensitive hydrophilic colloid layers, anti-photosensitive layers. A silver halide color photographic light-sensitive material having a total dry film thickness of 10 μm or more, such as a halation layer, an intermediate layer, and a colored layer, is preferred from the viewpoint of further achieving the object effect of the present invention. The upper limit of the total dry film thickness can be set within a range that does not affect the processing, but is generally 30 μm or less.

  When processing a silver halide color photographic light-sensitive material in which the total dry film thickness of the hydrophilic colloid constituent layer on the exposed surface side is 10 μm or more, each processing solution is retained by the thick hydrophilic colloid layer. As a result, the amount of carryover of the processing liquid to the next step increases, and in particular, contamination of a large amount of bleach-fixing liquid into the stabilization processing tank tends to generate yellow stain. Therefore, when processing a silver halide color photographic light-sensitive material having such a structure, the effect can be sufficiently exhibited by applying the processing method defined in the present invention.

  The dry total film thickness as used herein refers to a commercially available contact-type film thickness meter (for example, Anritsu Electric Co., Ltd. K-402B) after conditioning for 2 days under conditions of a temperature of 25 ° C. and a relative humidity of 55%. (STAND.) Is displayed as the value measured. The total dry film thickness (that is, dry total film thickness) of all hydrophilic colloid layers excluding the undercoat layer of the support on the surface side having the hydrophilic colloid layer is the total film thickness A of the dried sample and the exposed surface side. The film thickness B after removing all of the hydrophilic colloid layers in the substrate can be obtained and measured as the difference (total film thickness A−film thickness B), or, for example, a scanning electron microscope Can be obtained by enlarging and photographing the cross-section using and.

  In order to measure the film thickness of each layer of the silver halide color light-sensitive material having a multilayer structure, it is possible to magnify a cross section using a scanning electron microscope. In scanning electron microscope measurements, the sample must be placed under a normal vacuum, and the humidity-dried sample cannot be maintained. The film thickness may not be measured correctly due to loss. For this reason, a lyophilization sample preparation method has been attempted, but it is not sufficient. The measurement by cross-sectional photography of the scanning electron microscope is used as a measuring means for calculating the thickness of each layer of the dry sample based on the film thickness value obtained by the contact-type film thickness meter.

  Examples of the silver halide color photographic light sensitive material to which the processing method of the present invention can be applied include a color negative film, a color reversal film, a color paper, a color display, a color movie film, etc., preferably a color paper. is there. As commercial products of color paper, FUJICOLOR Crystal Archive paper, FUJICOLOR SUPER FA paper (above, manufactured by Fuji Photo Film Co., Ltd.), Kodak EKTACOLOR EDGE paper, Kodak EKTACOLOR Royal paper (above, manufactured by Eastman Co., Ltd., T , AGFACOLOR Prestige paper (manufactured by AGFA), KONICACOLOR QA paper (manufactured by Konica Minolta Photo Imaging) (all are trade names), and the like, but are not limited thereto.

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

  The automatic processor applicable to the processing method of the present invention preferably has a linear velocity of conveyance of 100 mm / second or less, more preferably 27.8 mm / second to 80 mm / second, particularly preferably 27.8 mm / second. ~ 50 mm / sec.

  In the transport of color paper automatic developing machines, the color paper is cut to the final size and then developed (sheet-type transport system), and developed with a roll-shaped silver halide color photographic light-sensitive material, and after drying There is a method of cutting to the final size (cine type conveyance method). In the treatment method of the present invention, a cine type conveyance method is preferable when the submerged conveyance method is applied.

In addition, it is preferable that the treatment liquid tank and the replenisher tank have a small area (opening area) where the liquid comes into contact with air. For example, the opening area (cm ² ) is divided by the liquid tank (cm ³ ) in the tank. When the value is an aperture ratio, the aperture 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 floating on the liquid surface in the treatment liquid tank and the replenishment liquid tank. Specifically, it is preferable to cover a plastic float or the like on a liquid surface, or a liquid that does not mix with the processing liquid and does not cause a chemical reaction. As examples of the liquid, liquid paraffin, liquid saturated hydrocarbon, and the like can be used.

  In addition, the transport between the processing tanks of the automatic developing machine (transport from the previous tank to the next tank) is carried out by using a cross-rack as described above and once transported in the air, or in-liquid transport means using the blade as described above. Etc. can be used. Further, when the blade submerged conveying means is used, a porous material pleated filter or the like can be installed in the liquid circulation structure described in JP-A-2002-339383 and the circulation system.

