JPH0854720A - Method for processing silver halide color photographic sensitive material - Google Patents

Abstract

PURPOSE:To provide a processing method to obtain a superior photosensitive material without occurrence of uneven processing and rise of density in minimum density parts through rapid processing by incorporating a specified compound in a color developing solution and dicarboxylic acid on a processing solution having a bleaching ability. CONSTITUTION:The silver halide color photographic sensitive material contains a kind of radical scavenger and has a transparent magnetic recording layer and an emulsion layer containing silver iodide, and it is processed with the color developing solution containing a kind of compound represented by the formula and then processed with a processing solution having bleaching ability and containing a dicarboxylic acid. In the formula, each of R1 and R2 is, independently, H atom or an alkyl or aromatic heterocyclic group and each may combine with each other to form a hetero ring together with N atom, and each is not H atom at the same time.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to processing of a silver halide color photographic light-sensitive material, and more particularly to a method of processing a silver halide color photographic light-sensitive material capable of rapid processing.

[0002]

2. Description of the Related Art Generally, processing of a silver halide photographic light-sensitive material comprises a developing process and a silver removing process. In the processing of color photosensitive materials, in the silver removal process, the developed silver generated in the color development process is oxidized (bleached) into a silver salt by a bleaching agent having an oxidizing action, and further, soluble silver is formed together with unused silver halide. Is removed from the photosensitive layer (fixing). Bleaching and fixing may be performed as independent bleaching and fixing steps, or may be performed simultaneously as a bleach-fixing step. For more information on these processing steps, see The Theory of Photographics by James.
Process, 4th Edition (James, “The Theory of Photograph
ic Process "4'th edition) (1977). The above processing steps are generally carried out by an automatic developing machine. In particular, in recent years, a small automatic developing machine called a minilab is available in stores. In such a minilab, the work load such as preparation of the processing solution and recovery of the waste solution is large, and it is possible to reduce the usage amount of the processing solution, that is, low replenishment. Against this background, there has been a strong demand in recent years especially for a rapid processing step and low replenishment, and also for the bleaching step, fixing step or bleach-fixing step, a drastic speedup and low replenishment are desired. There is.

In the bleaching process, as a bleaching agent, a bleaching agent of aminopolycarboxylic acid iron (III) complex salt such as ethylenediaminetetraacetic acid iron (III) complex salt is often used.
As a means to enhance the desilvering of this ethylenediaminetetraacetic acid iron (III) complex salt, it is known to make the pH of the solution having a bleaching ability as low as 5.5 or less. Known to be used. Among the aminopolycarboxylic acid iron (III) complex salt systems, as a bleaching agent capable of rapid bleaching, 1,3-diaminopropanetetraacetic acid iron (III) complex salt described in JP-A-62-222252 can be mentioned. It has been widely used in recent years. Such an aminopolycarboxylic acid iron (III) complex bleaching agent having a high oxidizing power at a high potential is effective in terms of speediness and the amount of the bleaching agent used can be reduced. For the purpose of preventing the bleaching fog that occurs due to
PH will be as low as 5.5 or less, and a buffer such as acetic acid is required. This acetic acid has been used practically in a processing solution having a bleaching ability of an aminopolycarboxylic acid iron (III) complex salt system because it is preferable in terms of performance such as preventing bleaching fog and having no adverse effect on desilvering, but it is used in a large amount. Then, the odor remains in the processing solution and the processed light-sensitive material to give an unpleasant sensation. Therefore, use of an odorless buffering agent instead of acetic acid has been studied.

For example, Japanese Patent Laid-Open No. 3-188443 proposes a treatment method using a dicarboxylic acid such as malonic acid, fumaric acid or succinic acid as an acetic acid substitute. However, although these acids are preferable from the standpoint of preventing odor, it has been found that in continuous processing, processing unevenness occurs and the density of the minimum density part increases.

[0005]

Although the reason why the above-mentioned problems occur by using the above-mentioned dicarboxylic acid is not clear, compared with acetic acid, dicarboxylic acid is a color developing solution adhered to the film during color development processing. If it is non-uniform, bleaching fog is likely to occur locally, resulting in uneven processing, and the color developer brought into the bleaching solution deteriorates.
It is presumed that the density will increase as it is more likely to adhere to the sensitive material. Therefore, it is an object of the present invention to provide a good processing method of a silver halide color photographic light-sensitive material which is rapid and does not cause processing unevenness or increase in density of the minimum density portion.

[0006]

The above object has been achieved by the following processing method. (1) A method in which a silver halide color photographic light-sensitive material is processed with a color developer and then with a processing solution having a bleaching ability, wherein the light-sensitive material has at least one emulsion layer containing silver iodide, Processing of a silver halide color photographic light-sensitive material, characterized in that the color developer contains at least one compound represented by the following general formula (I), and the processing solution having the bleaching ability contains a dicarboxylic acid. Method. General formula (I)

[0007]

Embedded image

(In the formula, R ¹ and R ² each independently represent a hydrogen atom, an alkyl group, or a heteroaromatic group,
R ¹ and R ² may be linked together to form a heterocycle together with the nitrogen atom. However, R ¹ and R ² are not hydrogen atoms at the same time. )

Next, the general formula (I) of the present invention will be described in detail. In the general formula (I), the alkyl group represented by R ¹ and R ² may be linear, branched or cyclic. The alkyl group represented by R ¹ and R ² may have a substituent, and these substituents include a halogen atom (F, Cl, Br, etc.), an aryl group (phenyl group, p
-Chlorophenyl group, etc.), alkyl group (methyl group, ethyl group, isopropyl group, etc.), alkoxy group (methoxy group, ethoxy group, methoxyethoxy group, etc.), aryloxy group (phenoxy group, etc.), sulfonyl group (methanesulfonyl) Group, p-toluenesulfonyl group, etc.), sulfonamide group (methanesulfonamide group, benzenesulfonamide group, etc.), sulfamoyl group (diethylsulfamoyl group, unsubstituted sulfamoyl group, etc.), carbamoyl group (unsubstituted carbamoyl group, Diethylcarbamoyl group, etc.), Amido group (acetamido group, benzamide group, naphthamido group, etc.), Ureido group (methylureido group, phenylureido group, etc.), Alkoxycarbonylamino group (methoxycarbonylamino group, etc.), Aryloxycarbo group Arylamino (such as phenoxycarbonylamino group) group, (such as methoxycarbonyl group) alkoxycarbonyl group (such as phenoxycarbonyl group) an aryloxycarbonyl group, a cyano group, hydroxy group,
Phosphono group, phosphinic acid residue, carboxy group, sulfo group, nitro group, amino group (unsubstituted amino group, diethylamino group, etc.), alkylthio group (methylthio group, etc.),
Arylthio group (phenylthio group etc.), hydroxyamino group, ammonio group and heterocyclic group (morpholyl group,
Pyridyl group). Here, R ¹ and R ² may be the same or different from each other, and the substituents of R ¹ and R ² may be the same or different.

The heteroaromatic groups represented by R ¹ and R ² are pyrrole, pyrazole, imidazole, 1,2,4.
-Triazole, tetrazole, benzimidazole,
Benzoxazole, benzthiazole, 1,2,4-
Thiadiazole, pyridine, pyrimidine, triazine (s-triazine, 1,2,4-triazine), indazole, purine, quinoline, isoquinoline, quinazoline, pyrimidine, isoxazole, oxazole, thiazole, selenazole, tetraazaindene, s-triazolo [1. , 5-a] pyrimidine, s-triazolo (1,5-b) pyridazine, pentaazaindene, s-
Triazolo (1,5-b) [1,2,4] triazine,
Examples thereof include s-triazolo (5,1-d) -us-triazine and triazaindene (imidazolo [4,5-b] pyridine etc.). The heteroaromatic group may be further substituted with a substituent. The substituent is the same as the substituent mentioned for the alkyl group. Examples of the nitrogen-containing heterocycle formed by connecting R ¹ and R ² include a piperidyl group, a pyrrolidyl group, an N-alkylpiperazyl group, a morpholyl group, an indolinyl group and a benztriazole group.

