JPH06161064A - Processing method for silver halide color photographic sensitive material - Google Patents

Abstract

PURPOSE:To effectively prevent contamination with microorganisms and to prevent the contamination of the unexposed parts of the photosensitive material and the formation of the colored suspended matter of liquid having bleachability even if the photosensitive material is processed by a processing liquid subjected to low replenishing or reproducing by incorporating specific compds. into the photosensitive material. CONSTITUTION:This photosensitive material contains at least one kind of the compds. of formula I, formula II, etc., or at least one kind of gentamycines, etc., at the hydrophilic colloidal layer on the supporting base. The liquid having bleachability contains the ferric complex of the compd. of formula III as the cleaning agent. In the formulas I, II, R1 to R5 denote a hydrogen atom, alkyl group or aryl group; R6 denotes a hydrogen atom, alkyl group, aryl group, nitro group, etc.; Y denotes a halogen atom,; Z denotes the non-metallic atom group necessary for constituting a thiazoryl ring; n denotes 0 or 1. In the formula III, Ra to Rf denote a hydrogen atom, aliphat. group, etc.; W denotes the combination group expressed by -(W1-Z)n-W2-; M1 to M4 denote a hydrogen atom or cation; W1 denotes an alkylene group or single bond; W2 denotes an alkylene group or -CO-; Z denotes a single bond; -O-, etc., n denotes an integer form 1 to 3.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for processing a silver halide color photographic light-sensitive material (hereinafter, simply referred to as a light-sensitive material), and particularly to coloring a liquid having a low replenishment and a bleaching ability at the time of processing in a small amount. The present invention relates to a treatment method that prevents the generation of floating matter and the contamination of color prints that accompany it.

[0002]

2. Description of the Related Art Generally, a silver halide color photographic light-sensitive material is imagewise exposed and then processed with a color developing solution containing an aromatic primary amine color developing agent to obtain a bleaching solution containing a bleaching agent. It is treated, then treated with a fixing solution containing a fixing agent, and finally washed with water or a stabilizing solution. Here, bleaching and fixing may be performed as independent bleaching solutions and fixing solutions, or may be performed simultaneously as bleach-fixing solutions. In the color developing step, the exposed silver halide grains are reduced by the color developing agent to silver, and the produced oxidation product of the color developing agent reacts with the coupler to form an image dye. The developed silver generated in the developing step is oxidized into a silver salt by a bleaching agent having an oxidizing action (bleaching),
Further, it is removed from the photosensitive layer together with the unused silver halide by a fixing agent that forms soluble silver (fixing).

In recent years, in the processing of silver halide color photographic light-sensitive materials, short-time processing and dealing with environmental problems have become the most important issues. The former is due to the desire to process films and prints in the shortest possible time in order to differentiate from other stores due to the spread of small-scale in-store processing labs called minilabs, and recent advances have been remarkable. was there. In the latter case, environmental pollution at the global level has been highlighted, and strict emission regulations have been implemented year by year in each country. Therefore, reduction of photographic waste liquid has become a major issue in the photographic industry. Photographic processing is usually performed using a processor called an automatic processor. This automatic developing machine has respective processing tanks for color development, bleach-fixing, washing with water, etc., and photosensitive materials such as films and color papers are successively processed through these processing tanks for processing. At this time, in order to keep the performance of the processing solution constant, each processing tank is replenished with a solution called a replenishing solution according to the area of the photosensitive material to be processed, and at this time, the solution overflowing from the processing tank is directly used as a photographic waste liquid. It is generally discharged as. In order to reduce this photographic waste liquid, there are "replenishment" to reduce the amount of replenisher to be replenished per unit area, "regeneration of treatment liquid" in which the overflowed treatment liquid is used again as the replenishment liquid, etc. Has been done.

However, in any case, components eluted from the light-sensitive material into the processing solution, for example, coloring substances such as sensitizing dyes and dyes in the light-sensitive material, various development-inhibiting substances contained in the emulsion layer, gelatin, etc. The accumulated amount of various organic or inorganic compounds in the treatment liquid increases, causing various problems. For example, due to the accumulation of colored substances, insufficient washing out of the colored substances during processing may cause "residual color", "desensitization and softening" caused by the accumulation of development inhibitors, or desilvering due to eluate. Since various problems such as "defective desilvering" occur due to the delay, countermeasures have been considered for each. On the other hand, since photosensitive materials often use gelatin and other organic substances, they always have a problem of microbial contamination such as bacteria and mold. In particular, if microbial contamination occurs during the production or processing of the light-sensitive material, it may cause problems such as stains and unevenness on the finished film or print, or the fungal hyphae of the mold itself that can be seen visually. Antibacterial agents and antifungal agents are required.

[0005]

Accordingly, effective antibacterial agents and antifungal agents have been selected from such a viewpoint. However, a light-sensitive material containing these effective antibacterial and antifungal agents has a low replenishing rate or a low replenishment rate. It has been found that the treatment with the regenerated processing liquid causes a problem that fine coloring substances are generated especially in a liquid having a bleaching ability and the coloring substances adhere to the photosensitive material to be contaminated. The present invention solves the above-mentioned problems, and an object of the present invention is to effectively prevent microbial contamination and to contaminate the unexposed portion of a light-sensitive material even when treated with a low replenishment or regenerated processing solution. Another object of the present invention is to provide a treatment method which prevents the formation of colored suspended matter of a liquid having a bleaching ability.

[0006]

The present inventor has analyzed the above problems and studied various methods, and found that the above objects can be achieved by the following means.
That is, the present invention provides at least one compound represented by any of the following general formulas (A) to (I) in any of the hydrophilic cotoid layers on the support, or gentamicin.
(Gentamicin), amikacin (Amikacin), tobramycin (Tobramicin), dibekacin (Dibekacin), arbekacin, micronomycin (Micronomicin), isepamicin
(Isepamicin), sisomycin (Sisomicin), netilmicin (Netilmicin) and at least one aminoglycoside selected from astromycin (Astromicin), and a liquid having the bleaching ability is represented by the following general formula (X) as a bleaching agent. It is characterized by containing a ferric complex of the compound described above.