  In addition, the automatic processor preferably has a mechanism for performing so-called evaporation correction, which supplies water corresponding to the evaporation amount of the processing solution. From the viewpoint of sex. A specific method for replenishing such water is not particularly limited, but a monitoring water tank different from the bleach-fixing tank described in JP-A-1-254959 and 1-254960 is installed. The amount of water evaporation in the monitor tank is calculated, the amount of water evaporation in the bleach-fixing tank is calculated from the amount of water evaporation, and the water level sensor is used to replenish the bleach-fixing tank in proportion to this amount of evaporation. Or an evaporation correction method using an overflow sensor is preferred. The most preferable evaporation correction method is to predict and add water corresponding to the amount of evaporation, and is described on page 26, right column, line 26 to page 3, left column, page 28 of the Japan Institute of Invention and Innovation, No. 94-49925. As described above, the amount of water calculated by a coefficient determined in advance based on information on the operation time, stop time, and temperature control time of the automatic processor is added. Further, a device for reducing the evaporation amount is also required, and it is required to reduce the opening area and adjust the air volume of the exhaust fan. For example, the preferred aperture ratio of the color development processing solution is as described above, but it is preferable to reduce the opening area in the other processing solutions as well.

As means for reducing the evaporation amount, it is particularly preferable to “keep the humidity of the upper space of the treatment tank at 80% RH or higher” described in JP-A-6-110171, and the evaporation prevention described in FIGS. It is particularly preferred to have a rack and roller automatic cleaning mechanism. Exhaust fans in order to prevent dew condensation at the temperature control is attached normally, a preferable exhaust amount per minute 0.1 m ³ to 1 m ^3, particularly preferably at 0.2m ³ ~0.4m ³ is there. The drying conditions of the silver halide color photographic light-sensitive material also affect the evaporation of the processing solution. The drying method is preferably a ceramic hot air heater is preferably min 4m ³ to 20 m ³ as feed air volume, particularly 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 mounted on the leeward or windward side through the radiating fin or 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 processing solution, but a bellows type replenishment pump is preferred. In addition, as a replenishment method, the treatment liquid concentrated composition may be added directly to the treatment tank, and water corresponding to the dilution ratio may be added directly to the treatment tank, and the treatment liquid concentrated composition is dissolved in the replenishment tank. It may be diluted and replenished as a replenisher, or the treatment liquid concentrated composition may be automatically dissolved and diluted in a replenisher tank using an automatic preparation device and replenished as a replenisher. As a method for improving the replenishment accuracy, it is effective to reduce the diameter of the liquid feeding tube to the replenishing nozzle in order to prevent backflow when the pump is stopped. A preferable inner diameter is 1 to 8 mm, and a particularly preferable inner diameter is 2 to 5 mm.

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

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

  Resin such as PVC (polyvinyl chloride), PP (polypropylene), PE (polyethylene), TPX (polymethylpentene) is suitable for the roller material of the processing section. These materials can also be used for other processing liquid contact portions. In addition, PE resin is preferable also for the material of the replenishment tank by blow formation. PA (polyamide), PBT (polybutylene terephthalate), UHMPE (ultra high molecular weight polyethylene), PPS (polyphenylene sulfide), LCP (fully aromatic polyester resin, liquid crystal polymer) ) Etc. are suitable. PA resin is polyamide resin such as 66 nylon, 12 nylon, and 6 nylon, and those containing glass fiber or carbon fiber are strong against swelling by the treatment liquid and can be used. Further, high molecular weight products such as MC nylon and compression formed products can be used without fiber reinforcement. UHMPE resin is suitable for unreinforced products. “Lubema”, “Hi-X Million” manufactured by Mitsui Petrochemical Co., Ltd., “New Light” manufactured by Sakushin Kogyo Co., Ltd., “Sunfine” manufactured by Asahi Kasei Kogyo Co., Ltd. Is suitable. The molecular weight is preferably 1,000,000 or more, more preferably 1,000,000 to 5,000,000. The PPS resin is preferably glass fiber or carbon fiber reinforced. Examples of the LCP resin include “Victrex” manufactured by ICI Japan, “Econol” manufactured by Sumitomo Chemical, “Zider” manufactured by Nippon Oil Co., Ltd., “Vectra” manufactured by Polyplastics, and the like. In particular, the material of the conveyor belt is preferably ultrahigh strength polyethylene fiber or polyvinylidene fluoride resin described in JP-A-4-151656. As soft materials such as a transport roller and 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, it is preferable that the automatic developing machine has an apparatus capable of collectively mounting a kit for supplying a replenisher solution to each process as a cartridge because the replenisher solution can be easily prepared.