In the general formula (I), it is preferred that R ¹ and R ² are alkyl groups, and the number of carbon atoms is preferably 1-10, particularly preferably 1-5. Preferred substituents of the alkyl group of R ¹ and R ² are a hydroxy group, an alkoxy group, an alkyl or aryl sulfonyl group, an amide group, a carboxy group, a cyano group, a phosphono group, a phosphinic acid residue, a sulfo group, a carbamoyl group and a sulfamoyl group. Group, nitro group,
An ammonio group and an amino group.

The hydroxylamine derivative represented by the general formula (I) of the present invention is preferably the one represented by the following general formula (IA). General formula (IA)

[0013]

[Chemical 3]

In the formula, L represents a linear or branched alkylene group having 1 to 10 carbon atoms which may be substituted, and preferably 1 to 5 carbon atoms. Specifically, preferred examples include methylene, ethylene, trimethylene, and propylene. Examples of the substituent of the alkylene group include a carboxy group, a sulfo group, a phosphono group, a phosphinic acid residue, a hydroxy group, and an ammonio group which may be alkyl-substituted, and a carboxy group, a sulfo group, a phosphono group, and a hydroxy group are preferred examples. As. A is a carboxy group,
A sulfo group, a phosphono group, a phosphinic acid residue, a hydroxy group, an amino group which may be alkyl-substituted, an ammonio group which may be alkyl-substituted, a carbamoyl group which may be alkyl-substituted, and a sulfamoyl group which may be alkyl-substituted. A carboxy group, a sulfo group, a hydroxy group, a phosphono group, or a carbamoyl group which may be alkyl-substituted may be mentioned as a preferable example.

Preferred examples of -LA include carboxymethyl group, carboxyethyl group, carboxypropyl group, sulfoethyl group, sulfopropyl group, sulfobutyl group, phosphonomethyl group, phosphonoethyl group and hydroxyethyl group. , Carboxymethyl group, carboxyethyl group, sulfoethyl group, sulfopropyl group, phosphonomethyl group and phosphonoethyl group can be mentioned as particularly preferable examples. R is a hydrogen atom,
It represents a linear or branched alkyl group having 1 to 10 carbon atoms which may be substituted, and preferably has 1 to 5 carbon atoms. As the substituent, a carboxy group, a sulfo group, a phosphono group, a phosphinic acid residue, a hydroxy group, an amino group which may be alkyl-substituted, an ammonio group which may be alkyl-substituted, a carbamoyl group which may be alkyl-substituted, an alkyl group It represents a sulfamoyl group which may be substituted. There may be two or more substituents. Preferred examples of R include a hydrogen atom, a carboxymethyl group, a carboxyethyl group, a carboxypropyl group, a sulfoethyl group, a sulfopropyl group, a sulfobutyl group, a phosphonomethyl group, a phosphonoethyl group and a hydroxyethyl group, and a hydrogen atom and carboxymethyl group. A group, a carboxyethyl group, a sulfoethyl group, a sulfopropyl group, a phosphonomethyl group and a phosphonoethyl group can be mentioned as particularly preferable examples. L and R may combine to form a ring. When the compound of the above general formula (I) has an acid group, it is an alkali metal salt,
It goes without saying that ammonium salts may be used. Specific compounds of the present invention will be described below, but the invention is not limited thereto.

[0016]

[Table 1]

[0017]

[Table 2]

[0018]

[Table 3]

[0019]

[Table 4]

[0020]

[Table 5]

[0021]

[Chemical 4]

The compound of the general formula (I) can be obtained as a commercial product. Also, US Pat. No. 3,661,99
No. 6, No. 3,362,961, No. 3,293,034
Issue No. 3,491,151 Issue 3,655,764
No. 3,467,711 and the like. Further, these compounds of the general formula (I) may be alkali metal (for example, sodium, potassium) salts,
Some may form salts with various organic and inorganic acids such as hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, oxalic acid and acetic acid. The compound of the general formula (I) of the present invention is 5.0 × 10 ^{−3 to} 5.0 × 10 ⁻¹ mol, preferably 3.0 × 10 ^{−2 to} 1.0 × 10 mol per liter of color developing solution. ^It is desirable to add it so that the concentration becomes ^-1 molar.

The light-sensitive material according to the present invention has the RD.
No.17643, pages 28 to 29, No. 18716, 651 left column to right column, and No. 307105, pages 880 to 881 can be developed by the usual methods. The color developing solution used for the development processing of the light-sensitive material of the present invention is preferably an alkaline aqueous solution containing an aromatic primary amine type color developing agent as a main component. As the color developing agent, aminophenol compounds are also useful, but p-phenylenediamine compounds are preferably used, and typical examples thereof include 3-methyl-4-amino-N, N diethylaniline and 3-methyl. -4-amino-N-ethyl-N-β-hydroxyethylaniline, 3-
Methyl-4-amino-N-ethyl-N-β-methanesulfonamidoethylaniline, 3-methyl-4-amino-N-ethyl-
β-methoxyethylaniline, 4-amino-3-methyl-N-
Methyl-N- (3-hydroxypropyl) aniline, 4-amino
-3-Methyl-N-ethyl-N- (3-hydroxypropyl) aniline, 4-amino-3-methyl-N-ethyl-N- (2-hydroxypropyl) aniline, 4-amino-3-ethyl-N -Ethyl-N
-(3-hydroxypropyl) aniline, 4-amino-3-methyl-N-propyl-N- (3-hydroxypropyl) aniline,
4-Amino-3-propyl-N-methyl-N- (3-hydroxypropyl) aniline, 4-amino-3-methyl-N-methyl-N- (4-
Hydroxybutyl) aniline, 4-amino-3-methyl-N-
Ethyl-N- (4-hydroxybutyl) aniline, 4-amino-3
-Methyl-N-propyl-N- (4-hydroxybutyl) aniline, 4-amino-3-ethyl-N-ethyl-N- (3-hydroxy-2
-Methylpropyl) aniline, 4-amino-3-methyl-N, N
-Bis (4-hydroxybutyl) aniline, 4-amino-3-
Methyl-N, N-bis (5-hydroxypentyl) aniline,
4-Amino-3-methyl-N- (5-hydroxypentyl) -N- (4-
Hydroxybutyl) aniline, 4-amino-3-methoxy-N
-Ethyl-N- (4-hydroxybutyl) aniline, 4-amino-
3-ethoxy-N, N-bis (5-hydroxypentyl) aniline, 4-amino-3-propyl-N- (4-hydroxybutyl)
Examples thereof include aniline, and their sulfates, hydrochlorides or p-toluenesulfonates. Among these, 3-methyl-4-amino-N-ethyl-N-β-hydroxyethylaniline, 4-amino-3-methyl-N-ethyl-N- (3-
Hydroxypropyl) aniline, 4-amino-3-methyl-N
-Ethyl-N- (4-hydroxybutyl) aniline, and their hydrochlorides, p-toluenesulfonates or sulfates are preferred. Two or more of these compounds can be used in combination depending on the purpose. In the present invention, it is preferable that the color developing solution contains p-toluenesulfonic acid because the effects of the present invention can be remarkably obtained. The p-toluenesulfonic acid may be added as a counter salt of the color developing agent or may be added separately. When it is added separately, it may be added as an alkali metal salt such as sodium salt or potassium salt.
The preferable content of p-toluenesulfonic acid is 0.1 to 100 g, more preferably 1 to 50 g, and particularly preferably 3 to 30 g as p-toluenesulfonic acid per liter of color developing solution.