[0007]

[Chemical 4]

[0008]

[Chemical 5]

(Where R is₁, R₂, R₃, R_Four, R_Five,
R₇And R₈Are a hydrogen atom, an alkyl group or
Represents a reel base. R₆Is a hydrogen atom, alkyl group,
Reel, nitro, carboxy, sulfo, sulf
Amamoyl group, hydroxy group, halogen atom, alkoxy
Represents a group or a thiazolyl group. L₁And L₂Is that
Represents an alkylene group or an arylene group. R₉,
R_Ten, And R₁₁Are halogen atom or alkyl
Represents a group. R₁₂And R₁₃Are hydrogen atom and
It represents a kill group, an aryl group or a nitrogen-containing heterocyclic residue. R
₁₄And R₁₅Are hydrogen atom, halogen atom,
It represents a kill group or an aryl group. Incidentally, R₁₄And R ₁₅Are each other
To form a benzene ring. R₁₆Is hydrogen
Represents an atom or an alkyl group. R₁₇Is an alkyl group or
Represents an aryl group. Y represents a halogen atom. Z
₁Is a group of non-metal atoms necessary to form the thiazolyl ring.
Represents Z₂Required to form a 6-membered hydrocarbon ring
Represents a non-metallic atomic group. n represents 0 or 1. m is
Represents 1 or 2. k represents an integer of 3 to 20. )

[0010]

[Chemical 6]

(In the formulae, R _a , R _b , R _c , R _d , R _e and R _f each represent a hydrogen atom, an aliphatic group, an aromatic group or a hydroxy group. W is represented by the following general formula (W ), M ₁ , M ₂ , M ₃ and M ₄ each represent a hydrogen atom or a cation General formula (W)-(W ₁ -Z) _n -W _2- (General formula In (W), W ₁ represents an alkylene group or a single bond, W ₂ represents an alkylene group or —CO—, and Z is a single bond, —O—, —S—, —CO—, or —. Represents N (R _w )-, R _w represents a hydrogen atom or an alkyl group, n represents an integer of 1 to 3, provided that Z and W ₁ are not a single bond at the same time. According to the invention, the production of a coloring substance in a liquid having a bleaching ability without causing microbial contamination and the purine resulting therefrom Without causing pollution, it is possible to achieve low waste of low replenishment or regeneration, or the like.

The present invention will be described in more detail below. First, the compounds represented by formulas (A) to (I) will be described. Among the compounds represented by the general formulas (A) to (I), preferred compounds are the general formulas (B), (G) and (H).
And more preferred are those represented by the general formulas (G) and (H). The alkyl group in R _{1 to} R ₁₇ may be substituted and is preferably a straight chain, branched or cyclic group having 1 to 30 carbon atoms, for example, methyl,
Examples thereof include ethyl, octyl, dodecyl, tetradecyl and octadecyl. The aryl group of R _{1 to} R ₈ may be substituted, may be a monocyclic ring or a condensed ring, and preferably has 6 to 20 carbon atoms, and examples thereof include phenyl and naphthyl. The sulfamoyl group for R ₆ may be substituted,
Those having 0 to 30 carbon atoms are preferable, and examples thereof include sulfamoyl and N, N′-dimethylsulfamoyl. The alkoxy group for R ₆ may be substituted and preferably has 1 to 30 carbon atoms, and examples thereof include methoxy, ethoxy, and octyloxy. The thiazolyl group in R ₆ may be substituted and may be bonded at the 2-position, 4-position or 5-position.

The alkylene group in L ₁ and L ₂ may be substituted, and is a straight chain having 1 to 10 carbon atoms,
Branched or cyclic ones are preferable, and examples thereof include methylene, ethylene, and propylene. The arylene group in L ₁ and L ₂ may be substituted and preferably has 6 to 10 carbon atoms, and examples thereof include phenylene and naphthylene.
Examples of the halogen atom in R ₆ , R ₉ , R ₁₀ , R ₁₁ , R ₁₄ , R ₁₅ and Y include a chlorine atom, a fluorine atom and a bromine atom. The nitrogen-containing heterocyclic residue in R ₁₂ and R ₁₃ is preferably a 5-membered to 8-membered saturated or unsaturated group, and as the hetero atom other than the nitrogen atom,
Oxygen atom and sulfur atom are preferred. Examples of the nitrogen-containing heterocyclic residue include 2-oxazolyl, 3-isoxazolyl,
3-pyrrolyl, 2-imidazolyl, 5-pyrazolyl, 5
-Isothiazolyl, 2-1,3,4-thiadiazolyl,
4-thiadiazolyl, 2-pyridyl, 2-pyrimidyl and the like can be mentioned. Z ₁ represents a group of non-metal atoms necessary for constituting the thiazolyl ring. The thiazolyl ring may be substituted and may be attached at the 2-position, 4-position or 5-position. Z ₂ represents a group of non-metal atoms necessary for forming a 6-membered hydrocarbon ring, and may be saturated or unsaturated. 6
Examples of the member hydrocarbon ring include a cyclohexane ring and a cyclohexene ring.