  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 each treatment liquid >>
A color developer solution, a bleach-fix solution and a stabilizing solution tank solution and replenisher solution were prepared as follows.

[Color developer: per liter]
Tank liquid Replenisher Polyethylene glycol # 4000 15.0 g 15.0 g
Sodium p-toluenesulfonate 10.0 g 10.0 g
Potassium chloride 4.0 g −
4-Amino-3-methyl-N-ethyl-N- (β-methanesulfonamidoethyl) aniline sulfate 6.0 g 12.0 g
N, N-bis (sulfoethyl) hydroxylamine disodium salt
4.0g 8.0g
Potassium carbonate 33.0g 33.0g
Diethylenetriaminepentaacetic acid 11.0 g 11.0 g
pH 10.05 11.00
Water was added to 1 L, and the pH was adjusted with potassium hydroxide or 50% sulfuric acid.

[Bleaching fixer per liter]
(Preparation of bleach-fixing solution A-1)
Tank liquid = replenisher ammonium sulfite (40% aqueous solution) 100.0 g
Ammonium thiosulfate 120.0g
Ethylenediamine tetraammonium iron acetate 75.0 g
Acetic acid 10.0g
Water was added to 1 L, the pH was adjusted to sulfuric acid or ammonia water, the replenisher was adjusted to pH 5.0, the tank solution was adjusted to 6.3, and this was designated as Bleach Fixer A-1.

  Further, the surface tension of this bleach-fixing solution A-1 at 20 ° C. was measured with an automatic surface tension meter CBVP-Z type manufactured by Kyowa Interface Chemical Co., Ltd. As a result, it was 58 mN / m.

(Preparation of bleach-fixing solutions A-2 to A-10)
In the preparation of the above-described bleach-fixing solution A-1, the same amount was used except that the amount of addition of the exemplified compound (I-21) was appropriately adjusted and the surface tension of the bleach-fixing solution was adjusted to the values shown in Table 1. Thus, bleach-fixing solutions A-2 to A-10 were prepared.

[Stabilizing liquid: per liter]
Tank liquid = replenisher 1-hydroxyethylidene-1,1-diphosphonic acid trisodium 3.0 g
Ethylenediaminetetraacetic acid 1.5g
o-Phenylphenol 0.1g
Sodium sulfite 0.5g
Chino Pearl SFP (Ciba Geigy) 1.0g
pH 7.5
Water was adjusted to 1 L, and the pH was adjusted to 7.2 using an aqueous ammonia solution or 50% sulfuric acid for both the replenisher and the tank solution to prepare Stabilizing Solution 1.

<Development processing>
Next, development processing 1-1 was performed using the prepared color developer (tank solution and replenisher), bleach-fix solution A-1, and stabilizing solution under the following conditions.

  The running process of development was performed using the automatic developing machine shown in FIG. Konica Minolta QA Paper Centuria for Digital (Konica Minolta Photo Imaging, Inc.) shot a standard daylight scene using a commercially available color negative film, subjected to specified development processing, and then exposed through this developed color negative film First, development processing 1-1 using the bleach-fixing solution A-1 is performed, and a running processing is performed at a processing amount equivalent to 0.2R per day until reaching 1.5R, and then the bleach-fixing converging solution 1-1 was obtained. Incidentally, 1R (round) in the present invention means that the total replenishment amount of the bleach-fixing replenisher is one time the tank capacity.

  Subsequently, in the preparation of the bleach-fixing astringent solution 1-1, a running process was performed in the same manner except that the bleach-fixing solutions A-2 to A-10 were used in place of the bleach-fixing solution A-1, and partly In the bleach-fixing solution, the pressure of the squeeze roller in the outside conveying section A from the bleach-fixing tank 2 to the stabilizing tank 3-1 is changed to 1.2 times the reference pressure set in a general automatic processor. Development processing 1-2 to 1-13 was carried out to obtain bleach-fixed astringent solutions 1-2 to 1-13.