The amount of the aromatic primary amine developing agent used is preferably 0.0002 mol to 0.2 mol, and more preferably 0.001 mol to 1 mol per liter of the color developing solution.
It is 0.1 mol.

The color developer contains a pH buffering agent such as an alkali metal carbonate, borate or phosphate 5-sulfosalicylate, a chloride salt, a bromide salt, an iodide salt, benzimidazoles and benzo. It generally contains a development inhibitor such as a thiazole or a mercapto compound or an antifoggant. If necessary, hydroxylamine, sulfite, hydrazines such as N, N-biscarboxymethylhydrazine, phenylsemicarbazides,
Various preservatives such as triethanolamine and catechol sulfonic acids, organic solvents such as ethylene glycol and diethylene glycol, benzyl alcohol, polyethylene glycol, quaternary ammonium salts, development accelerators such as amines, dye forming couplers and competitive couplers. , Chelating agents such as auxiliary developing agents such as 1-phenyl-3-pyrazolidone, tackifiers, aminopolycarboxylic acids, aminopolyphosphonic acids, alkylphosphonic acids, and phosphonocarboxylic acids, for example, ethylenediamine Tetraacetic acid, nitrilotriacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, hydroxyethyliminodiacetic acid, 1-hydroxyethylidene-1,1-diphosphonic acid,
Representative examples thereof include nitrilo-N, N, N-trimethylenephosphonic acid, ethylenediamine-N, N, N, N-tetramethylenephosphonic acid, ethylenediamine-di (o-hydroxyphenylacetic acid) and salts thereof. . Further, a compound having biodegradability is preferable as the chelating agent. Examples of this are Japanese Patent Laid-Open Nos. 63-146998 and 6-1988.
3-199295, JP-A-63-267750, JP-A-63-267751, and JP-A-2-229146.
No. 3, JP-A-3-186841, German Patent 373961
0, and chelating agents described in European Patent 468325 and the like. It is preferable that the processing solution in the color developing solution replenishing tank or the processing tank is shielded with a liquid agent such as a high-boiling point organic solvent to reduce the contact area with air. Liquid paraffin is most preferable as the liquid shield agent. It is particularly preferable to use it as a replenisher. The processing temperature of the color developing solution in the present invention is 20 to 55 ° C., preferably 3
It is 0 to 55 ° C. The processing time is 2 for the photosensitive material for photography.
It is 0 second to 5 minutes, preferably 30 seconds to 3 minutes and 20 seconds. More preferably, it is 1 minute to 2 minutes and 30 seconds, and for printing materials, it is 10 seconds to 1 minute and 20 seconds, preferably 10 seconds to 6 seconds.
It is 0 second, and more preferably 10 to 40 seconds.

When the reversal process is carried out, black and white development is usually carried out before color development. In this black-and-white developer, known black-and-white developing agents such as dihydroxybenzenes such as hydroquinone, 3-pyrazolidones such as 1-phenyl-3-pyrazolidone or aminophenols such as N-methyl-p-aminophenol are used alone. Alternatively, they can be used in combination. The color developing solution and the black and white developing solution generally have a pH of 9 to 12. The replenishing amount of these developers depends on the color photographic light-sensitive material to be processed, but it is generally 3 liters or less per 1 square meter of the light-sensitive material, and it is 800 ml or less by reducing the bromide ion concentration in the replenisher. Preferably. More preferably 50 to 600 ml, particularly preferably 100 to
It is 500 ml. When the replenishment rate is reduced, it is preferable to prevent evaporation of the liquid and air oxidation by reducing the contact area of the processing tank with the air. The contact area between the photographic processing liquid and air in the processing tank can be represented by the aperture ratio defined below. That is, aperture ratio = [contact area between treatment liquid and air (cm ² )] ÷ [volume of treatment liquid (cm ³ )] The above aperture ratio is preferably 0.1 or less, and more preferably 0.001 to 0.05. Is. As a method of reducing the aperture ratio in this way, in addition to providing a cover such as a floating lid on the photographic processing liquid surface of the processing tank, a method using a movable lid described in JP-A-1-82033 is disclosed. The slit development processing method described in 63-216050 can be mentioned. Reducing the aperture ratio is not limited to both the color development and black and white development steps, but also the subsequent steps such as bleaching, bleach-fixing,
It is preferably applied in all steps such as fixing, washing with water, and stabilization. Further, the amount of replenishment can be reduced by using a means for suppressing the accumulation of bromide ions in the developing solution.

The photographic emulsion layer after color development is usually bleached. 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 processing, a processing method of bleach-fixing processing after bleaching processing may be used. Further, treatment with two continuous bleach-fixing baths, fixing treatment before the bleach-fixing treatment, or bleaching treatment after the bleach-fixing treatment can be optionally carried out. As the bleaching agent, compounds of polyvalent metals such as iron (III), peracids, quinones, nitro compounds and the like are used. A typical bleaching agent is an iron (III) complex salt,
For example, ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, methyliminodiacetic acid, glycol etherdiaminetetraacetic acid, JP-A-4
No. 121739, a bleaching agent including a 1,3-propylenediaminetetraacetic acid iron complex salt in the lower right column of the fourth page to the upper left column of the fourth page, and a carbamoyl-based bleaching agent described in JP-A-4-73647. Bleaching agents, bleaching agents having a heterocycle described in JP-A-4-174432, bleaching agents described in European Patent Publication No. 520457, including N- (2-carboxyphenyl) iminodiacetic acid ferric complex salts. Bleaching agents described in JP-A-5-66527, including ethylenediamine-N-2-carboxyphenyl-N, N ′, N′-ferric triacetate, bleaching agents described in EP-A-501479, A bleaching agent described in JP-A-4-127145 and a ferric aminopolycarboxylic acid salt or a salt thereof described on page (11) of JP-A-3-144446 are preferably used. Among these, JP-A-4-121739,
Bleaching agents including the 1,3-propylenediaminetetraacetic acid iron complex salt in the lower left column of the fourth page to the upper left column of the fifth page are preferable, and the 1,3-propylenediaminetetraacetic acid iron complex salt is particularly preferable. In the present invention, the concentration of the bleaching agent contained in the liquid having a bleaching ability is suitably in the range of 0.003 to 3.0 mol / liter, and in the range of 0.02 to 2.0 mol / liter. Preferably 0.05-1.0 mol /
The liter range is particularly preferred.

The organic aminocarboxylic acid iron (III) complex salt is particularly useful in both the bleaching solution and the bleach-fixing solution.
The pH of the bleaching solution or bleach-fixing solution using these organic aminocarboxylic acid iron (III) complex salts is usually 4.0 to 8, but it is also possible to process at a lower pH in order to speed up the processing. Particularly in the bleaching solution, pH 3.0 to 6.0 is preferable,
Further, pH 3.2 to 5.0 is preferable. The replenishing amount of the bleaching solution of the present invention is 30 to 15 per 1 m ² of the light-sensitive material.
00 ml is preferable, but more preferably 50 to 800 m
It is l. More preferably, it is 60 to 200 ml. The lower the replenishment amount, the more remarkable the effect of the present invention.