The substituent in the above-mentioned optionally substituted group is, for example, an alkyl group (eg methyl, ethyl), an aralkyl group (eg phenylmethyl), an alkenyl group (eg allyl), an alkynyl group, an alkoxy group (eg Methoxy, ethoxy), aryl groups (eg phenyl, p-methylphenyl), amino groups (eg dimethylamino), acylamino groups (eg acetylamino), sulfonylamino groups (eg methanesulfonylamino), ureido groups, urethane groups, aryl Oxy group (eg phenyloxy), sulfamoyl (eg methylsulfamoyl), carbamoyl group (eg carbamoyl, methylcarbamoyl), alkylthio group (eg methylthio), arylthio group (eg phenylthio), sulfonyl group (eg Methanesulfonyl), sulfinyl group (eg methanesulfinyl), hydroxy group, halogen atom (eg chlorine atom, bromine atom, fluorine atom), cyano group, sulfo group, carboxy group, phosphono group, aryloxycarbonyl group (eg phenyloxy) Carbonyl), acyl groups (eg acetyl, benzoyl), alkoxycarbonyl groups (eg methoxycarbonyl), acyloxy groups (eg acetoxy), carbonamido groups, sulfonamide groups, nitro groups and the like.

In the general formula (A), R ₁ , R ₂ , R
₃ and R ₄ are preferably alkyl groups, R ₁ ,
At least one of R ₂ , R ₃ and R ₄ has 5 to 20 carbon atoms.
More preferably, it is an alkyl group. A chlorine atom is particularly preferable as Y. In the general formula (B), R ₅
And R ₆ are preferably hydrogen atoms, n is preferably 0, and Z ₁ is preferably a group of non-metal atoms necessary for forming an unsubstituted 4-thiazolyl ring. In the general formula (C), R ₇ is preferably a hydrogen atom, R ₈ is preferably an alkyl group, and has 5 to 5 carbon atoms.
More preferred are 20 alkyl groups. In the general formula (D), L ₁ is preferably an alkylene group having 5 to 10 carbon atoms, and k is preferably 3 to 10. In the general formula (E), R ₉ , R ₁₀ and R ₁₁ are each preferably an alkyl group or a halogen atom substituted with at least one halogen atom, and particularly preferably a halogen atom. Z
₂ is preferably a group of non-metal atoms necessary for forming a cyclohexene ring. In the general formula (F), R ₁₂ and R ₁₃
Is preferably a hydrogen atom, an alkyl group or a nitrogen-containing heterocyclic residue, and R ₁₂ is more preferably a hydrogen atom,
₁₃ is preferably a hydrogen atom or a 5- or 6-membered nitrogen-containing unsaturated heterocyclic residue. In formula (G), R ₁₄ and R ₁₅ are preferably hydrogen atoms or bonded to each other to form a benzene ring, more preferably bonded to each other to form a benzene ring, and R ₁₆ is A hydrogen atom is preferred. In the general formula (H), R ₁₇ is preferably an unsubstituted alkyl group having 1 to 4 carbon atoms. General formula (I)
In, L ₂ is preferably an unsubstituted alkylene group having 2 to 4 carbon atoms. General formula (A) used in the present invention
Specific examples of the compound represented by (I) are shown below, but the present invention is not limited thereto.

[0016]

[Chemical 7]

[0017]

[Chemical 8]

[0018]

[Chemical 9]

[0019]

[Chemical 10]

In addition to these examples, the compounds represented by the general formulas (A) to (I) include, for example, JP-A-60-263938, JP-A-59-228247, JP-A-54-27424 and JP-A-1-211751. And the examples of such compounds are included. In the present invention, the general formula (A) ~
The compound represented by (I) may be contained in any hydrophilic colloid layer such as a silver halide emulsion layer and an auxiliary layer such as a gelatin intermediate layer. The addition amount of the compounds of the general formulas (A) to (I) is preferably 1 to 1000 ^-3 mg / m ^{2, and} more preferably 5 to ²⁰⁰ (mg / m ² ). General formulas (A) to (I)
When containing the compound represented by in the photosensitive material, dissolved in an organic solvent such as methanol, ethanol, ethylene glycol, diethylene glycol, triethylene glycol, benzyl alcohol, ethanolamine, diethanolamine, triethanolamine, or added, It is preferably added in the form of an emulsion (as an emulsion). The above aminoglycosides used in the present invention will be described. The aminoglycosides of the present invention are compounds known as antibiotics and, for example, gentamicins are described in US Pat. No. 3,091,57.
No. 2, 3,136,704, Amikacin in US Pat. No. 3,781,268, Arbekasi in US Pat. No. 4,107,424, German Patent 2,35.
No. 0,169, German patent 2,1 for dibekacin
35,191, US Pat. No. 4,002,742 for isepaicin, US Pat. No. 4,045,298 for micronomycin, and German Patent 2,326.
No. 781, US Pat.
2,742, 4,029,882, German Patent 2,437,160, and with respect to sisomycin, US Pat. No. 3,832,286 can be referred to. In the present invention, it is particularly preferable to use gentamicins among these aminoglycosides. Representative specific examples of gentamicin are listed below.

Compound No. B-1 (gentamicin A ₂ ) B-2 (gentamicin A) B-3 (gentamicin A ₁ ) B-4 (gentamicin B) B-5 (gentamicin X ₂ ) B-6 (antibiotic) JI-20A) B-7 (gentamicin B ₁₎ B-8 (anti-biotic G418) B-9 (anti-biotic JI-20B) B-10 (gentamycin C ₁₎ B-11 (gentamycin C _1a) B- 12 (gentamycin C ₂₎ B-13 (gentamycin C _2a) B-14 (gentamycin C _2b)

The method for producing the aminoglycoside used in the present invention is described in the above-mentioned patent, but a commercially available one can be used. Also, regarding these properties, etc., the MERCK IND
EX AN ENCYCLOPEDIA OF CHEMICALS, DRUGS, AND BIOLOG
ICALS) 11th edition (1989) MERCK & CO., INC.