(Processing conditions)
Processing process Processing temperature Processing time Tank capacity Replenishment amount
(° C) (seconds) (L) (ml / m ² )
Color development 39.8 22 15.5 50
Bleach fixing 36.8 22 15.2 40
Stabilization-1 33.0 22 15.0
Stabilization-2 33.0 22 15.0
Stabilization-3 33.0 22 15.0 150
Dry 75.0 22
<< Evaluation of each characteristic >>
(Evaluation of stain resistance on white background after storage)
Using the above bleach-fixed astringent solutions 1-1 to 1-13, a silver halide color photographic light-sensitive material (color paper) having a dry film thickness of 5.5 μm of all hydrophilic colloid layers is processed under the same processing conditions as above. The image samples thus obtained were stored for 14 days in a thermostat bath at 70 ° C. and 90% RH, and then the stain on the back of each sample was evaluated on the 7th and 14th days of storage.

  The stain was evaluated using a densitometer equipped with an international standard ISO5 density measuring optical system, and the blue filter light density Dmin (B) on the back surface of the sample before storage was measured using blue filter light (status A). . Next, Dmin (B) was measured in the same manner on the 7th and 14th days from the start of storage, and the Dmin (B) of the sample before storage and each Dmin (B) on the 7th and 14th days of storage Concentration difference ΔDmin (B) was determined and used as a measure of white background stain resistance on the back side.

(Scratch resistance / stain resistance evaluation)
In the above running process, a silver halide color photographic light-sensitive material having a dry film thickness of 5.5 μm of the total hydrophilic colloid layer using the bleach-fixed astringent solution 1-1 to 1-13 after completion of 1.5 rounds ( Color paper) 2000 sheets / L size (127 mm × 178 mm) was continuously processed, and the surface state of the processed sample was visually observed, and scratch resistance and dirt resistance were evaluated according to the following criteria.

◎: No scratches or stains are observed in all samples ○: No scratches are observed in all samples, but there are 3 or less samples where thin stains can be confirmed △: Scratches Or, there are four samples that can confirm at least one of dirt. ×: There are 5 or more and 19 or less samples that can confirm at least one of scratches or dirt. XX: At least one of scratches or dirt can be confirmed. The number of samples is 20 or more. Table 1 shows the results obtained as described above.

  As is clear from the results shown in Table 1, when the surface tension of the bleach-fixing solution is larger than 45 mN / m as defined in the present invention, the stain resistance on a white background during print storage is remarkably inferior. In particular, as in Development 1-3, when a bleach-fixing solution with a surface tension of 50 mN / m is used and the squeeze roller pressure is 1.2 times the current pressure, the amount brought into the next tank is reduced. Although there was a slight improvement in white stain resistance, many scratches and stains were observed on the sample.

  It can be seen that when the surface tension of the bleach-fixing solution is 45 mN / m or less, the white background stain resistance during storage is improved. In addition, it can be seen that development processing 1-9 to 1-13 in which the surface tension of the bleach-fixing solution is 35 mN / m or less is more excellent in white background stain resistance during storage.

  In the present invention, stable running processing performance was obtained irrespective of the nip pressure of the squeeze roller, and print scratches and dirt were hardly confirmed.

Example 2
<Preparation of bleach-fixing astringent solution>
In the development processing described in Example 1, the same color developer, stabilizing solution tank solution and replenisher solution were used.

  For the bleach-fixing solution, each compound shown in Table 2 was used, and bleach-fixing solutions B-1 to B-14, each of which was appropriately adjusted so as to have the surface tension value shown in Table 2, were used. In the same manner as described in No. 1, a running treatment up to 1.5R was performed to obtain bleach-fixed astringent solutions 2-1 to 2-15. Note that the bleach-fixing astringent solution 2-11 uses the bleach-fixing solution B-10, and the squeeze roller pressure of the conveying section A from the bleach-fixing tank 2 to the stabilizing tank 3-1 is changed to 1.2 times. And run.

  The surfactants X and Y used for the preparation of the bleach-fixing solutions B-13 and B-14 shown in Table 2 are as follows.