The present invention is characterized by containing a dicarboxylic acid in a liquid having a bleaching ability. The dicarboxylic acid compound means a saturated dicarboxylic acid having two carboxyl groups in one molecule, an unsaturated dicarboxylic acid, an aromatic carboxylic acid, and an alkali metal salt or ammonium salt thereof. In the present invention, dicarboxylic acids represented by the following general formula (B) and salts thereof are preferred. General formula (B) HOOC-Q-COOH (In the formula, Q represents a single bond or a saturated or unsaturated aliphatic group having 1 to 4 carbon atoms.) In formula (B), a fat represented by Q. The group group is a linear or branched, saturated or unsaturated aliphatic group having 1 to 4 carbon atoms. The aliphatic group represented by Q may have a substituent or may be unsubstituted. The substituent of the aliphatic group may be any group as long as it can be a substituent. Preferably, a hydroxy group, a halogen atom (eg chlorine atom, bromine atom, fluorine atom), an amino group, an alkoxy group (eg methoxy, ethoxy) and the like can be mentioned. The preferable addition amount is 0.1 in 1 liter of the bleaching solution.
Mol to 2.0 mol, more preferably 0.5 mol to 1.5
It is in the molar range. Examples of preferable dicarboxylic acids are shown below, but the present invention is not limited thereto. Examples thereof include oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, maleic acid, fumaric acid, malic acid, tartaric acid, phthalic acid, diglycolic acid, aspartic acid and glutamic acid. Of these, particularly preferred are malonic acid, succinic acid, glutaric acid, and maleic acid, which are preferably used in combination of two or more, and more preferably used in combination of two or three, Particularly, it is most preferable to use two kinds of succinic acid and maleic acid together.

In the liquid having a bleaching ability of the present invention, an organic acid having an acid dissociation constant (pKa) of 2 to 5.5 is used in addition to the above dicarboxylic acid as long as the effect of the present invention is not impaired. be able to. Specific compounds include acetic acid, propionic acid, hydroxyacetic acid and the like.

The bleaching treatment of the present invention is particularly preferable to be carried out immediately after color development in order to exert the effects of the present invention, but like a reversal treatment, it may be conditioned through a conditioning bath (which may be a bleaching accelerating bath). You may do it. These adjusting baths may contain an image stabilizer described later. In the present invention, the desilvering bath contains a bleaching agent and the above-mentioned JP-A-3-144
Rehalogenating agents, pH buffers and known additives described on page (12) of Japanese Patent No. 446, aminopolycarboxylic acids, organic phosphonic acids and the like can be used. Further, in the present invention, various bleaching accelerators can be added to the bleaching solution or its prebath. Regarding such a bleaching accelerator, for example, U.S. Pat. No. 3,893,858, German Patent No. 1,290,821, British Patent No. 1,138,842, JP-A No. 53-956
Publication No. 30, Research Disclosure No. 1712
No. 9 (July 1978), a compound having a mercapto group or a disulfide group, JP-A-50-1401.
29, a thiazolidine derivative described in U.S. Pat. No. 3,706,561
The iodide described in JP-A-58-16235, the polyethylene oxides described in German Patent 2,748,430, and the polyamine compound described in JP-B-45-8836 can be used. . Further, the compounds described in U.S. Pat. No. 4,552,834 are also preferred. These bleaching accelerators may be added to the light-sensitive material. These bleaching accelerators are particularly effective when bleach-fixing a color photographic material for photography. Particularly preferably British Patent No. 1,13
A mercapto compound as described in the specification of JP-A-8-842 and JP-A-2-190856 is preferable.

The total time of the desilvering process is preferably as short as possible so long as no desilvering failure occurs. Preferred time is 1 to 3 minutes
Minutes, more preferably 1 minute to 2 minutes. The treatment temperature is 25 ° C to 50 ° C, preferably 35 ° C to 45 ° C. In the preferable temperature range, the desilvering rate is improved, and the stain generation after the processing is effectively prevented. The processing solution having a bleaching ability of the present invention is particularly preferably subjected to aeration during processing because the photographic performance is kept extremely stable. Means known in the art can be used for the aeration, and blowing of air into the processing liquid having a bleaching ability or absorption of air using an ejector can be performed. At the time of blowing air, it is preferable to discharge the air into the liquid through an air diffusing tube having fine pores. Such an air diffuser is widely used as an aeration tank in activated sludge treatment. Regarding aeration, Z-121, Eusing Process C-41 3rd edition (1982), Eastman Kodak Company, BL-1 to BL
-The items described on page 2 can be used. In the processing using the processing solution having the bleaching ability of the present invention, it is preferable that the stirring is intensified, and the practice is disclosed in JP-A-3-3384.
The contents described on page 8, upper right column, line 6 to lower left column, line 2 of Japanese Patent Publication No. 7 can be used as they are.

In the desilvering step, it is preferable that the stirring is strengthened as much as possible. Specific examples of the method for strengthening stirring include a method in which a jet of a processing solution is made to collide with the emulsion surface of a light-sensitive material described in JP-A-62-183460, and JP-A-62-1834.
A method of increasing the stirring effect using the rotating means of No. 61, and further moving the light-sensitive material while bringing the emulsion surface into contact with the wiper blade provided in the liquid to make the emulsion surface turbulent, thereby further improving the stirring effect. Examples thereof include a method for improving the method and a method for increasing the circulation flow rate of the entire processing solution. Such a stirring improving means is effective for any of the bleaching solution, the bleach-fixing solution and the fixing solution. It is considered that the improvement of the stirring speeds up the supply of the bleaching agent and the fixing agent into the emulsion film, and consequently the desilvering rate. Further, the above-mentioned means for improving the stirring is more effective when a bleaching accelerator is used, and can significantly increase the accelerating effect or eliminate the fixing inhibiting effect of the bleaching accelerator. The automatic developing machine used for the light-sensitive material of the present invention is disclosed in JP-A-60-191257, JP-A-60-191258, and JP-A-60-191258.
It is preferable to have the photosensitive material conveying means described in 60-191259. As described in the above-mentioned JP-A-60-191257, such a conveying means can remarkably reduce the carry-in of the treatment liquid from the front bath to the rear bath, and is highly effective in preventing the performance deterioration of the treatment liquid. Such an effect is particularly effective for reducing the processing time in each step and reducing the replenishing amount of the processing solution.

The processing solution having bleaching ability of the present invention is
The overflow solution after use in the treatment can be recovered, the components can be added to modify the composition, and then the overflow solution can be reused. Such usage is usually called regeneration, but the present invention can also favor such regeneration. For details of the reproduction, see Fuji Film Processing Manual issued by Fuji Photo Film Co., Ltd., Fuji Color Negative Film, CN-16 processing (revised August 1990), pp. 39-.
The matters described on page 40 can be applied. The kit for adjusting the processing solution having a bleaching ability of the present invention may be a liquid or a solid (powder, granules, tablets, etc.), but when ammonium salts are excluded, most of the raw materials are supplied as a solid, and It also has low hygroscopicity, which makes it easier to make solids. From the viewpoint of reducing the amount of waste liquid, the above-mentioned regenerating kit is preferably a solid because it can be added directly without using extra water.

