JP2006267353A - Method for processing silver halide color photosensitive material - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for processing a silver halide color photosensitive material having, as a support, a plastic resin film containing white pigment in which transportability is improved and rear stain is reduced. <P>SOLUTION: The method for processing a silver halide color photosensitive material where a silver halide color photosensitive material for reflective admiration has a plastic resin film containing white pigment as a support comprises: cutting the silver halide color photosensitive material to a fixed size; subjecting the cut material to a color developing step, to a bleaching-fixing step or a bleaching step, to a fixing step, to a stabilizing step or a rinsing step and to a drying step, a color developing solution used in the color developing step contains a compound expressed by general formula (I). <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a method for processing a silver halide color photographic light-sensitive material, and more particularly to a method for processing a silver halide color photographic light-sensitive material having a plastic resin film containing a white pigment as a support.

  Silver halide color photographic light-sensitive materials are used in a very wide range of fields because of their high sensitivity, high quality image quality, and simplicity of image forming methods.

  In recent years, as a print material for reflection viewing, for example, in addition to a silver halide color photographic light-sensitive material for reflection viewing using a support in which both sides of a paper support are coated with a resin layer, so-called general color paper, Reflective ornamental silver halide color photographic materials, in which a silver halide photosensitive layer is provided on a plastic resin film containing a white pigment, for example, a polyethylene terephthalate film (hereinafter also referred to as white PET), are used.

  The above-mentioned silver halide color photographic light-sensitive material for reflection viewing using white PET is mainly used for indoor and outdoor displays. Therefore, in order to maintain high flatness during installation, a thick polyethylene terephthalate film is used. A film is used. As a result, the silver halide color photographic light-sensitive material is extremely stiff and has high rigidity.

  When processing such a silver halide color photographic light-sensitive material for reflection ornamentation using white PET, the processing at a large developing station is carried out in a large amount using a large automatic developing machine. Is not a “sheet transport method” in which a silver halide color photographic light-sensitive material is cut into a sheet and transported by a transport roller, but is processed continuously using a roll-shaped silver halide color photographic light-sensitive material. Since this is a “roll conveyance method” and uses a large automatic processor, the turn radius where the silver halide color photographic light-sensitive material changes direction between processing tanks is sufficiently large. Even a silver halide color photographic light-sensitive material for reflection viewing using PET can be stably transported without causing poor transport.

  On the other hand, in the photographic processing service industry in recent years, as a part of improving services for users and as a means of improving productivity, a small automatic processor such as a so-called minilab is used, for example, a silver halide color photographic light-sensitive material. Processing in which the processing speed from development to drying is greatly shortened has been widespread.

  In the above-described small automatic processor, a silver halide color photographic light-sensitive material with a small amount of processing is often processed in a sheet form by a sheet conveying method, not by a roll conveying method. In such a situation, if the reflective silver halide color photographic light-sensitive material using white PET having high rigidity is processed by the sheet conveying method, the radius of curvature of the turn portion is small because the automatic processor itself is small. It is extremely small, and as a result, it has a serious problem of being caught at the turn part and causing poor conveyance.

  In order to improve the transportability of silver halide color photographic light-sensitive materials, attempts have been made to improve from an automatic processor.

  For example, a permanent magnet is built in one of a pair of rollers, the roller with a built-in permanent magnet is rotationally driven by an electric field or a magnetic field from outside the processing solution system, and the photosensitive material is conveyed by this roller pair, thereby increasing the processing path length. There has been disclosed a developing apparatus for a photosensitive material that has good transportability of the photosensitive material even in a long (long processing time) color processing (see, for example, Patent Document 1). In addition, by defining the relationship between the radius of curvature of the outer turn part between the treatment tanks, the path length of the treatment liquid immersion part of the treatment tank, and the conveyance speed within a specific range, it is possible to prevent conveyance, scratches, broken edges, and edge contamination. An improved paper development processing apparatus is disclosed (for example, see Patent Documents 2 and 3).

  However, in a minilab or the like where the development processing apparatus is miniaturized as described above, it is difficult only by improvement from the above-described apparatus surface, and in particular, a silver halide color for reflection ornamentation using white PET having high rigidity. There is a limit to the processing of photographic light-sensitive materials, and immediate improvement is required.

On the other hand, in the processing of a silver halide color photographic light-sensitive material, in a large-scale developing laboratory that performs intensive processing, the processing amount increases as the processing is performed for about 24 hours per day, and as a result, a large amount of replenisher is added. The renewal rate of the processing liquid is increased. On the other hand, in the storefront processing using the minilab, the operation time is about 6 to 12 hours, and the silver halide color photographic light-sensitive material is processed intermittently. For this reason, in processing using a minilab, if the processing interval is widened, tar-like foreign matter adheres to the transport roller, etc., and the attached foreign matter adheres to the back surface of the silver halide color photosensitive material to be processed later, resulting in poor transport. It is becoming easy to cause dirt on the back side. In particular, in the silver halide color photographic light-sensitive material for reflection ornamentation using white PET having high rigidity described above in order to maintain high flatness, a hydrophilic colloid layer is coated on the back surface to provide a curl balance between the front and back surfaces. In many cases, such a silver halide color photographic light-sensitive material has been found to exhibit conveyance defects and backside stains more remarkably, and is required to be improved immediately.
JP-A-11-109589 (Claims) JP-A-11-223912 (Claims) JP-A-11-223914 (Claims)

  The present invention has been made in view of the above problems, and its object is to process a silver halide color photographic light-sensitive material having as a support a plastic resin film containing a white pigment with improved transportability and backside contamination. Is to provide.

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

(Claim 1)
A silver halide color photographic light-sensitive material for reflection viewing, which is a plastic resin film containing a white pigment as a support, is cut to a certain size, and then a color development process, bleach-fixing process or bleach-fixing process and fixing process, stabilization A method for processing a silver halide color photographic light-sensitive material processed through a processing step comprising a step or a rinsing step and a drying step, wherein the color developer used in the color development step is represented by the following general formula [I]: A method for processing a silver halide color photographic light-sensitive material comprising a compound represented by the formula:

[In the formula, L represents an alkylene group, A represents a carboxyl group, a sulfo group, a phosphono group, a phosphine group, a hydroxyl group, an amino group, an ammonio group, a carbamoyl group, a sulfamoyl group, an alkylsulfonyl group, a hydrogen atom, an alkoxyl group, Or -O- (B-O) _n- R ', R and R' each represent a hydrogen atom or an alkyl group. B represents an alkylene group, and n represents an integer of 1 to 4. ]
(Claim 2)
2. The method for processing a silver halide color photographic material according to claim 1, wherein the plastic resin film is polyethylene terephthalate.