Surfactant X: Diapon (manufactured by NOF Corporation)
Surfactant Y: Adeka Coal PS (Asahi Denka)
<Evaluation of bleach-fixed astringent solution>
Using the bleach-fixed astringent solutions 2-1 to 2-15 prepared above and the bleach-fixed astringent solutions 1-1, 1-5, and 1-6 prepared in Example 1, similar to the method described in Example 1 Using a silver halide color photographic light-sensitive material (color paper) with a dry film thickness of 5.5 μm of the total hydrophilic colloid layer on the exposed surface side, white background stain resistance and scratch resistance / dirt after storage processing Resistance was evaluated.

  The results obtained are shown in Table 2.

  As is apparent from the results shown in Table 2, the bleach-fixing of the present invention in which the surface tension was adjusted to a range of 45 mN / m or less using the compounds represented by the general formulas (I) to (IV) according to the present invention. It can be seen that the astringent solution is excellent in white background stain resistance after the storage treatment, has excellent scratch resistance and stain resistance, and provides stable running performance.

  As shown in the development process 2-1 (bleach-fixing astringent solution 2-1), if the surface tension is 45 mN / m or more even if the compound represented by the general formula (I) is contained, the white background after the storage process It was confirmed that the stain resistance deteriorated, and there were many scratches and stains on the print even during the running process.

  In the development treatment 2-10, even when the compound represented by the general formula (IV) is contained, the surface tension is 45 mN / m or more and the white background stain resistance is poor.

  In the development process 2-11, in order to improve this, the nip pressure of the squeeze roller was set to 1.2 times the current level. As a result, the stain resistance on the white background was slightly improved, but on the other hand, it caused re-scratches and dirt during running.

Example 3
<Preparation of bleach-fixing astringent solution>
In the development processes 2-1 and 2-3 to 2-5 described in the second embodiment, the structure of the conveyance processing unit of the automatic developing machine is the submerged conveyance type automatic developing machine illustrated in FIGS. 2, 3, and 4. In the same manner as above except that the change was made, development processing was performed to prepare bleach-fixed astringent solutions 3-1 to 11-11.

<Evaluation of bleach-fixed astringent solution>
Using the prepared bleach-fixing astringent solutions 3-1 to 3-11 and the bleach-fixing astringent solutions 2-1, 2-3, and 2-5 prepared in Example 2, similar to the method described in Example 1. Using a silver halide color photographic light-sensitive material (color paper) with a dry film thickness of 5.5 μm of the total hydrophilic colloid layer on the exposed surface side, white background stain resistance and scratch resistance / dirt after storage processing Resistance was evaluated.

  The results obtained are shown in Table 3.

  In addition, the measurement of the contamination rate (%) of the bleach-fixing solution to the stabilization processing tank 3-3 shown in Table 3 is the bleach-fixing solution composition contained in the processing solution in the stabilization processing tank 3-3. It was calculated by quantifying the iron content, which is a constituent element.

  As is apparent from the results shown in Table 3, in the comparative example in which the surface tension of the bleach-fixing solution is 50 mN / m, at least one of the conveying modes from the bleaching process step to the final tank is in-liquid conveyance. In this case, since the amount of the processing liquid brought from the previous tank to the next tank increases, the contamination ratio of the bleach-fixing liquid to the stabilization processing tank 3-3, which is the final tank in this embodiment, greatly increases. Along with this, the white stain resistance at the time of print storage is greatly deteriorated.

  On the other hand, within the scope of the present invention, even when at least one of the conveyance modes from the bleaching process step to the final tank is in-liquid conveyance, the white background stain resistance at the time of print storage is equivalent to that in the case of conventional out-of-liquid conveyance. It is.

  That is, it can be seen that the effect of the present invention can be obtained more remarkably when at least one of the modes of conveyance between the bleaching process and the final tank is in-liquid conveyance.

Example 4
<Evaluation of bleach-fixed astringent solution>
Using the bleach-fixing astringent solutions 1-5, 2-1, 2-7, and 2-12 prepared in Examples 1 and 2, in the same manner as in Example 1, a dry film of a completely hydrophilic colloid layer Using the silver halide color photographic light-sensitive materials listed in Table 4, the white background stain resistance after the storage treatment was evaluated.

  Table 4 shows the obtained results.

  As is apparent from the results shown in Table 4, in the development processing using a bleach-fixing solution having a surface tension exceeding 45 mN / m, the hydrophilic colloid layer film on the exposed surface side of the silver halide color photographic light-sensitive material to be processed It can be seen that as the thickness increases, the resistance to white background stain after storage processing deteriorates. In particular, when the film thickness was 10 μm or more, the degree of deterioration tended to be remarkable.