Regarding the regeneration of the processing solution having the bleaching ability,
In addition to the aeration mentioned above, "Basics of photographic engineering-silver salt photography-" (edited by the Photographic Society of Japan, published by Corona Publishing Co., 1979)
Year)) etc. can be used. Specifically, in addition to electric field regeneration, there is a method for regenerating bleaching solution with bromic acid, zincic acid, bromine, bromine precursor, persulfate, hydrogen peroxide, hydrogen peroxide using catalyst, bromic acid, ozone, etc. Can be mentioned.
In the electrolytic regeneration, the cathode and the anode are put in the same bleaching bath, or the diaphragm and the anode tank and the cathode bath are separated into different baths, and the bleaching solution and the developer and / or the diaphragm are also used. Alternatively, the fixing solution can be regenerated at the same time. The fixing solution and the bleach-fixing solution are regenerated by electrolytically reducing accumulated silver ions. Other,
It is also preferable to remove accumulated halogen ions with an anion exchange resin in order to maintain the fixing performance. In order to reduce the amount of washing water used, ion exchange or ultrafiltration is used, but it is particularly preferable to use ultrafiltration.

Next, the processing liquid having fixing ability of the present invention will be described. The processing liquid having fixing ability of the present invention specifically refers to a fixing liquid, a bleach-fixing liquid, a fixing stabilizing liquid, and the like.
A fixer and a bleach-fixer are preferred. The fixer contains a fixing agent. Examples of the fixing agent include thiosulfates such as sodium thiosulfate, ammonium thiosulfate, sodium ammonium thiosulfate and potassium thiosulfate, thiocyanates (rhodan salts) such as sodium thiocyanate, ammonium thiocyanate and potassium thiocyanate, thiosulfates. Examples thereof include urea and thioether. Of these, thiosulfate is preferable. The amount of thiosulfate used is preferably 0.1 to 3 mol, preferably 0.5 to 1.5 mol, per liter of the fixing solution.

The fixer contains sulfites (eg, sodium sulfite, potassium sulfite, ammonium sulfite), hydroxylamines, hydrazines, bisulfite adducts of aldehyde compounds (eg, acetaldehyde sodium bisulfite) as preservatives, and The sulfinic acid compound or alkylsulfinic acid (for example, ammonium methanesulfinate, sodium methanesulfinate) etc. which are described in Kaihei 1-223151 can be contained. In particular, the addition of sulfinic acids is preferable for improving the liquid stability. Further, various fluorescent whitening agents, antifoaming agents or surfactants, polyvinylpyrrolidone, organic solvents such as methanol and the like can be contained.

Further, various chelating agents such as aminopolycarboxylic acids and organic phosphonic acids are preferably added to the fixing solution for the purpose of stabilizing the processing solution. Preferred chelating agents include nitrilotriacetic acid, hydroxyethyliminodiacetic acid, nitriloacetic acid dipropionic acid, ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, 1,2-propylenediaminetetraacetic acid, ethylenediaminedisuccinic acid, 1 And aminopolycarboxylic acids such as 3-propylenediamine disuccinic acid. The amount of the chelating agent added is 0.01 to 0.3 mol, preferably 0.03 to 1 mol, per liter of the treatment liquid.
It is 0.2 mol.

The present invention is a fixing accelerator or fixing agent such as ammonium thiocyanate (rhodanammonium),
Thiourea, thioether (eg 3,6-dithia-1,
8-octanediol) and thiosulfinic acid (for example, ammonium methanethiosulfinate, sodium methanethiosulfinate) are preferably used. The amount of these compounds used is 0.0 per liter of fixer.
It is used in an amount of 1 to 1 mol, preferably 0.1 to 0.5 mol.

Bleach-fixing solution at the start of processing (start solution)
Is prepared by dissolving the above-mentioned compound used in the bleach-fixing solution in water, but it may be prepared by mixing an appropriately prepared bleaching solution and a separately-prepared fixing solution.

The pH of the fixing solution for the color light-sensitive material is preferably 5-9, more preferably 6-7.5. Further, in the bleach-fixing solution, it is preferably 5.5 to 8.0, and more preferably 6.0 to 7.5.

In order to adjust the fixing solution and the bleach-fixing solution in such a pH range, and as a buffering agent, pKa is 6.0 to 6.0.
It is preferable to contain the compound in the range of 9.0 because the stability of the treatment liquid is improved. These compounds include:
Examples thereof include phosphates, imidazoles such as imidazole, 1-methyl-imidazole, 2-methyl-imidazole, 1-ethyl-imidazole, triethanolamine, N-allylmorpholine, N-benzoylpiperazine and the like. Most preferred are imidazole compounds. Preferred imidazole compounds are the compounds represented by the general formula (I) of JP-A-4-130432, and specific examples thereof are the imidazole compounds (1) to (12) of the same specification. Of these, particularly preferred are imidazole and 2-methylimidazole. These compounds are preferably 0.01 to 2 mol, preferably 0.05 mol to 0.
It is 5 mol.

In addition to the replenishment of the fixing replenisher, it is preferable to introduce washing water for the post-bath or a stabilizing solution into the fixing solution. In this case, a part or all of the overflow solution of the processing solution in the post-bath may be introduced into the fixing bath, or the processing solution in the processing bath may be directly pumped to the fixing bath. When the replenishing method is adopted, the total replenishing amount of the fixing solution (including the amount of washing water or stabilizing solution when it is introduced into the fixing bath) is 100 to 2000 m per 1 m ² of the light-sensitive material.
1 is preferable, but 100 to 800 ml is more preferable. The lower the replenishment amount, the more remarkable the effect of the present invention.

Further, in the present invention, the total processing time of the processing having fixing ability is 0.5 to 4 minutes, preferably 0.5 to 2
Min, particularly preferably 0.5 to 1 min. In the present invention, the total processing time of the desilvering process consisting of a combination of bleaching, bleach-fixing and fixing is preferably 45 seconds to 4 minutes, more preferably 1 minute to 2 minutes. The processing temperature is 25 to 50.
C., preferably 35 to 45.degree.

The fixing solution of the present invention can be subjected to silver recovery by a known method, and a regenerating solution subjected to such silver recovery can be used. As a silver recovery method, an electrolysis method (described in French Patent No. 2,299,667), a precipitation method (described in Japanese Patent Laid-Open No. 52-73037, German Patent No. 2,331,220), an ion exchange method (Japanese Patent Application Laid-Open No. 51-17114, German Patent No. 2,548,237) and metal substitution method (English Patent No. 1,353,805) are effective. These silver recovery methods are preferable when they are carried out in-line from the tank solution because the suitability for rapid processing is further improved.

After the fixing process, a washing process is usually performed. It is also possible to use a simple processing method in which after the treatment with the fixing solution, the stabilizing treatment using the stabilizing solution is carried out without substantially washing with water.

The light-sensitive material of the present invention is generally washed with water and / or stabilized after the desilvering process. 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. Of these, the relationship between the number of washing tanks and the water volume in the multi-stage countercurrent system is described in the Journal of the
Society of MotionPicture and Television Engineers
It can be determined by the method described in Volume 64, P. 248 to 253 (May 1955 issue). According to the multi-stage countercurrent method described in the above-mentioned document, the amount of washing water can be greatly reduced, but due to the increase in the residence time of water in the tank, bacteria propagate, and the suspended matter produced adheres to the photosensitive material, etc. Problem arises. In the processing of the color light-sensitive material of the present invention, the method of reducing calcium ion and magnesium ion described in JP-A-62-288838 can be used very effectively as a solution to such a problem. In addition, JP-A-57
-8542, isothiazolone compounds, siabendazoles, chlorinated fungicides such as chlorinated sodium isocyanurate, and other benzotriazoles, etc. Hiroshi Horiguchi "Chemistry of Antibacterial and Antifungal Agents" (1986) Sankyo Publishing "Sterilization, Sterilization, and Antifungal Technology of Microorganisms" edited by the Sanitary Engineers Association (1982) Industrial Technology Association, "Antibacterial and Antifungal Encyclopedia" edited by Japan Society for Antibacterial and Antifungal Agents (1986)
It is also possible to use the bactericide described in.