The aminoglycosides used in the present invention are contained in at least one of the silver halide emulsion layer coated on the support and the hydrophilic colloid layer of the auxiliary layer as exemplified above, preferably in all layers. Can be made. The aminoglycosides are preferably dissolved in water and added to a coating solution containing a hydrophilic colloid for use. The amount of aminoglycoside used is preferably about 0.01 to 20 mg / m ^{2, and} more preferably 0.1 to 5 mg / m ² . The light-sensitive material of the present invention is preferably at least one layer of a photosensitive silver halide emulsion layer containing a yellow dye-forming coupler, at least one layer of a photosensitive silver halide emulsion layer containing a magenta dye-forming coupler, and at least one layer on a support. A light-sensitive silver halide emulsion layer containing a cyan dye forming coupler and at least 1
A silver halide color photographic light-sensitive material having a non-light-sensitive hydrophilic colloid layer.

Next, the compound represented by the general formula (X), which is used as the ferric iron complex in the bath having the bleaching ability in the processing method of the present invention, will be described. In the general formula (X), the aliphatic group represented by R _a , R _b , R _c , R _d , R _e and R _f is a linear, branched or cyclic alkyl group, an alkenyl group or an alkynyl group, Those having 1 to 10 carbon atoms are preferable. The aliphatic group is more preferably an alkyl group, further preferably an alkyl group having 1 to 4 carbon atoms, and particularly preferably a methyl group or an ethyl group. R _a , R
_The aromatic group represented by _b , R _c , R _d , R _e and R _f is a monocyclic or bicyclic aryl group, and examples thereof include a phenyl group and a naphthyl group, and a phenyl group is more preferable.

The aliphatic group and aromatic group represented by R _a , R _b , R _c , R _d , R _e and R _f may have a substituent, for example, an alkyl group (eg methyl, ethyl). ), Aralkyl groups (eg phenylmethyl), alkenyl groups (eg allyl), alkynyl groups, alkoxy groups (eg methoxy, ethoxy), aryl groups (eg phenyl, p).
-Methylphenyl), amino group (eg dimethylamino), acylamino group (eg acetylamino), sulfonylamino group (eg methanesulfonylamino), ureido group, urethane group, aryloxy group (eg phenyloxy), sulfamoyl (eg methyl Sulfamoyl), carbamoyl group (eg carbamoyl, methylcarbamoyl), alkylthio group (eg methylthio), arylthio group (eg phenylthio), sulfonyl group (eg methanesulfonyl), sulfinyl group (eg methanesulfinyl), hydroxy group, halogen atom (Eg chlorine atom, bromine atom, fluorine atom), cyano group, sulfo group, carboxy group, phosphono group, aryloxycarbonyl group (eg phenyloxycarbonyl), acyl group (eg Cetyl, benzoyl), an alkoxycarbonyl group (eg methoxycarbonyl), an acyloxy group (eg acetoxy), a carbonamido group, a sulfonamide group, a nitro group, a hydroxamic acid group and the like, and if possible, a dissociation product or salt thereof. May be When the above substituent has a carbon atom, it preferably has 1 to 4 carbon atoms. R _a , R _b ,
R _c , R _d , R _e and R _f are preferably a hydrogen atom or a hydroxy group, more preferably a hydrogen atom.

The linking group represented by W is represented by the following general formula (W). Formula _{(W) - (W 1 -Z} ) n -W 2 - W 1 represents an alkyl group or a single bond. The alkylene group represented by W ₁ is preferably a linear or branched alkylene group having 1 to 8 carbon atoms (for example, a methylene group, an ethylene group, a propylene group), a cycloalkylene group having 5 to 10 carbon atoms (for example, 1, 2-cyclohexylene group). W
₂ represents an alkylene group or -CO-. The alkylene group represented by W ₂ has the same meaning as the alkylene group represented by W ₁ . The alkylene groups represented by W ₁ and W ₂ may be the same or different from each other, or may have a substituent. As the substituent, those mentioned as the substituent of R _a are applicable, and the substituent is preferably an alkyl group, a hydroxy group or a carboxy group. W ₁ and W
₂ is more preferably an alkyl group having 1 to 3 carbon atoms, and a methylene group or an ethylene group is particularly preferable. Z
It is a single bond, -O -, - S -, - CO -, - N (R W)
Represents-. R _W represents a hydrogen atom or an alkyl group.
The alkyl group may be substituted, and the substituent is R
_Although those mentioned as the substituent of _a can be applied, a carboxy group, a phosphono group, a sulfo group, a hydroxy group or an amino group is preferable. Z is preferably a single bond. n is preferably 1 or 2, and more preferably 1. Specific examples of W include the following.

[0027]

[Chemical 11]

Examples of the cation represented by M ₁ , M ₂ , M ₃ and M ₄ include alkali metals (eg lithium, sodium, potassium), ammonium (eg ammonium, tetraethylammonium) and pyridinium. it can. In the present invention, specific examples of the compound represented by the above general formula (X) are shown below, but the present invention is not limited thereto.

[0029]

[Chemical 12]

[0030]

[Chemical 13]

[0031]

[Chemical 14]

[0032]

[Chemical 15]

[0033]

[Chemical 16]

The compounds represented by formula (X) of the present invention are disclosed in JP-A-63-199295 and JP-A-3-17.
It can be synthesized according to the description in Japanese Patent No. 3857 or the like. As described in these documents, the compound represented by the general formula (X) of the present invention includes optical isomers ([R, R], [S, S], [S, R] , [R, S])
Exists. For example, the exemplary compound (X-1) of the compound represented by the general formula (X) of the present invention has three optical isomers ([R, R], [S, S], [S, R]). Exist and these can be synthesized individually or as a mixture. It goes without saying that the present invention includes these individual optical isomers and mixtures thereof. In the present invention, a compound synthesized from an L-amino acid such as [S, S] -form as a starting material is more preferable than other optical isomers. These compounds are described in Springer and Copecca Chem.
Zvesti. 20 (6): 414-422 (196.
6) and the method described in JP-A-3-173857.