(Claim 3)
3. The method for processing a silver halide color photographic light-sensitive material according to claim 1 or 2, wherein the silver halide color photographic light-sensitive material is conveyed and processed at a feed width of 130 mm or less.

(Claim 4)
The silver halide according to any one of claims 1 to 3, wherein the color developer contains at least one selected from compounds represented by the following general formulas [II] to [V]. Processing method of color photographic 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. ]
General formula [III]
R _6- (O) _x SO ₃ M ₆
[Wherein R ₆ represents an aliphatic group or a heterocyclic group, x represents 0 or 1, and M ₆ represents a hydrogen atom or a cation. ]

[Wherein R ₁ represents an alkyl group having 1 to 2 carbon atoms or a hydrogen atom, R ₂ represents an alkyl group having 1 to 3 carbon atoms, a sulfo group, a carboxyl group, a hydroxyl group, or a hydrogen atom, R ₃ represents a hydrogen atom or a hydroxyl group. p represents an integer of 0 to 2, and r represents an integer of 1 to 3. A may be substituted with a hydrogen atom at any position of the benzene ring. Further, s represents 0 to 50, t represents an integer of 0 or 1, and u represents an integer of 2 to 150. ]
General formula [V]
_{HO- (CH 2 CH 2 O)} n - (CH 2 CH (CH 3) O) m -H
[In formula, n represents the integer of 0-200, m represents the integer of 0-50, and m and n do not become 0 simultaneously. ]
(Claim 5)
The processing method of a silver halide color photographic material according to any one of claims 1 to 4, wherein the processing temperature of the color developer is 38 ° C or higher.

  According to the present invention, it is possible to provide a method for processing a silver halide color photographic light-sensitive material having, as a support, a plastic resin film containing a white pigment with improved transportability and backside contamination.

  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 cut the silver halide color photographic light-sensitive material for reflection viewing, which is a plastic resin film containing a white pigment, into a certain size, A method for processing a silver halide color photographic light-sensitive material processed through a processing step comprising a color development step, a bleach-fixing step or a bleaching step and a fixing step, a stabilization step or a rinsing step, and a drying step. A color developer used in the development step contains a compound represented by the above general formula [I], and is a white color having improved transportability and backside stains by a processing method of a silver halide color photographic light-sensitive material. The present inventors have found that a processing method for a silver halide color photographic light-sensitive material having a plastic resin film containing a pigment as a support can be realized. Was is up.

  Details of the present invention will be described below.

  First, each processing solution composition, processing conditions, and development processor applicable to the processing method of the silver halide color photographic light-sensitive material of the present invention will be described.

  In the processing method of the silver halide color photographic light-sensitive material of the present invention (hereinafter also simply referred to as processing method), a color development step using a color developer, a bleach-fixing step using a bleach-fixing solution, or a bleaching step and fixing using a bleach-solution. Fixing process using a liquid, a stabilizing process using a stabilizing liquid or a rinsing process using a rinsing liquid, and a processing process consisting of a drying process, and a replenishing color developer, a replenishing bleaching liquid, and a replenishing fixing liquid, respectively. Alternatively, the development can be continuously performed while replenishing a replenishing bleach-fixing solution, a replenishing stabilizing solution, a replenishing rinse solution, or the like.

  In the processing method of the present invention, the color developer used in the color development step contains the compound represented by the general formula [I].

  By containing the compound represented by the above general formula [I] according to the present invention, the color developer drastically improves the stability of the color developer, and the color developing agent can be used even under a low processing amount. In particular, when processing silver halide color photographic light-sensitive materials for reflection viewing, which is a plastic resin film containing a white pigment having a backcoat layer, by preventing oxidation and the like, and preventing the generation of foreign substances such as tar. Back surface contamination can be effectively prevented.

  Hereinafter, the compound represented by the general formula [I] according to the present invention will be described.

  In the general formula [I], L represents an optionally substituted alkylene group, and A represents a carboxyl group, a sulfo group, a phosphono group, a phosphine group, a hydroxyl group, an amino group, an ammonio group, a carbamoyl group, a sulfamoyl group, an alkyl group. A sulfonyl group, a hydrogen atom, an alkoxyl group, or —O— (B—O) n—R ′ is represented, and R and R ′ each represent a hydrogen atom or an alkyl group. B represents an alkylene group, and n represents an integer of 1 to 4.

  In the general formula [I], the alkylene group represented by L includes those having a substituent, 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 phosphine group, a hydroxyl group, and an ammonio group. 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, an amino group, an ammonio group, a carbamoyl group, a sulfamoyl group, an alkylsulfonyl group or an alkoxy group, and each may have a substituent. Particularly preferred examples include a carboxyl group, a sulfo group, a hydroxyl group, a phosphono group and a 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. When R is an alkyl group, the alkyl group preferably has 1 to 10 carbon atoms, particularly preferably 1 to 5 carbon atoms. Further, it may have a substituent, and preferred substituents include a carboxyl group, a sulfo group, a phosphono group, a phosphinic acid group, a hydroxyl group, an amino group, an ammonio group, a carbamoyl group, a sulfamoyl group, an alkylsulfonyl group, and an alkoxyl group. , —O— (B—O) n—R ′ and the like. B and R ′ are synonymous with those described in the description of A. There may be two or more substituents. 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. Carboxymethyl group, carboxyethyl group, sulfoethyl group, sulfopropyl group, phosphonomethyl group and phosphonoethyl group can be mentioned as particularly preferred examples. L and R may be linked to form a ring.

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

The compound represented by the general formula [I] according to the present invention is contained in a color developing solution and a color developer replenisher at a concentration of 1 × 10 ⁻³ mol / L to 1 × 10 ⁻¹ mol / L. It is preferable.

  The color developer according to the present invention may contain at least one selected from the compounds represented by the general formulas [II] to [V] together with the compound represented by the general formula [I]. From the viewpoint that the object and effects of the present invention can be further exhibited.

In the general formula [II], 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 Represents a hydrogen atom, an alkyl group or a hydroxyalkyl group), 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. .

In the general formula [II], 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 the general formula [II] are shown below.

  In addition to the above exemplified compounds, for example, 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 compound represented by the general formula [III] will be described.

In the general formula [III], R ₆ represents an aliphatic group or a heterocyclic group, and may have a substituent. x represents 0 or 1, and M ₆ represents a hydrogen atom or a cation.