Rinsing water in processing the light-sensitive material of the present invention
The pH is 4-9, preferably 5-8. The washing water temperature and the washing time can be variously set depending on the characteristics of the light-sensitive material, the use, etc., but in general, it is 20 seconds to 10 minutes at 15 to 45 ° C., preferably
A range of 30 seconds to 5 minutes at 25-40 ° C is selected. Further, the light-sensitive material of the present invention can be directly processed with a stabilizing solution instead of the above washing with water. In such stabilization treatment, all known methods described in JP-A-57-8543, JP-A-58-14834 and JP-A-60-220345 can be used.

In the stabilizing solution, compounds that stabilize the dye image, for example, benzaldehydes such as formalin and m-hydroxybenzaldehyde, formaldehyde bisulfite adducts, hexamethylenetetramine and its derivatives, hexahydrotriazine and its derivatives, It includes N-methylol compounds such as dimethylol urea and N-methylol pyrazole, organic acids and pH buffering agents. The addition amount of these compounds is preferably 0.001 to 0.02 mol per liter of the stabilizing solution, but the lower the free formaldehyde concentration in the stabilizing solution is, the less the formaldehyde gas is scattered, which is preferable. From this point of view, examples of the dye image stabilizer include m-hydroxybenzaldehyde, hexamethylenetetramine, N-methylolpyrazole, N-methylolazoles described in JP-A-4-270344, N, N'-bis (1 , 2,4-Triazol-1-ylmethyl) piperazine etc.
Azolylmethylamines described in 13753 are preferred. Particularly, azoles such as 1,2,4-triazole described in JP-A-4-359249 (corresponding to European Patent Publication No. 519190A2) and 1,4-bis (1,2,4)
The combined use of azolylmethylamine and its derivatives such as -triazol-1-ylmethyl) piperazine is preferable because of high image stability and low formaldehyde vapor pressure. In addition, if necessary, ammonium compounds such as ammonium chloride and ammonium sulfite, metal compounds such as Bi and Al, optical brighteners, hardeners, US Pat.
It is also preferable to contain an alkanolamine described in JP-A-86,583 or a preservative that can be contained in the fixing solution or the bleach-fixing solution, for example, a sulfinic acid compound described in JP-A-1-231510. .

The washing water and the stabilizing solution may contain various surfactants in order to prevent unevenness of water droplets when the photosensitive material after processing is dried. Among these, it is preferable to use a nonionic surfactant, and an alkylphenol ethylene oxide adduct is particularly preferable. Octyl, nonyl, dodecyl and dinonylphenol are particularly preferable as the alkylphenol, and 8 to 14 are particularly preferable as the number of moles of ethylene oxide added. Further, it is also preferable to use a silicon-based surfactant having a high defoaming effect.

Various chelating agents are preferably contained in the washing water and the stabilizing solution. Preferred chelating agents include aminopolycarboxylic acids such as ethylenediaminetetraacetic acid and diethylenetriaminepentaacetic acid, 1-hydroxyethylidene-1,1-diphosphonic acid, N, N, N'-trimethylenephosphonic acid and diethylenetriamine-N, N,
Examples thereof include organic phosphonic acids such as N ', N'-tetramethylenephosphonic acid, and hydrolyzates of maleic anhydride polymers described in European Patent 345,172A1.

The overflow solution accompanying the washing with water and / or the supplement of the stabilizing solution can be reused in other steps such as the desilvering step. In the processing using an automatic processor, etc., when the above processing solutions are concentrated by evaporation,
In order to correct the concentration by evaporation, it is preferable to replenish an appropriate amount of water or a correction solution or a processing replenishing solution. The specific method for replenishing water is not particularly limited, but among them, a monitor water tank different from the bleaching tank described in JP-A-1-254959 and 1-254960 is installed, and water in the monitor water tank is installed. The amount of water vaporized in the bleaching tank is calculated from the amount of water vaporized in the bleaching tank, and the bleaching tank is replenished with water in proportion to the amount of water vaporized.
No. 3-249644, 3-249645, 3-249646, and an evaporation correction method using a liquid level sensor or an overflow sensor, and the Institute of Invention and Innovation Technical Report 94-4992, page 1, right column 26. The evaporation correction method described in line 28 to page 3, left column, line 28 is preferable. As the water for correcting the evaporation of each treatment liquid, tap water may be used, but deionized water or sterilized water which is preferably used in the above washing step is preferably used.

Various treatment liquids in the present invention are used at 10 ° C to 50 ° C. Normally, a temperature of 33 ° C to 38 ° C is standard, but a higher temperature accelerates the processing to shorten the processing time, and a lower temperature lowers the image quality to improve the stability of the processing liquid. be able to.

The form of supply of various processing liquids in the present invention is as follows.
Concentrated liquid, powder (powder, granules), tablets and the like may be supplied, or may be supplied in the state of a use liquid that can be used in the supplied liquid form. As the above powder, Japanese Patent Laid-Open No. 2-10
9042, 2-109043 and 4-2534.
The powder described in No. 53 and the like and the above-mentioned tablets are described in JP-A-5-
-10039, 5-113646, 5-134
The tablet described in No. 362 is preferably used. Concentrated liquids, powders (powder, granules), tablets and other processing agents may be diluted by the user and used as a replenishing solution, or a processing amount of the processing agent that remains in the supplied form may be stored in a tank. Alternatively, water may be added to the tank separately and water corresponding to the amount of the treatment agent added may be added to the tank.

In the present invention, each processing solution can be commonly used for processing two or more kinds of photosensitive materials. For example,
By processing the color negative film and the color paper or the color paper and the direct positive photosensitive material using the same processing liquid, it is possible to reduce the cost of the processor and simplify the processing.

Next, the light-sensitive material of the present invention will be described. The photographic material of the present invention preferably contains at least one radical scavenger in at least one of the photographic constituent layers. The radical scavenger in the present invention means galvinoxyl 0.05 mm at 25 ° C.
oldm ^-3 2.5mmoldm ethanol solution and the test compound ^-3
It is a compound which is mixed with an ethanol solution by the stopped-flow method, and the time change of the absorbance at 430 nm is measured to substantially decolor galvinoxyl (decrease the absorbance at 430 nm). Preferably, the decolorization rate constant of galvinoxyl determined by the above method is 0.01 mmol ⁻¹ s ⁻¹ dm ³ or more, more preferably 0.1
It is more than mmol ^-1 s ^-1 dm ³ . For the method of determining radical scavenging rate using galvinoxyl, see Microchemical Jo
urnal 31 , 18-21 (1985), the stopped-flow method is described in, for example, Spectroscopic Research Vol. 19, No. 6 (1970) 321.
Page. In the present invention, it is more preferable to use a compound represented by the following general formula [A] as the radical scavenger. The compound represented by formula (A) is described in detail below.

[0057]

[Chemical 5]

In the general formula [A], R _a1 is an alkyl group, an alkenyl group, an aryl group, a heterocyclic group, an acyl group, a sulfonyl group, a sulfinyl group, a carbamoyl group,
It represents a sulfamoyl group, an alkoxycarbonyl group or an aryloxycarbonyl group, and R _a2 represents a hydrogen atom or the group represented by R _a1 . However, when R _a1 is an alkyl group, an alkenyl group or an aryl group, R _a2 is a heterocyclic group, an acyl group, a sulfonyl group, a sulfinyl group, a carbamoyl group, a sulfamoyl group, an alkoxycarbonyl group or an aryloxycarbonyl group. R _a1 and R
_a2 may combine with each other to form a 5- to 7-membered ring.