The ferric complex of the compound represented by the general formula (X) which is the bleaching agent of the present invention can be prepared by mixing a trivalent iron ion with the compound of the general formula (X). it can. When used as a bleaching agent, it may be isolated and used as a ferric chelate complex. In this case, it can be isolated, for example, as an ammonium salt, a sodium salt, or a potassium salt. The amount of the ferric iron complex of the present invention used is 0.02 mol to 1.0 mol, preferably 0.04 mol to 0.5 mol, per liter of the bleaching liquid. Further, it is preferable that a chelating agent (free form) that does not chelate ferric iron be present in excess of about 10 to 20% other than the ferric iron complex. Among the compounds represented by the general formula (X), X-1, X-2, X-3, X-1
Compounds of 5, X-16 and X-17 are particularly preferable. The solution having a bleaching ability in the present invention may be either a bleaching solution or a bleach-fixing solution, but the bleaching-fixing solution is more effective. The ferric iron complex of the compound represented by the general formula (X) is added to and contained in the bleaching solution or the bleach-fixing solution.

The compound represented by the general formula (X) used in the present invention is used as a builder in the field of detergent (JP-A-63-199295, JP-A-3-173857).
Although it is a known substance, it has never been used as a ferric complex in photographic processing, is a novel substance in this field, and is an ethylenediaminetetraacetic acid secondary compound conventionally used as a bleaching agent. Compared to iron complexes,
It has an excellent bleaching effect.

The silver halide color photographic light-sensitive material which can be processed by the processing method of the present invention may be any light-sensitive material such as so-called color negative or color paper, but it is particularly suitable for color paper. . Silver halide emulsions and other materials (additives, etc.) and photographic constituent layers (layer arrangement, etc.) used in these light-sensitive materials, and processing methods and processing additives applied to process the light-sensitive material. As the above, those described in the following patent publications, particularly European Patent EP 0,355,660A2 (JP-A-2-139544) are preferably used. The places where the photographic components are described in the following patent publications are shown as a list.

[0038]

[Table 1]

[0039]

[Table 2]

[0040]

[Table 3]

[0041]

[Table 4]

[0042]

[Table 5]

As the silver halide used in the present invention, silver chloride, silver bromide, silver chlorobromide, silver iodochlorobromide, silver iodobromide, silver iodochloride and the like can be used. For the purpose of the invention, a silver chloride content substantially free of silver iodide is 9
Preference is given to using 0 to 100 mol%, more preferably 95 to 100 mol%, especially 98 to 100 mol% of silver chlorobromide or silver chloride emulsion.

As the support used in the light-sensitive material according to the present invention, a white polyester support for display or a layer containing a white pigment is provided on the support having a silver halide emulsion layer. A support may be used. In particular, the transmission density of the support is preferably set in the range of 0.35 to 0.8 so that the display can be viewed with both reflected light and transmitted light. Further, a light-sensitive material in which a gelatin layer is coated on the back surface of the support (the side opposite to the emulsion layer) is more preferable because the effect of the present invention becomes more remarkable. In this case, an ultraviolet light absorber or the like may be included. Also, the thickness of the back surface is 1
To 10 micron are preferable, and 3 to 8 micron is particularly preferable. The layer structure of the light-sensitive material used in the present invention is not particularly limited, but by providing two or more intermediate layers between the green-sensitive layer and the red-sensitive layer, it is possible to suppress an increase in stain of the processed light-sensitive material over time. Therefore, it is preferable. Furthermore, in the present invention, it is preferable to use two or more of the following development inhibitors in the light-sensitive material, and it is particularly preferable to use three kinds together.

[0045]

[Chemical 17]

With these compounds, the effect of the present invention becomes more remarkable. The preferable addition amount of these is such that the total amount of the following compounds is 1 × 10 ⁻⁶ to 1 × 10 1 per mol of silver halide.
^-2 mol, more preferably 1 x 10 ^-5 to 1 x 10 ^-3
It is a mole.

Next, the processing method of the present invention will be further described. The imagewise exposed light-sensitive material is subjected to color development processing. The color developing solution used for developing the light-sensitive material is preferably an alkaline aqueous solution containing an aromatic primary amine type color developing agent as a main component. The color developer contains a pH buffer such as an alkali metal carbonate, borate or phosphate, a bromide salt, an iodide salt, a benzimidazole, a benzothiazole or a mercapto compound, or a development inhibitor or a fog. Generally, it contains an inhibitor and the like. If necessary, hydroxylamine, N, N-
Various preservatives such as di (sulfoethyl) hydroxylamine, diethylhydroxylamine, sulfites, hydrazines, catechol disulfonic acids, organic solvents such as diethylene glycol, benzyl alcohol, polyethylene glycol, quaternary ammonium salts, amines such as amines Add a development accelerator. The pH of these color developing solutions is 9 to
It is generally 12. In the present invention, it is preferable to contain the chelating agent represented by the general formula (X) because the effect of the present invention becomes remarkable.

The replenishment amount of these color developing solutions depends on the color photographic light-sensitive material to be processed, but in general, the light-sensitive material 1 is used.
Less than 1 liter per square meter, 300 ml by reducing the bromide ion concentration in the replenisher
It can also be: Preferably 30 ml to 150
ml / m ² . When the replenishment amount is reduced, the contact area with the air in the processing tank is reduced to evaporate the liquid,
It is preferable to prevent air oxidation. Further, the amount of replenishment can be reduced by using means for suppressing the accumulation of bromide ions in the developing solution. The photosensitive material after color development is
Usually, it is subsequently bleached with a solution having a bleaching ability. The bleaching process may be performed simultaneously with the fixing process (bleach-fixing process), or may be performed individually. Further, in order to speed up the process, a bleach-fixing process may be performed after the bleaching process. As the bleaching agent, it is necessary to use the ferric iron complex of the compound represented by the general formula (X) as described above, but other bleaching agents may be used in combination if necessary. Representative bleaching agents that can be used in combination are ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, ethyliminodiacetic acid, 1,3-diaminopropanetetraacetic acid,
It is a ferric complex of aminopolycarboxylic acids such as glycol ether diamine tetraacetic acid.