  On the other hand, in the development processing using a bleach-fixing solution having a surface tension in the range of 45 mN / m or less, as the film thickness of the hydrophilic colloid layer of the silver halide color photographic material to be processed increases. The white background stain resistance tended to deteriorate somewhat, but when the film thickness was 10 μm or more as seen in the development process 4-3, the white background stain resistance did not tend to deteriorate significantly.

  From this, it can be seen that the effect of the present invention is more remarkable when the dry thickness of the hydrophilic colloid layer on the exposed surface side of the silver halide color photographic material to be processed is 10 μm or more.

It is a schematic sectional drawing which shows an example of the automatic developing machine of a liquid conveyance system. It is a schematic sectional drawing which shows an example of the automatic processor which incorporated the submerged conveyance system in a part between processing tanks. It is a schematic sectional drawing which shows another example of the automatic processor which incorporated the submerged conveyance system in the part between processing tanks. It is a schematic sectional drawing which shows another example of the automatic processor which incorporated the submerged conveyance system in the part between processing tanks.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Color development processing tank 2 Bleach fixing processing tank 3-1, 3-2, 3-3 Stabilization processing tank 4 Guide roller 5, 8 Support roller 6 Squeeze roller 7 Blade conveyance mechanism A Out-of-liquid conveyance part P Silver halide color Photosensitive material

Claims (5)

In the method for processing a silver halide color photographic material, the silver halide color photographic material is processed through a color development processing step, a bleach-fixing processing step, a rinsing, a stabilization or washing step, and a drying processing step. A method for processing a silver halide color photographic light-sensitive material, wherein the bleach-fixing solution used in the step has a surface tension at 20 ° C. of 45 mN / m or less. 2. The method for processing a silver halide color photographic light-sensitive material according to claim 1, wherein the bleach-fixing solution has a surface tension at 20 ° C. of 35 mN / m or less. The silver halide color photograph according to claim 1 or 2, wherein the bleach-fixing solution contains at least one compound selected from compounds represented by the following general formulas (I) to (IV). Processing method of photosensitive material.

[Wherein, R ₁ represents an alkyl group or an alkenyl group, R ₂ represents a hydrogen atom, an alkyl group or a hydroxyalkyl group, and R ₃ and R ₄ independently represent a hydrogen atom, a hydroxyl group, an alkyl group or —COOM ₄ ( M ₄ represents a hydrogen atom or an alkali metal atom), X represents —CO— or —SO ₂ —, Y represents —O—, —S— or —CONR ₅ — (R ₅ represents a hydrogen atom, alkyl) M ₃ represents a hydrogen atom or an alkali metal atom, k represents 0 or 1, m1 represents an integer of 0 to 2, and n1 represents an integer of 1 to 3. ]
Formula (II)
R _6- (O) _x SO ₃ M ₆
[Wherein R ₆ represents an aliphatic group, alicyclic group, aromatic group or heterocyclic group, x represents 0 or 1, and M ₆ represents a cation. ]

[Wherein R ₇ represents an alkyl group having 1 to 2 carbon atoms, or a hydrogen atom, and R ₈ represents a substituted or unsubstituted alkyl group having 1 to 3 carbon atoms, a sulfonic acid group, a carboxyl group, a hydroxyl group, Alternatively, it represents a hydrogen atom, and R ₉ represents a hydrogen atom or a hydroxyl group. p represents an integer of 0 to 2, and r represents an integer of 1 to 3. A may be substituted with a hydrogen atom at any position of the benzene ring. Further, s represents 0 to 50, t represents an integer of 0 or 1, and u represents a number of 2 to 150. ]

[Wherein, R ¹ represents an alkyl group or an alkenyl group having 8 to 21 carbon atoms in total. M represents a hydrogen atom or a metal cation. Z ¹ represents NH ₂ or OM ′, M ′ represents a hydrogen atom or a metal cation, and may be the same as or different from M. n represents 1 or 2. ] 4. At least one of the modes of transporting the silver halide color photographic light-sensitive material between the bleach-fixing step and the final processing step is a submerged transport method. A method for processing a silver halide color photographic light-sensitive material described in 1. The silver halide according to any one of claims 1 to 4, wherein the total dry film thickness of the hydrophilic colloid constituent layer on the exposed surface side of the silver halide color photographic light-sensitive material is 10 µm or more. Processing method of color photographic material.

Images