The compound represented by formula [A] will be described in more detail. In the general formula [A], R _a1 is an alkyl group (eg, methyl, ethyl, i-propyl, cyclopropyl, butyl, isobutyl, cyclohexyl, t-octyl, decyl, dodecyl, hexadecyl, benzyl), an alkenyl group (eg, allyl). , 2-butenyl,
Isopropenyl, oleyl, vinyl), aryl groups (eg phenyl, naphthyl), heterocyclic groups (5- to 7-membered heterocyclic rings having at least one of nitrogen atom, sulfur atom, oxygen atom or phosphorus atom as a ring-constituting atom) A group that forms, for example, 1,3,5-triazin-2-yl, 1,2,4-triazin-3-yl, pyridin-2
-Yl, pyrazinyl, pyrimidinyl, purinyl, quinolyl, imidazolyl, 1,2,4-triazol-3-yl, benzimidazol-2-yl, thienyl, furyl, imidazolidinyl, pyrrolinyl, tetrahydrofuranyl, morpholinyl), an acyl group (for example, Acetyl, benzoyl, pivaloyl, α- (2,4-di-tert-amylphenoxy) butyryl, myristoyl, stearoyl, naphthoyl, m-pentadecylbenzoyl, isonicotinoyl), sulfonyl group (for example, methanesulfonyl, octanesulfonyl, benzenesulfonyl, Toluenesulfonyl), sulfinyl group (eg methanesulfinyl, benzenesulfinyl), carbamoyl group (eg N-ethylcarbamoyl, N-phenylcarbamoyl, N, N-dimethylcarbyl) Moil, N- butyl -N-
Phenylcarbamoyl), sulfamoyl group (eg N
-Methylsulfamoyl, N, N-diethylsulfamoyl, N-phenylsulfamoyl, N-cyclohexyl-N-phenylsulfamoyl, N-ethyl-N-dodecylsulfamoyl), alkoxycarbonyl group (for example, Methoxycarbonyl, cyclohexyloxycarbonyl, benzyloxycarbonyl, isoamyloxycarbonyl, hexadecyloxycarbonyl) or an aryloxycarbonyl group (eg phenoxycarbonyl, naphthoxycarbonyl). R _a2 represents a hydrogen atom or the group represented by R _a1 . R _a1 and R _a2 may combine with each other to form a 5- to 7-membered ring, and examples thereof include a succinimide ring, a phthalimide ring, a triazole ring, a furazole ring, a hydantoin ring, and a 2-oxo-4-oxazolidinone ring.

R _a1 and R _a2 represented by the general formula [A]
The group may be further substituted with a substituent. Examples of these substituents include an alkyl group, an alkenyl group, an aryl group, a heterocyclic group, a hydroxy group, an alkoxy group, an aryloxy group, an alkylthio group, an arylthio group, an amino group, an acylamino group, a sulfonamide group, an alkylamino group, Arylamino group, carbamoyl group, sulfamoyl group, sulfo group, carboxyl group, halogen atom, cyano group, nitro group, sulfonyl group, acyl group, alkoxycarbonyl group, aryloxycarbonyl group,
Examples thereof include an acyloxy group and a hydroxyamino group.

Among the compounds represented by the general formula [A],
R _a1 is preferably a heterocyclic group. More preferably, R _a1 is a heteroaromatic ring group (including a heterocyclic group that can formally form a heteroaromatic ring in the equilibrium structure; hereinafter used in this sense). More preferable ones are represented by the following general formula [AI].

[0062]

[Chemical 6]

In the general formula [AI], R _a2 ′ represents a hydrogen atom, an alkyl group, an alkenyl group or an aryl group. Z represents a heteroaromatic ring group.

Of the compounds represented by the general formula [AI], those in which R _a2 ′ is a hydrogen atom or an alkyl group are preferable. Further, Z is preferably such that the ring-constituting atom is a carbon atom or a nitrogen atom. Most preferably, the general formula [A-I
It is a compound represented by I].

[0065]

[Chemical 7]

[0066] In general formula [A-II], R _a2 'is R _a2 in the general formula [A-I]' represents the same group as. R _a3 and R _{a4, which} may be the same or different, each represents a hydrogen atom or a substituent. Among the compounds represented by the general formula [A-II], R _a3 and R _a4 are hydroxyamino groups,
A hydroxyl group, amino group, alkylamino group, arylamino group, alkoxy group, aryloxy group, alkylthio group, arylthio group, alkyl group or aryl group is preferred. More preferred are a hydroxyamino group and an alkylamino group, and most preferred are a hydroxyamino group and an alkylamino group having 7 or more carbon atoms. Specific examples of the compound represented by formula (A) of the present invention are shown below, but the present invention is not limited thereto.

[0067]

Embedded image

[0068]

[Chemical 9]

[0069]

[Chemical 10]

[0070]

[Chemical 11]

[0071]

[Chemical 12]

In the present invention, these compounds are referred to as J. Org.
Chem., 27, 4054 ('62), J. Amer. Chem. Soc., 73, 298
It can be easily synthesized by the method described in 1 ('51), JP-B-49-10692 or the like or a method analogous thereto. The layer in which the radical scavenger is added to the light-sensitive material may be any layer, but an emulsion layer is preferable, and particularly when the total carbon number of the radical scavenger is 11 or more, it is preferable to add to the layer containing a coupler. Similarly, when the total number of carbon atoms is 10 or less, it is preferable to add it to the layer containing no coupler. The preferable addition amount of the radical scavenger in the present invention is, when added to the light-sensitive material, 0.05 to 100 m ² per 1 m ² of the light-sensitive material.
g is preferable, 0.1 to 50 mg is more preferable, and 1 is especially preferable.
~ 20 mg is preferred. The method for adding the radical scavenger in the present invention to the light-sensitive material is not particularly limited, but it is preferably added directly as it is, or after being dissolved in a water-soluble organic solvent (eg, methyl alcohol, ethyl alcohol, etc.) and then added. Is mentioned.

The light-sensitive material of the present invention may be provided with at least one layer of a blue-sensitive layer, a green-sensitive layer and a red-sensitive silver halide emulsion layer on a support. There is no particular limitation on the number and order of layers of the silver halide emulsion layer and the non-photosensitive layer. As a typical example, a silver halide photographic light-sensitive material having on a support at least one light-sensitive layer consisting of a plurality of silver halide emulsion layers having substantially the same color sensitivity but different sensitivities. And the photosensitive layer is a unit photosensitive layer having a color sensitivity to any of blue light, green light, and red light. The arrangement is such that the red-sensitive layer, the green-sensitive layer and the blue-sensitive layer are arranged in this order from the support side. However, even if the above installation order is reversed depending on the purpose,
Further, the order of installation may be such that different photosensitive layers are sandwiched in the same color-sensitive layer. Non-photosensitive layers such as various intermediate layers may be provided between the above-described silver halide photosensitive layers and as the uppermost layer and the lowermost layer. The intermediate layer includes JP-A-61-43748 and
59-113438, 59-113440, 61-20037, 61-2
A coupler, a DIR compound or the like as described in the specification may be contained, and a color mixing inhibitor may be contained as is usually used. The plural silver halide emulsion layers constituting each unit light-sensitive layer preferably have a two-layer constitution of a high-sensitivity emulsion layer and a low-sensitivity emulsion layer as described in West German Patent No. 1,121,470 or British Patent No. 923,045. be able to. Usually, it is preferable to arrange them so that the light sensitivity decreases sequentially toward the support, and a non-photosensitive layer may be provided between the respective halogen emulsion layers. Also,
JP 57-112751, JP 62-200350, JP 62-206541
No. 62-206543, etc., a low-sensitivity emulsion layer may be provided on the side farther from the support, and a high-sensitivity emulsion layer may be provided on the side closer to the support.