The processing time of the bleaching solution is preferably 15 seconds to 60 seconds for the purpose of speeding up. More preferably, it is 20 seconds to 50 seconds. When the length is short, desilvering failure occurs, and when the length is long, the effect of the present invention cannot be sufficiently obtained.

Examples of the fixing agent include thiosulfates, thiocyanates, thioether compounds, thioureas, and a large amount of iodide salts, and the use of thiosulfates is common, especially ammonium thiosulfate. Is the most widely used. As a bleach-fixing solution or a preservative for the fixing solution, sulfite, bisulfite, benzenesulfonic acid or carbonyl bisulfite adduct is preferable. The photographic material of the present invention is generally subjected to washing and / or stabilizing steps after desilvering. The amount of rinsing water in the rinsing step depends on the characteristics of the photosensitive material (for example, depending on the materials used such as couplers), application, and further, the rinsing water temperature, the number of rinsing tanks (number of stages), replenishment method such as countercurrent, forward flow, and various other conditions. It can be set in a wide range.
Further, it is preferable to add the antibacterial and antifungal agents represented by the general formulas (I) to (IX). The pH of washing water in the processing of the light-sensitive material of the present invention is 4 to 9, preferably 5 to 8. The washing water temperature and washing time can be variously set depending on the characteristics of the light-sensitive material, application, etc., but in the present invention, it is 10 to 2 minutes at 15 to 45 ° C.
It is preferable to select the range of 20 to 1 minute and 30 seconds at 25 to 40 ° C. Further, the light-sensitive material of the present invention is preferably directly processed with a stabilizing solution instead of the above washing with water. In such stabilization treatment, Japanese Patent Laid-Open No. 57-
No. 8,543, No. 58-14, 834, No. 60-22
All known methods described in No. 0,345 can be used.

Various treatment liquids in the present invention are 10 ° C. to 50 ° C.
Used at ° C. Normally, a temperature of 33 ° C. to 42 ° C. is standard, but a higher temperature is used to accelerate the processing to shorten the processing time, and a lower temperature is used to improve the image quality and the stability of the processing liquid. be able to. Further, in order to save silver in the light-sensitive material, processing using cobalt intensification or hydrogen peroxide intensification described in West German Patent No. 2,226,770 or US Pat. No. 3,674,499 may be performed. It is preferable that the amount of replenishment in each processing step is small. The amount of replenisher is preferably 0.1 to 50 times, more preferably 3 to 50 times the carry-in amount of the pre-bath per unit area of the light-sensitive material.
30 times.

[0052]

In the present invention, a silver halide color photographic light-sensitive material containing an antibacterial / antifungal agent of the general formulas (I) to (IX) or an aminoglycoside is used as a second compound of the general formula (X). By treating with a solution having an bleaching ability containing an iron complex as a bleaching agent, contamination of the finished light-sensitive material can be prevented more than in the case of combining with a bleaching agent of a ferric iron complex such as conventional ethylenediaminetetraacetic acid (EDTA). Is less. The ferric iron complex of the compound represented by the general formula (X) used in the present invention is a novel compound which belongs to ferric polyaminocarboxylic acid as a general concept but has never been used for photographic processing. Therefore, when the ferric iron complex is used as a bleaching agent in the present invention, an extremely excellent effect is exhibited in combination with the use of the antibacterial and fungicide of the general formulas (I) to (IX) or aminoglycosides.

[0053]

The present invention is described in detail below with reference to examples, but the present invention is not limited to these. Example 1 The surface of a paper support laminated on both sides with polyethylene was subjected to a corona discharge treatment and then provided with a gelatin subbing layer containing sodium dodecylbenzene sulfonate, and various photographic constituent layers were further applied to form a layer shown below. A multilayer color photographic paper sample A having the constitution was prepared. The following spectral sensitizing dyes were used for the silver chlorobromide emulsion of each photosensitive emulsion layer.

[0054]

[Table 6]

[0055]

[Table 7]

[0056]

[Table 8]

AF-1 was added to each of the blue-sensitive emulsion layer, the green-sensitive emulsion layer and the red-sensitive emulsion layer in an amount of 5.5 × 10 ^-4 mol per mol of silver halide. Further, 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene was added to the blue-sensitive emulsion layer and the green-sensitive emulsion layer in an amount of 1 × 10 ⁻⁴ mol and 2 mol, respectively, per mol of silver halide. × 10 ⁻⁴ mol was added. Further, the following dyes (the amount in parentheses represents the coating amount) were added to the emulsion layer to prevent irradiation.

[0058]

[Chemical 18]

Further, sodium dodecylbenzene sulfonate was used as a coating aid. (Layer constitution) The composition of each layer is shown below. Numbers are coating amount (g
/ M ² ). The silver halide emulsion represents the coating amount in terms of silver. Support: polyethylene laminated paper [white pigment (TiO ₂ ) 4 g / m ² on polyethylene on the first layer side]
First layer (white pigment-containing hydrophilic colloid layer) TiO ₂ 2.50 gelatin 0.63 second layer (blue sensitive emulsion layer) silver chlorobromide emulsion (cubic, large size with average grain size 0.88 μm) 3: 7 mixture of emulsion and small size emulsion of 0.70 μm (silver molar ratio) Grain size distribution coefficient of variation is 0.08 and 0.10 respectively, and silver bromide 0.3% for each size emulsion 0.27 Gelatin 1.36 Yellow coupler (ExY) 0.79 Color image stabilizer (Cpd-1) 0.08 Color image stabilizer (Cpd-2) 0. 04 Color image stabilizer (Cpd-3) 0.08 Solvent (Solv-1) 0.13 Solvent (Solv-2) 0.13