In the general formula [III], 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 of each group include butyl, pentyl, cyclopentyl, hexyl, cyclohexyl, octyl, and dodecyl. 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), An aryloxy group (eg, phenoxy, naphthyloxy, etc.), an alkoxycarbonyl group (eg, methoxycarbonyl, ethoxycarbonyl, butoxycarbonyl, 2-ethylhexylcarbonyl, etc.), an alkenyl group (eg, vinyl, allyl, etc.) Each group), a heterocyclic group (for example, 2-pyridyl, 3-pyridyl, 4-pyridyl, morpholyl, piperidine, piperazyl, pyrimidine, pyrazoline, furyl, etc.), an alkynyl group (for example, propargyl group, etc.), An amino group (eg amino, N, N-dimethylamino) Each group anilino), a cyano group, sulfonamido group (e.g., methylsulfonylamino, ethylsulfonylamino, butylsulfonylamino, octyl sulfonylamino, may be substituted by each group) such as phenylsulfonylamino.

  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.

The above-mentioned alkenyl group, alkynyl group, and heterocyclic group can 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 [III] are listed below, but the present invention is not limited thereto.

III-1: CH ₃ (CH ₂ ) ₅ SO ₃ Na
III-2: CH ₃ (CH ₂ ) ₆ SO ₃ Na
III-3: CH ₃ (CH ₂ ) ₇ SO ₃ Na
III-4: CH ₃ (CH ₂ ) ₅ OSO ₃ Na
_{III-5: CH 3 (CH} 2) 6 OSO 3 Na
_{III-6: CH 3 (CH} 2) 7 OSO 3 Na
III-7: CH ₃ O (CH ₂ ) ₂ SO ₃ Na

III-11: CH ₃ (CH ₂ ) ₅ SO ₃ Na
Next, the compound represented by the general formula [IV] will be described.

In the general formula [IV], R ₁ represents an alkyl group having 1 or 2 carbon atoms (for example, a methyl group or an ethyl group) or a hydrogen atom, and R ₂ represents a linear or branched substituted or unsubstituted carbon atom number. 1 to 3 alkyl groups (for example, methyl group, ethyl group, propyl group, (i) propyl group, hydroxymethyl group, sulfomethyl group, hydroxyethyl group, sulfoethyl group, disulfoethyl group, dihydroxyethyl group, 1-hydroxypropyl group) , 2-hydroxypropyl group, 1-sulfopropyl group, 2-sulfopropyl group, trihydroxy (i) propyl group, 1,2-disulfopropyl group), sulfo group, carboxyl group, hydroxyl group and hydrogen atom, R3 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 an integer of 2 to 150.

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

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

  Next, the compound represented by the general formula [V] will be described.

General formula [V]
_{HO- (CH 2 CH 2 O)} n - (CH 2 CH (CH 3) O) m -H
In the general formula [V], n represents an integer of 100 to 200, m represents an integer of 10 to 50, and specific compounds are shown below, but the present invention is not limited to these compounds. .

V-1: HO— (CH ₂ CH ₂ O) ₁₅₀ — (CH ₂ CH (CH ₃ ) O) ₃₀ —H
_{V-2: HO- (CH 2} CH 2 O) 100 - (CH 2 CH (CH 3) O) 10 -H
_{V-3: HO- (CH 2} CH 2 O) 100 - (CH 2 CH (CH 3) O) 15 -H
_{V-4: HO- (CH 2} CH 2 O) 100 - (CH 2 CH (CH 3) O) 20 -H
_{V-5: HO- (CH 2} CH 2 O) 150 - (CH 2 CH (CH 3) O) 20 -H
_{V-6: HO- (CH 2} CH 2 O) 150 - (CH 2 CH (CH 3) O) 40 -H
_{V-7: HO- (CH 2} CH 2 O) 200 - (CH 2 CH (CH 3) O) 30 -H
_{V-8: HO- (CH 2} CH 2 O) 200 - (CH 2 CH (CH 3) O) 40 -H
_{V-9: HO- (CH 2} CH 2 O) 200 - (CH 2 CH (CH 3) O) 50 -H
_{V-10: HOCH 2 CH 2} OH
V-11: HOCH ₂ CH ₂ OCH ₂ CH ₂ OH
_{V-12: HOCH 2 CH (} CH 3) OH
In the present invention, the amount of the compound represented by the general formulas [II] to [V] is 0.0001 to 0.06 mol per liter for both the color developing solution and the replenisher.

  Next, the color developer, bleaching solution, bleach-fixing solution, fixing solution, stabilizing solution and rinsing solution used in the present invention will be described.

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

1) N, N-diethyl-p-phenylenediamine 2) 4-amino-3-methyl-N, N-diethylaniline 3) 4-amino-N- (β-hydroxyethyl) -N-methylaniline 4) 4 -Amino-N-ethyl-N- (β-hydroxyethyl) aniline 5) 4-amino-3-methyl-N-ethyl-N- (β-hydroxyethyl) aniline 6) 4-amino-3-methyl-N -Ethyl-N- (3-hydroxypropyl) aniline 7) 4-Amino-3-methyl-N-ethyl-N- (4-hydroxybutyl) aniline 8) 4-Amino-3-methyl-N-ethyl-N -(Β-Methanesulfonamidoethyl) aniline 9) 4-Amino-N, N-diethyl-3- (β-hydroxyethyl) aniline 10) 4-Amino-3-methyl-N-ethyl-N- (β- Me Xylethyl) aniline 11) 4-Amino-3-methyl-N- (β-ethoxyethyl) -N-ethylaniline 12) 4-Amino-3-methyl-N- (3-carbamoylpropyl) -Nn-propyl -Aniline 13) 4-amino-N- (4-carbamoylbutyl) -Nn-propyl-3-methylaniline 14) N- (4-amino-3-methylphenyl) -3-hydroxypyrrolidine 15) N- (4-Amino-3-methylphenyl) -3- (hydroquinmethyl) pyrrolidine 16) N- (4-amino-3-methylphenyl) -3-pyrrolidinecarboxamide Among the p-phenylenediamine derivatives, particularly preferred Illustrative compounds 5), 6), 7), 8) and 12), among which exemplary compounds 5) and 8) are preferred. These p-phenylenediamine derivatives are in the form of salts such as sulfates, hydrochlorides, sulfites, naphthalene disulfonates, p-toluenesulfonates, or free base types (also referred to as free forms). The concentration of the aromatic primary amine developing agent in the working solution is preferably 2 mmol to 200 mmol, more preferably 6 mmol to 100 mmol, and particularly preferably 10 mmol to 40 mmol per liter of the developing solution.

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

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

  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), and 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 color developing composition of the organic preservative is preferably contained at 1 × 10 ⁻³ mol or more and 1 × 10 ⁻¹ mol or less per liter. In addition, the color developer may contain a small amount of sulfite ions or may not substantially contain sulfite ions depending on the type of silver halide color photographic light-sensitive material to be used. It is preferable to include. Moreover, you may contain a small amount of hydroxylamine. Hydroxylamine (usually used in the form of hydrochloride or sulfate, but omits the salt form below) acts as a developer preservative like sulfite ion, but at the same time hydroxylamine itself has silver developing activity. Therefore, it is necessary to keep the addition amount small.

  The color developer may contain an arylsulfinic acid such as benzenesulfinic acid, p-toluenesulfinic acid, m-carboxybenzenesulfinic acid.

  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 may contain an alkali agent, a buffering agent and, if necessary, an acid so that the pH value can be maintained.

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

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

  The addition amount of the buffer is preferably 0.01 to 2 mol, more preferably 0.1 to 0.5 mol per liter for both the color developing solution and its replenisher.

  For example, calcium or magnesium precipitation inhibitors or various chelating agents that are also stability improvers can be added to the color developing solution as other color developer components. For example, nitrilotriacetic acid, diethylenetriaminepentaacetic acid, ethylenediaminetetraacetic acid, N, N, N-trimethylenephosphonic acid, ethylenediamine-N, N, N ′, N′-tetramethylenesulfonic acid, transsirohexasidiaminetetraacetic acid, 1,2-diaminopropan tetraacetic acid, glycol ether diamine tetraacetic acid, ethylenediamine orthohydroxyphenylacetic acid, ethylenediamine disuccinic acid (SS form), N- (2-carboxylateethyl) -L-aspartic acid, β-alanine diacetic acid, 2-phosphonobutane-1,2,4-tricarboxylic acid, 1-hydroxyethylidene-1,1-diphosphonic acid, N, N′-bis (2-hydroxybenzyl) ethylenediamine-N, N′-diacetic acid, 1,2 -Dihydroxybenzene-4,6-disulfonic acid and the like It is. These chelating agents may be used in combination of two or more as required. Further, the amount of these chelating agents may be an amount sufficient to sequester metal ions in the color developer. 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 developing solution. Examples of the development accelerator include JP-B-37-16088, JP-A-37-5987, JP-A-38-7826, JP-A-44-12380, JP-A-45-9019, and U.S. Pat. No. 3,813,247. Or neo ether compounds represented in the specification, p-phenylenediamine compounds represented in JP-A-52-49829 and JP-A-50-15554, JP-A-50-137726, JP-B 44-30074 Quaternary ammonium salts, U.S. Pat. Nos. 2,494,903, 3,128,182, and 4,230,796, which are described in JP-A-56-156826 and JP-A-52-43429. No. 3,253,919, Japanese Patent Publication No. 41-11431, U.S. Pat. Nos. 2,482,546, 2,596,926, and 3,582,346. Or the amine compounds described in the specification, JP-B-37-16088, JP-A-42-25201, U.S. Pat. No. 3,128,183, JP-B-41-11431, JP-A-42-23883 and U.S. Pat. , 532, 501 and the like, polyalkylene oxides represented in the respective publications and specifications, other 1-phenyl-3-virazolitones or imidazoles can be added as necessary. The added amount in the composition is determined so that the concentration of both the color developer and its replenisher is 0.001 to 0.2 mol, preferably 0.01 to 0.05 mol, per liter.

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

  Various surfactants such as alkyl sulfonic acid, aryl sulfonic acid, aliphatic carboxylic acid, and aromatic carboxylic acid may be added to the color developing solution as necessary. Their concentration is preferably 0.0001 to 0.2 mol per liter for both the color developer and its replenisher, and more preferably 0.001 to 0.05 mol.

  In the color developing solution, a fluorescent brightening agent can be used as necessary. As the optical brightener, a bis (triazinylamino) stilbene sulfonic acid compound is preferred. As the bis (triazinylamino) stilbene sulfonic acid compound, known or commercially available products can be used. As the known bis (triazinylamino) stilbene sulfonic acid compound, for example, compounds described in JP-A-6-329936, JP-A-7-140625, JP-A-10-14049 and the like are preferable. Commercially available compounds are described, for example, in “Dyeing Note”, 9th edition (Colored Dyeing), pages 165 to 168, and among the compounds described therein, Blankophor BSU liq. And HakkolBRK are preferred.

  Other bis (triazinylamino) stilbene sulfonic acid compounds include compounds I-1 to I-48 described in paragraphs [0038] to [0049] of JP-A No. 2001-281823 and JP-A No. 2001-281823. The compounds II-1 to II-16 described in paragraph Nos. [0050] to [0052] of 2001-281823 can also be mentioned. The addition amount of the optical brightener is preferably 0.1 to 0.1 mol per liter for both the color developing solution and the replenisher.

Further, when bromine ions are contained in the color developing solution, it is preferably 1.0 × 10 ⁻³ mol / liter or less. The color developing solution preferably contains chlorine ions of 3.5 × 10 ^{−2 to} 1.5 × 10 ⁻¹ mol / liter, but chlorine ions are usually released to the developer as a by-product of development. Therefore, it may not be necessary to add to the replenisher.

In the present invention, the processing temperature of color development that can be applied in the processing method is usually in the range of 30 to 55 ° C., but is 38 ° C. or more from the viewpoint that the objective effect of the present invention can be fully exhibited. Is more preferable, it is 38-55 degreeC, More preferably, it is 38-45 degreeC. The color development processing time is preferably from 5 to 90 seconds, more preferably from 15 to 60 seconds. The replenishment amount is preferably small, but 15 to 600 ml per 1 m ^{2 of} the light-sensitive material is suitable, preferably 15 to 120 ml, particularly preferably 30 to 60 ml. In the present invention, the color development time refers to the time from when the photosensitive material enters the color developer to the next processing step (for example, bleach-fixing solution). When processed by an automatic developing machine or the like, the time during which the photosensitive material is immersed in the color developer (so-called submerged time) and the photosensitive material leave the color developer, and the solution is prepared for the next processing step. The total of both the time for transporting outside (so-called crossover time) is called color development time. The crossover time is preferably 10 seconds or less, more preferably 5 seconds or less.

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

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

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

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

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

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

  Bleaching solutions, fixing solutions, bleach-fixing solutions are sulphites as preservatives, for example, sodium sulfite, potassium sulfite, ammonium sulfite, potassium bisulfite, sodium bisulfite, sodium metabisulfite, potassium metabisulfite, metabisulfite. Addition of ammonium sulfate or the like is common, but in addition, ascorbic acid, a carbonyl bisulfite adduct, a carbonyl compound, or the like may be added.

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

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

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

  Next, the rinse process or the stabilization process and the treatment liquid used therein will be described.