Third Layer (Color Mixing Prevention Layer) Gelatin 0.99 Color Mixing Prevention Agent (Cpd-4) 0.08 Solvent (Solv-2) 0.25 Solvent (Solv-3) 0.25 Fourth Layer (Green Sensitivity) Emulsion layer) Silver chlorobromide emulsion (cubic, 1: 3 mixture of a large size emulsion having an average grain size of 0.55 μm and a small size emulsion of 0.39 μm (Ag mole ratio). Coefficients of variation of grain size distributions 0.10 and 0.08, 0.8 mol% of AgBr was locally contained in a part of the grain surface in each size emulsion) 0.12 Gelatin 1.45 Magenta coupler (ExM) 0.16 Color image stabilizer (Cpd-6) 0.15 Color image stabilizer (Cpd-2) 0.03 Color image stabilizer (Cpd-7) 0.01 Color image stabilizer (Cpd-8) 0.01 Color image stabilizer (Cpd -9) 0.08 Solvent (Solv-3) 0 50 solvent (Solv-4) 0.15 solvent (Solv-5) 0.15

Fifth layer (color mixing prevention layer) Gelatin 0.70 Color mixing inhibitor (Cpd-4) 0.04 Color image stabilizer (Cpd-5) 0.02 Solvent (Solv-2) 0.18 Solvent (Solv -3) 0.18 Sixth layer (red-sensitive emulsion layer) Silver chlorobromide emulsion (cubic, 1: 4 mixture of a large size emulsion having an average grain size of 0.58 μm and a small size emulsion of 0.45 μm (Ag) (Mole ratio). Coefficient of variation of grain size distribution is 0.09 and 0.11, and 0.6 mol% of AgBr is locally contained in a part of grain surface in each size emulsion) 0.23 Gelatin 0.85 Cyan Coupler (ExC) 0.33 UV absorber (UV-2) 0.18 Color image stabilizer (Cpd-1) 0.33 Color image stabilizer (Cpd-10) 0.15 Color image stabilizer (Cpd-11) ) 0.15 color image stabilizer (Cpd-12) 0 01 Color image stabilizer (Cpd-9) 0.01 Color image stabilizer (Cpd-8) 0.01 Solvent (Solv-6) 0.22 Solvent (Solv-1) 0.01 Seventh layer (UV absorbing layer) ) Gelatin 0.55 UV absorber (UV-1) 0.40 Color image stabilizer (Cpd-13) 0.15 Color image stabilizer (Cpd-6) 0.02 Eighth layer (protective layer) Gelatin 1. 13 Acrylic modified copolymer of polyvinyl alcohol (modification degree 17%) 0.15 Liquid paraffin 0.03 Color image stabilizer (Cpd-14) 0.01 The compounds used here are shown below.

[0062]

[Chemical 19]

[0063]

[Chemical 20]

[0064]

[Chemical 21]

[0065]

[Chemical formula 22]

[0066]

[Chemical formula 23]

Sample A was phenol as an antibacterial and antifungal agent.
Was used. Further, instead of phenol, the antibacterial and antibacterial agent of the present invention may be used.
Molds were added as shown in Table-A to prepare samples B to K. This
Here, phenol and general formulas (A) to (I) or amino groups
Addition of lycosides to each compound, gelatin of each layer
50mg / m with the ratio of ²
It was done so that Also, for sample K,
1 mg / m²It was done so that Both make samples
The antiseptic effect during manufacturing was sufficient.

A running test was carried out on each of the above samples using two bleaching agents. During the running test, the above light-sensitive material is the automatic printer FAP3.
Imagewise exposure using 500 (Fuji Photo Film Co., Ltd.),
Continuous processing (running test) was performed using the following processing steps and processing solutions until the bleach-fix solution was replenished twice.
However, as for the composition of the bleach-fixing solution, a running test was conducted for each level in which the bleaching agent was changed as shown in Table-A. The running test was conducted for 60 days at each level.

Processing process Temperature Time Replenishment amount Tank capacity (sec) (ml / m ² ) (liter) Color development 38.5 ℃ 45 60 8 Bleach fixing 36 ℃ 45 40 8 Stable 36 ℃ 20 − 4 Stable 36 ℃ 20 − 4 Stable 36 ° C 20 − 4 Stable 36 ° C 30 180 4 Stability was a 4-tank countercurrent system of →→→. The composition of each processing liquid is as follows.

[Color Developer] Tank Solution Replenisher Water 800 ml 800 ml EDTA.2Na 3 g 3 g Catechol-3,5-sodium disulfonate 0.3 g 0.3 g Triethanolamine 8.0 g 8.0 g Potassium bromide 0.03 g --Sodium chloride 6.0 g --N, N-di (sulfoethyl) hydroxylamine 5.0 g 8.0 g Optical brightener (WHITEX 4, manufactured by Sumitomo Chemical Co., Ltd.) 1.0 g 2.0 g Sodium sulfite 0.2 g 2 g N-ethyl-N- (β-methanesulfonamidoethyl) 3-methyl-4-aminoaniline sulfate 5.0 g 12.0 g Water was added to 1000 ml 1000 ml pH (25 ° C) 10.05 11.15

[Bleach-fixing tank liquid] Water 800 ml Ammonium thiosulfate (750 g / l) 120 ml Ammonium sulfite 17 g Bleach (ferric ammonium complex salt of the compound shown in Table-A) 0.15 mol Glacial acetic acid 8 g Water was added 1000 ml pH (25%) 5.00