  The rinse or stabilizing solution used in the stabilization step includes chelating agents (for example, ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, 1-hydroxyethylidene-1,1-diphosphonic acid, etc.), buffering agents (for example, potassium carbonate, borate) , Acetates, phosphates, etc.), antifungal agents (eg, Dearside 702 (made by Dearborn, USA), p-chloro-m-cresol, benzoisothiazolin-3-one, etc.), fluorescent whitening agents (eg, , Triazinyl stilbene compounds, etc.), antioxidants (eg, ascorbate, etc.), water-soluble metal salts (eg, zinc salt, magnesium salt, etc.), etc. Can do.

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

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

  The temperature of the stabilization step or the rinsing step can be variously set depending on the use and characteristics of the silver halide color photographic light-sensitive material to be processed, but is generally preferably 15 to 45 ° C, more preferably 20 to 40 ° C. Although the time can be set arbitrarily, a shorter time is desirable from the viewpoint of reducing the processing time. The time is preferably 5 seconds to 2 minutes 30 seconds, and more preferably 10 seconds to 1 minute. However, when the silver halide color photographic light-sensitive material is color paper, the time required for the stabilization processing step is 8 to 8 minutes. It is preferably 26 seconds.

  The time required for the stabilization process or the rinsing process here refers to the time until the photosensitive material is transported to the subsequent drying process, for example, when the process is one tank. Means the time from when the photosensitive material is immersed in the first tank until it leaves the final tank, and includes the crossover time. The crossover time is the time from when the silver halide color photographic light-sensitive material comes out of the stabilizing solution or the rinsing solution to the next drying step, when the stabilization step or the rinsing step is one tank. When the stabilization process or rinsing process is composed of a plurality of tanks, the time until the silver halide color photographic light-sensitive material discharged from the liquid in the front tank penetrates into the next tank liquid. It refers to the total time of the out-of-liquid time and the total time from the time when the liquid in the final tank is discharged to the time when the next drying process is started. The out-of-solution time between each tank in the stabilization process or the rinsing process, and the time from the end of the liquid in the final tank to the start of the next drying process may be all equal or It may be set at different times. In the present invention, the ratio of each crossover time to the processing time of each process is defined as the crossover time ratio.

  In the stabilization process or the rinsing process according to the present invention, a preferred crossover time ratio is 12% to 20%.

A smaller replenishment amount is preferable from the viewpoints of running cost, reduction of discharge amount, handleability, and the like, but a specific preferable replenishment amount is a silver halide color photographic light-sensitive material, and a replenishment amount of 0. It is preferably 5 to 50 times, more preferably 3 to 40 times. Alternatively, the amount is preferably 1 liter or less per 1 m ^{2 of} silver halide color photographic light-sensitive material, more preferably 500 ml or less. The replenishment may be performed continuously or intermittently.

  In the treatment method of the present invention, the structure of the stabilization process or the rinsing process using the stabilizing solution or rinsing may be composed of one tank or two or more tanks. It is preferable to use a multistage counter-current system composed of two or more tanks.

  The multi-stage counter-current system is a silver halide photographic photosensitive system in which a stabilizing solution overflows into each multi-stage divided stabilization tank in a plurality of stabilization tanks or rinse tanks from the downstream to the upstream in the conveyance direction of the photosensitive material. This is a system in which the material flows along a material conveyance path and is subjected to stabilization treatment or rinsing treatment.

  Next, the drying process that can be used in the present invention will be described.

  The drying temperature in the drying step applied to the treatment method of the present invention is preferably 50 ° C. or higher, more preferably 75 ° C. or higher, more preferably the effect of the present invention is exhibited, and further preferably 75 to 85 ° C. . The drying time is preferably 20 seconds to 2 minutes, particularly preferably 40 seconds to 80 seconds. Furthermore, as a means for shortening the drying time in order to perform rapid development processing, as a means on the photosensitive material side, improvement by reducing the amount of moisture brought into the film by reducing the amount of hydrophilic binder such as gelatin. Is possible. Also, from the viewpoint of reducing the amount of moisture brought into the drying process, it is possible to accelerate drying by absorbing water with a squeeze roller or cloth immediately after being transported from the final tank. As a matter of course as an improvement means from the dryer side, it is possible to speed up drying by increasing the temperature or increasing the drying air. Further, as described in JP-A-3-157650, drying can be accelerated by adjusting the blowing angle of the dry air to the photosensitive material or by the method of removing the exhaust air.

  In the processing method of the present invention, it is preferable to perform processing using an automatic processor.

  Hereinafter, an automatic processor preferably used in the present invention will be described.

  FIG. 1 is an overall configuration diagram showing an example of an automatic developing machine for color paper in which an automatic developing machine and a printing machine for a silver halide color photographic light-sensitive material are integrated.

  In FIG. 1, a magazine M in which unexposed silver halide color photographic light-sensitive material is stored in a roll shape is set in the lower left part of the photographic printing machine B of the automatic processor AP for silver halide color photographic light-sensitive material. . The silver halide color photographic light-sensitive material p pulled out from the magazine is cut into a predetermined size via the feed roller R1 and the cutter part Ct, and becomes a sheet-like silver halide color photographic light-sensitive material p. This sheet-like silver halide color photographic light-sensitive material p is conveyed by the belt conveying means Be, and the image of the original image O is exposed by the light source and the lens L in the exposure unit E. The exposed sheet-like silver halide color photographic light-sensitive material p is further transported by a plurality of pairs of feed rollers R2, R3, and R4 and introduced into the self-machine AP. In the automatic machine AP, the sheet-like silver halide color photographic light-sensitive material p is contained in each of the color developing tank 1A, the bleach-fixing tank 1B, the stabilizing tanks 1C, 1D, and 1E (substantially three tanks). The processing solution tank 1) having the structure is sequentially conveyed by a roller conveying means (reference symbol pear), and is subjected to color development processing, bleach-fixing processing, and stabilization processing, respectively. The sheet-shaped photographic paper p subjected to the above-described processes is dried in the drying unit 6 and discharged outside the apparatus. A solid processing agent supply device 3A for supplying the processing baths of the color developing tank 1A, the bleach-fixing tank 1B, and the stabilizing tank 1E to the dissolution tanks 2A, 2B and 2E, the circulation tanks 2C and 2D, and the solid processing agent, 3B and 3E are provided. A replenishing water tank 4 supplies replenishing water to the color developing tank 1A and the stabilizing tank 1E.

  In the processing method of the present invention, the silver halide color photographic light-sensitive material for reflection viewing, which is a plastic resin film containing the white pigment according to the present invention, is processed by the sheet conveying method using the automatic processor as described above. In particular, when the silver halide color photographic light-sensitive material is transported at a feed width of 130 mm or less, the excellent transportability that is the object effect of the present invention can be realized, and preferably 70 mm or more and 130 mm or less. This is more remarkable when the feed width is.

  In the automatic processor according to the present invention, the linear velocity of conveyance is preferably 100 mm / second or less, more preferably 27.8 mm / second to 80 mm / second, and particularly preferably 27.8 mm / second to 50 mm / second. is there.

  In the transport of color paper automatic developing machines, the development process is performed after the color paper is cut to the final size (sheet type transport system) and the roll-shaped silver halide color photographic light-sensitive material. There is a method of cutting to the final size (cine type conveyance method). The cine type conveyance method is preferably a sheet type conveyance method because a photosensitive material of about 2 mm is wasted between images.

In each processing liquid according to the present invention, it is preferable that the area (opening area) where the liquid contacts the air in the processing tank and the replenishing liquid tank is as small as possible. For example, when the opening ratio is a value obtained by dividing the opening area (cm ² ) by the liquid tank (cm ³ ) in the tank, the opening ratio is preferably 0.08 (cm ⁻¹ ) or less, more preferably 0.01 ( 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 tank and the replenishment tank. Specifically, it is preferable to cover a plastic float or the like on a liquid surface or a liquid that does not mix with the processing liquid and does not cause a chemical reaction. As examples of the liquid, liquid paraffin, liquid saturated hydrocarbon, and the like can be used.

  In the present invention, in order to prevent the processing solution in the previous tank from being mixed into the next tank when the photosensitive material is transported, a structure of a crossover rack provided with a mixing prevention plate is preferable. Each processing solution according to the present invention is preferably subjected to so-called evaporation correction in which water corresponding to the evaporated amount of the processing solution is supplied, and particularly preferably applied to a color developer or a bleach-fixing solution.

  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 1-2254960 is installed, Calculate the amount of water evaporation in the monitor tank, calculate the amount of water evaporation in the bleach-fixing tank from this amount of water evaporation, replenish the water in the bleach-fixing tank in proportion to this amount of evaporation, a liquid level sensor, 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 developer is as described above, but it is preferable to reduce the aperture 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, per minute 0.1 m ³ to 1 m ³ is preferred emissions, particularly preferably is 0.2-0.4 m ² . The drying conditions of the silver halide color photographic light-sensitive material also affect the evaporation of the processing solution. As the drying method, it is preferable to use a ceramic warm air heater, and the supply air volume is preferably 4 to 20 m ³ per minute, particularly 6 to 10 m ³ . 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 processing tank of the automatic developing machine described above may be provided with a heater, a temperature sensor, a liquid level sensor, a circulation pump, a filter, a squeegee, a nitrogen stirrer, an air stirrer, and the like as necessary.

  In the processing method of the present invention, it is possible to attach a pump to each processing tank of the color development step, the bleach-fixing step or the bleaching step and the fixing step, the stabilization step or the rinsing step to provide a liquid circulation path. This is an effective means for maintaining the temperature and increasing the efficiency of liquid temperature control. In this invention, it is preferable from the viewpoint that the effect of this invention is exhibited more that the circulation amount of the process liquid in each process is 50-300 ml / min.

  Normally, a replenishing pump is used for replenishing the processing solution, but a bellows type replenishing 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 and crossovers.

  Resin such as PVC (polyvinyl chloride), PP (polypropylene), PE (polyethylene), TPX (polymethylpentene) is suitable for the roller material of the processing section. These materials can also be used for other processing liquid contact portions. In addition, PE resin is preferable also for the material of the replenishment tank by blow formation.

  PA (polyamide), PBT (polybutylene terephthalate), UHMPE (ultra high molecular weight polyethylene), PPS (polyphenylene sulfide), LCP (fully aromatic polyester resin, liquid crystal polymer) ) Etc. are suitable.

  PA resin is polyamide resin such as 66 nylon, 12 nylon, and 6 nylon, and those containing glass fiber or carbon fiber are strong against swelling by the treatment liquid and can be used.

  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-Zex 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 a soft material such as a squeeze roller, a foamed vinyl chloride resin, a foamed silicon resin, and a foamed urethane resin are suitable. Examples of the urethane foam resin include “Rubicel” manufactured by Toyo Polymer Co., Ltd. EPDM rubber, silicon rubber, Viton rubber and the like are preferable as rubber materials such as a pipe joint, an agitation jet pipe joint, and a sealing material. The treatment liquid concentrated composition used in the present invention may be used in the form of a cartridge that is combined into a set, in addition to individually forming the treatment liquid concentrated composition for each step into a product form. In this case, it is preferable that the automatic developing machine has an apparatus that can mount cartridges in a batch.

  Next, the reflective ornamental silver halide color photographic light-sensitive material according to the present invention will be described.

  In the silver halide color photographic light-sensitive material according to the present invention, a plastic resin film containing a white pigment is used as a support.

  In the present invention, the polymer that forms the plastic resin film constituting the support includes homopolymers and copolymers such as polyester (for example, polyethylene terephthalate), vinyl alcohol, vinyl chloride, fluorinated vinyl, and vinyl acetate, cellulose acetate, and acrylonitrile. And homopolymers and copolymers of acrylic acid alkyl ester, methacrylic acid alkyl ester, methacrylonitrile, alkyl vinyl ester, alkyl vinyl ether, polyamide and the like.

  Of these polymers, polyester resins are particularly preferable. The term “polyester resin” as used herein includes not only thermoplastic resins composed solely of polyester, but also those added with other polymers, additives, etc. within a range that does not practically change the resin properties of the main component polyester. The

  As the polyester resin, in addition to terephthalic acid as the aromatic dicarboxylic acid, isophthalic acid, 2,6-naphthalenedicarboxylic acid and the like, and lower alkyl esters thereof (derivatives capable of forming esters such as anhydrides and lower alkyl esters) are used. Can be used. Examples of the glycol include ethylene glycol, propylene glycol, butanediol, neopentyl glycol, 1,4-cyclohexanedimethanol, diethylene glycol, and p-xylylene glycol. In the present invention, the support is preferably polyethylene terephthalate (also referred to as PET) obtained by the reaction of terephthalic acid and ethylene glycol.

  The main component being polyethylene terephthalate means that it contains 80% by mass or more of a polyethylene terephthalate copolymer or a copolymer containing 80 mol% or more of a repeating unit of polyethylene terephthalate.

  PET film does not penetrate water, has excellent smoothness, excellent mechanical properties such as tensile strength and tear strength, excellent dimensional stability such as heat shrinkage, and excellent chemical resistance during development processing .

  The plastic resin film support of the present invention contains a white pigment to provide reflectivity.

  As the white pigment, inorganic and / or organic white pigments can be used, preferably inorganic white pigments, specifically, alkaline earth metal sulfates such as barium sulfate and alkaline earths such as calcium carbonate. Examples thereof include carbonates of metal salts, finely divided silicic acid, silicas of synthetic silicate, calcium silicate, alumina, alumina hydrate, titanium oxide, zinc oxide, talc, clay and the like. The white pigment is preferably barium sulfate, calcium carbonate, or titanium oxide.