[Bleach-fixing replenisher] Water 500 ml Ammonium thiosulfate (50% by weight) 250 ml Ammonium sulfite 35 g Bleach (ferric ammonium complex salt of compound shown in Table-A) 0.35 mol Glacial acetic acid 25 g Water added 1000 ml pH (25 ° C) 4.50 [Stabilizer] (tank solution and replenisher are the same) 1-Hydroxyethylidene-1,1-diphosphonic acid 1 g Ammonium chloride 2 g Ammonia water 1.5 ml Benzotriazole 1 g Water is added 1000 ml pH (25 ° C) 7.00

The cyan density of the unexposed area density of each sample processed at the end of each running test was measured using a FSD-103 densitometer manufactured by Fuji Photo Film Co., Ltd.
Further, in order to evaluate the degree of colored suspended matter, 1 liter of each bleach-fixing solution after the completion of the running process was filtered with a micro filter FM110 manufactured by Fuji Photo Film Co., Ltd., and the coloration of the filter was visually determined. The degree of filter coloring was evaluated according to the following criteria. Level 1 No coloration 2 Lightly colored 3 Colored to the extent that it can be clearly seen 4 Filtered material adheres to the hand when the filter is rubbed by hand 5 Visually noticeable buildup of filtered material on the filter The cyan density of the unexposed area at the start of each running was 0.09. The results are shown in Table-A.

[0074]

[Table 9]

According to the present invention, the white background is less contaminated and excellent. Further, it can be seen that the colored insoluble matter is also less produced.

Example 2 No. 2 of Example 1. 19, in which a 1-micron gelatin layer was provided between the fifth layer and the sixth layer of Sample H to form two intermediate layers between the green-sensitive layer and the red-sensitive layer (referred to as Sample L). At the end of the running test, the cyan density of the unexposed area did not change, but after this treatment, samples H and L were stored under the condition of 60 ° C. and 50% RH for 2 months. When measured, the sample L is H
It was 0.03 lower than Further, AF-1 of each emulsion layer of Sample L was set to 2 × 10 ⁻⁴ mol per mol of silver halide, and AF-2 and AF-3 were further added to AF-1.
Using the sample M added in the same amount each as above, When the same test as in No. 23 was performed, the cyan density at the start of running did not change, but the cyan density at the unexposed area after running decreased by 0.02.

Example 3 No. 1 of Example 1 19, the base of Sample H was changed to polyethylene terephthalate, and the following U
When a sample M coated with a V absorbing layer was prepared and the same test was conducted, the cyan density at the start of running was not changed, but the cyan density of the unexposed area after running was further improved by 0.02. Back surface first layer gelatin 3.0 g / m ² UV absorber (UV-1) 0.40 g / m ² Back surface second layer gelatin 1.0 g / m ² However, hardening agents and coating aids, etc. Was used similarly to the emulsion side.

[0078]

According to the method of processing a silver halide color photographic light-sensitive material of the present invention, even if a low replenishment processing is carried out, contamination of an unexposed area and formation of a colored suspended matter of a liquid having a bleaching ability can be prevented. Has the remarkable effect of Further, in the present invention, as compared with the case of treatment with a ferric complex such as ethylenediaminetetraacetic acid which is a typical bleaching agent conventionally used,
It has a remarkably excellent effect among the above effects.

Claims (1)

[Claims] 1. A method in which a silver halide color photographic light-sensitive material is subjected to color development and then treated with a liquid having a bleaching ability, wherein the light-sensitive material is at least one hydrophilic colloid layer on a support.
In the layer, at least one compound represented by any of the following general formulas (A) to (I), or gentamicins,
A liquid containing at least one aminoglycoside selected from amikacin, tobramycin, dibekacin, arbekacin, micronomycin, isepamycin, sisomycin, netilmycin and astromicin, and having the bleaching ability is represented by the following general formula (X) as a bleaching agent. A method for processing a silver halide color photographic light-sensitive material, which comprises a ferric complex of the compound represented. [Chemical 1] [Chemical 2] (In the formula, R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₇ and R ₈
Each represent a hydrogen atom, an alkyl group or an aryl group. R ₆ is a hydrogen atom, an alkyl group, an aryl group, a nitro group, a carboxy group, a sulfo group, a sulfamoyl group,
It represents a hydroxy group, a halogen atom, an alkoxy group or a thiazolyl group. L ₁ and L ₂ each represent an alkylene group or an arylene group. R ₉ , R ₁₀ and R ₁₁ are
Each represents a halogen atom or an alkyl group. R ₁₂ and R ₁₃ each represent a hydrogen atom, an alkyl group, an aryl group or a nitrogen-containing heterocyclic residue. R ₁₄ and R ₁₅ each represent a hydrogen atom, a halogen atom, an alkyl group or an aryl group. Incidentally, R ₁₄ and R ₁₅ may combine with each other to form a benzene ring. R ₁₆ represents a hydrogen atom or an alkyl group. R ₁₇ represents an alkyl group or an aryl group.
Y represents a halogen atom. Z ₁ represents a group of non-metal atoms necessary for constituting the thiazolyl ring. Z ₂ represents a group of non-metal atoms necessary for forming a 6-membered hydrocarbon ring. n represents 0 or 1. m represents 1 or 2. k
Represents an integer of 3 to 20. ) [Chemical 3] (In the formula, R _a , R _b , R _c , R _d , R _e, and R _f each represent a hydrogen atom, an aliphatic group, an aromatic group, or a hydroxy group. W is the following general formula (W). Represents a linking group represented by M ₁ , M ₂ , M ₃ and M ₄ each represent a hydrogen atom or a cation General formula (W)-(W ₁ -Z) _n -W _2- (General formula ( In W), W ₁ represents an alkylene group or a single bond, W ₂ represents an alkylene group or —CO—, and Z is a single bond, —O—, —S—, —CO— or —.
Represents N (R _w ) −. R _w represents a hydrogen atom or an alkyl group. n represents an integer of 1 to 3. However, Z
And W ₁ cannot be a single bond at the same time. ))