  When the white pigment is contained in the plastic resin film support, the white pigment is preferably present in the range of 5 to 50% by mass with respect to the mass of the polymer forming the plastic resin film.

The whiteness is, for example, a value (L ^* a ^* b ^* ) measured in accordance with a method defined in JIS Z-8722 and Z-8730, and L ^* is preferably 80% or more according to this value. More preferably, L ^* is 90% or more, a ^* is in the range of -1.0 to +1.0, and b ^* is in the range of -2.0 to -5.0.

  Various constituent layers of the silver halide color photographic light-sensitive material are provided on the plastic resin film containing the white pigment according to the present invention.

  The main components of the silver halide color photographic light-sensitive material according to the present invention will be described below.

  The silver halide color photographic light-sensitive material according to the present invention is mainly composed of a photosensitive silver halide emulsion layer, for example, a blue-sensitive silver halide emulsion layer containing a yellow dye-forming coupler, on a plastic resin film containing a white pigment. A photographic composition layer comprising at least one of a magenta dye-forming coupler-containing green light-sensitive silver halide emulsion layer, a cyan dye-forming coupler-containing red light-sensitive silver halide emulsion layer, and a non-light-sensitive hydrophilic colloid layer. It is preferable. A silver halide emulsion layer containing a yellow dye-forming coupler is used as a yellow coloring layer, a silver halide emulsion layer containing a magenta dye-forming coupler is used as a magenta coloring layer, and a silver halide emulsion layer containing a cyan dye-forming coupler is used as 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 it. The silver halide color photographic light-sensitive material has an antihalation layer, an intermediate layer, and a colored layer as a non-photosensitive hydrophilic colloid layer described later, if desired, in addition to the yellow coloring layer, the magenta coloring layer, and the cyan coloring layer. May be.

  The details of an example of the components of the silver halide color photographic light-sensitive material according to the present invention are described in the following Research Disclosure (hereinafter abbreviated as RD) and can be referred to.

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

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

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

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

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

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

Example 1
<< Preparation of silver halide color photographic material >>
As the support, a white polyester reflective support made of polyethylene terephthalate having a thickness of 175 μm containing 4.0 g / m ^{2 of} barium sulfate was used, and after providing a gelatin subbing layer on both sides, Tables 1 and 2 Each constituent layer having the structure shown was coated to prepare Sample 101, which is a silver halide color photographic light-sensitive material for reflection viewing.

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

  The details of each additive listed in Tables 1 and 2 are as follows.

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

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

  The following compounds were used for the above EMP-1, and chemical sensitization was performed so that the sensitivity-fogging relationship was optimized. Similarly, EMP-1B is chemically sensitized so that the sensitivity-fogging relationship is optimized, and then sensitized EMP-1 and EMP-1B are mixed in a silver ratio of 1: 1. A blue-sensitive silver halide emulsion (Em-B) was prepared.

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

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

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

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

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

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

<< Preparation of 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 Diethylene glycol 80.0 g 110 g
Sodium p-toluenesulfonate 9.1g 13.0g
Potassium chloride 5.0g 7.0g
4-Amino-3-methyl-N-ethyl-N- (β-methanesulfonamidoethyl) aniline sulfate 10.5 g 15.0 g
Compounds listed in Table 3 Amounts listed in Table 3 Amounts listed in Table 3 Potassium carbonate 30.0 g 30.0 g
Diethylenetriaminepentaacetic acid pentasodium 6.0 g 8.6 g
pH 10.02 10.6
Water was added to 1 L, and the pH was adjusted with potassium hydroxide or 50% sulfuric acid.

  In addition, the detail of each compound described by the abbreviation in Table 3 is as follows.

HAS: Hydroxylamine sulfate DEHA: Diethylhydroxylamine Exemplary compound I-27: Disodium-N, N-bis (sulfonate ethyl) hydroxylamine Exemplary compound I-15: Disodium-N, N-bis (carbonate ethyl) ) Hydroxylamine [Bleaning Fixer per liter]
Tank liquid Replenisher Ethylenediaminetetraacetic acid ferric ammonium acetate 0.15 mol 0.20 mol Sodium thiosulfate 0.54 mol 0.72 mol Ammonium sulfite 0.15 mol 0.20 mol Succinic acid 20.0 g 27.0 g
Imidazole 5.0 g 9.5 g
pH 5.8 5.4
Water was added to 1 L, and the pH was adjusted with ammonium hydroxide or 50% sulfuric acid.

[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
pH 7.0
Water was added to 1 L, and the pH was adjusted with potassium hydroxide or 50% sulfuric acid.

<< Exposure and development process >>
After cutting the prepared sample 101 to 2 L size (127 × 178 mm), photographing a standard daylight scene, and exposing it with a printer described below using a tungsten lamp through a developed color negative film The development processing was performed under the following development processing conditions.

  A printer processor NPS-808 Gold manufactured by Konica Minolta Photo Imaging was used. The 2L size sample was exposed and developed by cut conveyance with a feed width of 178 mm.

  Each of the above processing solutions is obtained by using a Konica Minolta QA Paper Centuria for Digital (manufactured by Konica Minolta Photo Imaging Co., Ltd.) obtained by photographing a standard daylight scene and exposing through a developed color negative film. Converging liquids 1 to 7 were prepared by performing a running treatment at a treatment amount equivalent to 0.2 R per day until 1 R was reached according to the replenishment amount condition. In the present invention, 1R (round) means that the total replenishment amount of the color developer replenisher is one time the tank capacity.

(Processing conditions)
Processing process Processing temperature Processing time Tank capacity Replenishment amount
(° C) (seconds) (L) (ml / m ² )
Color development 40.0 22 15.5 125
Bleach fixing 39.0 22 15.2 200
Stabilization-1 39.0 22 15.0
Stabilization-2 39.0 22 15.0
Stabilization-3 39.0 22 15.0 248
Dry 60-85 180
The stabilization process was a multi-stage countercurrent system of stabilization-3 → stabilization-2 → stabilization-1.

<< Evaluation of silver halide color photographic material >>
Using the astringent liquids 1 to 7 obtained according to the above method, the prepared 2L size samples were processed to prepare processed samples 1-1 to 1-7. Evaluation was performed.

[Evaluation of stain resistance on back side]
The state of adhesion of foreign matter or the like to the back side (the side opposite to the side having the image forming layer) of each of the developed samples was visually observed, and the backside stain resistance was evaluated according to the following criteria.

◎: No dirt adherence to back side ○: Slight dirt adheres to back side, but acceptable quality △: Dirt is recognized on back side, impairing aesthetics in practical use Table 3 shows the results obtained as described above. The quality is a problem that is a problem in practical use.

  As is apparent from the results shown in Table 3, a plastic resin containing a 2 L-size white pigment after continuous processing with a color developer containing a compound represented by the general formula [I] according to the present invention It can be seen that the present invention, in which a sample having a film was processed, reduced the adhesion of processing stains to the back surface as compared with the comparative example.

Example 2
<Development processing>
Samples prepared in Example 1 using the astringent solution 2 (DEHA addition: Comparative Example) and the astringent solution 3 (Exemplary Compound I-27) prepared in Example 1 were prepared according to the sizes shown in Table 4 (E size, (L size, 2L size, 6 size size), and the processing direction (feed width) at the time of processing was changed to Table 4, and 1000 sheets were processed in the same manner. 2-14 was produced.

<Evaluation of transportability>
In each of the 1000 sheets, the number of occurrences of conveyance failure due to catching or the like in the conveyance process of the automatic developing machine was measured, and the conveyance property was evaluated according to the following criteria.

◎: No conveyance failure occurred and 1000 sheets could be processed without problems. ○: The number of conveyance failures occurred was 1 or more and 3 or less. △: The number of conveyance failures occurred was 4 or more. 10 or less ×: The number of sheets with conveyance failure is 11 or more and 20 or less. XX: The number of sheets with conveyance failure is 21 or more. 4 shows.

  As is apparent from the results shown in Table 4, in the treatment using the astringent liquid 2, it can be seen that when the feed width is 127 mm or less, a conveyance failure occurs remarkably, and it cannot be put into practical use. It can be seen that the process using the astringent solution 3 can stably convey even if the feed width is 127 mm or less.

Example 3
<Preparation of color developer>
In the preparation of the color developer tank solution 3 and the color developer replenisher 3 prepared in Example 1, the compounds represented by the general formulas [II] to [V] are added to the color developer tank solution and the color developer replenisher. Color developer (color developer tank solution and color developer replenisher) 9 to 16 were prepared in the same manner except that the amounts shown in Table 5 were added.

《Running processing》
Processing samples 3-1 to 3-9 were produced in the same manner as in the development processing described in Example 1, except that the color developing solutions 9 to 16 prepared above were used as the color developing solution.

  In the running process, the sample 101 produced in Example 1 was cut into a roll having a width of 127 mm and a length of 200 m, cut into an L size and exposed, and a total of 1,000 sheets were processed.

  Next, each processing solution was allowed to stand for 24 hours while being kept at a predetermined temperature, and then a further 100 sheets were processed.

<Evaluation of resistance to backside dirt>
Visual observation of the adherence of foreign matter etc. on the back side (the side opposite to the side having the image forming layer) of the 91st to 100th samples among the 100 sheets processed last in each of the development processes. The backside dirt resistance was evaluated according to the following criteria. In addition, evaluation was made into the average value of ten evaluation samples.

◎: No dirt adherence to back side ○: Slight dirt adheres to back side, but acceptable quality △: Dirt is recognized on back side, impairing aesthetics in practical use Table 5 shows the results obtained in the above manner. The result is as follows.

  As is clear from the results shown in Table 5, when continuous processing is performed with a color developer containing the compound represented by the general formula [I] according to the present invention, the general formulas [II] to [II] according to the present invention are further performed. It can be seen that the presence of the compound represented by V] further improves the resistance to back surface contamination.

1 is an overall configuration diagram showing an example of an automatic developing machine for a silver halide color photographic light-sensitive material in which an automatic processor and a printing machine for a silver halide color photographic light-sensitive material are integrated. FIG.

Explanation of symbols

AP Automatic processing machine for silver halide color photographic light sensitive material B Photo printing machine C Replenisher part E Exposure part p Sheet-like silver halide color photographic light sensitive material 1A Color developing tank 1B Bleach fixing tank 1C, 1D, 1E, 1F Stabilization tank (rinse tank)
2A, 2B, 2E Dissolution tank 2C, 2D Circulation tank 3A, 3B, 3E Solid processing agent supply device 4 Replenishment water tank 6 Drying section

Claims (5)

A silver halide color photographic light-sensitive material for reflection viewing, which is a plastic resin film containing a white pigment as a support, is cut to a certain size, and then a color development process, bleach-fixing process or bleach-fixing process and fixing process, stabilization A method for processing a silver halide color photographic light-sensitive material processed through a processing step comprising a step or a rinsing step and a drying step, wherein the color developer used in the color development step is represented by the following general formula [I]: A method for processing a silver halide color photographic light-sensitive material comprising a compound represented by the formula:

[In the formula, L represents an alkylene group, A represents a carboxyl group, a sulfo group, a phosphono group, a phosphine group, a hydroxyl group, an amino group, an ammonio group, a carbamoyl group, a sulfamoyl group, an alkylsulfonyl group, a hydrogen atom, an alkoxyl group, Or -O- (B-O) _n- R ', R and R' each represent a hydrogen atom or an alkyl group. B represents an alkylene group, and n represents an integer of 1 to 4. ] 2. The method for processing a silver halide color photographic material according to claim 1, wherein the plastic resin film is polyethylene terephthalate. 3. The method for processing a silver halide color photographic light-sensitive material according to claim 1, wherein the silver halide color photographic light-sensitive material is conveyed and processed at a feed width of 130 mm or less. The silver halide according to any one of claims 1 to 3, wherein the color developer contains at least one selected from compounds represented by the following general formulas [II] to [V]. Processing method of color photographic 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. ]
General formula [III]
R _6- (O) _x SO ₃ M ₆
[Wherein, R ₆ represents an aliphatic group or a heterocyclic group, x represents 0 or 1, and M ₆ represents a hydrogen atom or a cation. ]

[Wherein R ₁ represents an alkyl group having 1 to 2 carbon atoms, or a hydrogen atom, R ₂ represents an alkyl group having 1 to 3 carbon atoms, a sulfo group, a carboxyl group, a hydroxyl group, or a hydrogen atom, R ₃ represents a hydrogen atom or a hydroxyl group. p represents an integer of 0 to 2, and r represents an integer of 1 to 3. A may be substituted with a hydrogen atom at any position of the benzene ring. Further, s represents 0 to 50, t represents an integer of 0 or 1, and u represents an integer of 2 to 150. ]
General formula [V]
_{HO- (CH 2 CH 2 O)} n - (CH 2 CH (CH 3) O) m -H
[Wherein, n represents an integer of 0 to 200, m represents an integer of 0 to 50, and m and n are not 0 at the same time. ] The processing method of a silver halide color photographic material according to any one of claims 1 to 4, wherein the processing temperature of the color developer is 38 ° C or higher.

Images