As a specific example, from the side farthest from the support,
Low sensitivity blue photosensitive layer (BL) / High sensitivity blue photosensitive layer (BH) / High sensitivity green photosensitive layer (GH) / Low sensitivity green photosensitive layer (GL) / High sensitivity red photosensitive layer (RH) / Low sensitivity red photosensitive layer (RL) order, or BH / BL / GL / GH / RH / RL order, or BH / BL / GH /
It can be installed in the order of GL / RL / RH. In addition,
As described in JP-A-55-34932, the blue-sensitive layer / GH / RH / GL / RL may be arranged in this order from the side farthest from the support. In addition, JP-A-56-25738 and 62-63936
It is also possible to arrange in the order of blue-sensitive layer / GL / RL / GH / RH from the side farthest from the support, as described in the specification. Also, as described in JP-B-49-15495, the upper layer is the most sensitive silver halide emulsion layer, the middle layer is the less sensitive silver halide emulsion layer, and the lower layer is more sensitive than the middle layer. An arrangement in which a silver halide emulsion layer having a low degree of sensitivity is arranged, and three layers having different sensitivities are sequentially reduced in sensitivity toward a support, may be mentioned. Even when it is composed of three layers having different sensitivities, as described in JP-A-59-202464, a medium-sensitivity emulsion from the side remote from the support in the same color-sensitive layer. Layers / high-speed emulsion layers / low-speed emulsion layers may be arranged in this order. In addition, the layers may be arranged in the order of high-speed emulsion layer / low-speed emulsion layer / medium-speed emulsion layer, or low-speed emulsion layer / medium-speed emulsion layer / high-speed emulsion layer. Also, in the case of four or more layers, the arrangement may be changed as described above. In order to improve color reproducibility, U.S. Pat.Nos. 4,663,271 and 4,705,7
No. 44, No. 4,707,436, JP-A No. 62-160448, No. 63-
It is also preferable to dispose a donor layer (CL) having a multilayer effect, which has a spectral sensitivity distribution different from that of the main photosensitive layer such as BL, GL and RL described in 89850, adjacent to or in proximity to the main photosensitive layer.
As described above, various layer configurations and arrangements can be selected according to the purpose of each light-sensitive material.

The color light-sensitive material of the present invention contains at least one layer of silver iodide in the photographic emulsion layer. The silver iodide may be any of silver iodobromide, silver iodochloride and silver iodochlorobromide. Particularly, silver iodobromide, silver iodochloride or silver iodochlorobromide containing 0.1 to 30 mol% of silver iodide is preferable. Particularly, silver iodobromide, silver iodochloride or silver iodochlorobromide containing 1 to 25 mol% of silver iodide is preferable. The silver halide contained in the emulsion layers other than the above may be of any silver halide composition, for example, silver chloride, silver bromide, silver chlorobromide, silver iodobromide, silver iodochloride or silver iodochlorobromide. However, silver iodobromide, silver iodochloride, and silver iodochlorobromide containing silver iodide are particularly preferable.

The silver halide grains in the photographic emulsion have regular crystals such as cubes, octahedra and tetradecahedrons, and irregular crystal forms such as spheres and plates.
It may have a crystal defect such as a twin plane or a composite form thereof. The grain size of the silver halide may be fine grains of about 0.2 μm or less or large grains having a projected area diameter of up to about 10 μm, and may be a polydisperse emulsion or a monodisperse emulsion. The silver halide photographic emulsion which can be used in the present invention is, for example, Research Disclosure (RD) No. 17643 (197).
Dec. 8), pp. 22-23, "I. Emulsionprep
aration and types) ”, and No. 18716 (November 1979)
Mon), p. 648, ibid. 307105 (Nov. 1989), 863-865.
Page, and "Graphics and Chemistry of Photography" by Graphide, published by Paul Montel (P.Glafkides, Chemie et Phisique Phot
Ographique, Paul Montel, 1967), "Photoemulsion Chemistry" by Duffin, published by Focal Press (GFDuffin, Photogr
aphic Emulsion Chemistry (Focal Press, 1966)), "Production and coating of photographic emulsions" by Zelikman et al., published by Focal Press (VL Zelikman et al., Making and Coatin).
g Photographic Emulsion, Focal Press, 1964) and the like.

Monodisperse emulsions described in US Pat. Nos. 3,574,628 and 3,655,394 and British Patent 1,413,748 are also preferable. Further, tabular grains having an aspect ratio of about 3 or more can be used in the present invention. Tabular grains are described by Gatov, Photographic Science and Engineering (Gutoff, PhotographicScience
and Engineering), Vol. 14, pp. 248-257 (1970);
U.S. Pat.Nos. 4,434,226, 4,414,310, 4,433,0
It can be easily prepared by the method described in 48, 4,439,520 and British Patent 2,112,157. Particularly, it is preferable to use an emulsion having a tabularity of 50 to 25,000 as described in US Pat. No. 5,183,727. The crystal structure may be uniform, may have different halogen compositions inside and outside, may have a layered structure, and may have a different composition by epitaxial bonding. Alternatively, it may be bonded to a compound other than silver halide such as silver rhodanide and lead oxide. Also, a mixture of particles having various crystal forms may be used. The above emulsion may be either a surface latent image type which forms a latent image mainly on the surface, an internal latent image type which is formed inside the grain or a type which has a latent image both on the surface and inside, but a negative type emulsion. It is necessary to be. Among the internal latent image types, JP-A-63-
The core / shell type internal latent image type emulsion described in No. 264740 may be used. The method for preparing this core / shell type internal latent image type emulsion is described in JP-A-59-133542. The thickness of the shell of this emulsion is 3-4 depending on the development process etc.
0 nm is preferable, and 5 to 20 nm is particularly preferable.

The silver halide emulsion is usually one which has been physically ripened, chemically ripened and spectrally sensitized. Additives used in such a process are described in Research Disclosure No. 17643, No. 18716 and No. 307105, and the corresponding portions are summarized in the table below. In the light-sensitive material of the present invention, two or more kinds of emulsions having different characteristics of at least one of the grain size, grain size distribution, halogen composition, grain shape and sensitivity of the light-sensitive silver halide emulsion are mixed in the same layer. Can be used. U.S. Pat. No. 4,082,553 described above, the surface of which is covered with silver halide grains, U.S. Pat. No. 4,626,498, JP-A-59-
The grain-fogged silver halide grains and colloidal silver described in 214852 can be preferably used in the photosensitive silver halide emulsion layer and / or the substantially non-photosensitive hydrophilic colloid layer. The fogged silver halide grain inside or on the surface is a silver halide grain that enables uniform (non-imagewise) development regardless of the unexposed area and exposed area of the light-sensitive material. . A method for preparing a silver halide grain in which the inside or surface of the grain is fogged is described in U.S. Patent No. 4,626,498,
It is described in JP-A-59-214852. The silver halide forming the inner nucleus of a core / shell type silver halide grain having a fogged grain inside may have the same halogen composition or different halogen compositions. As the silver halide whose inside or surface is fogged, any of silver chloride, silver chlorobromide, silver iodobromide and silver chloroiodobromide can be used. The grain size of these fogged silver halide grains is not particularly limited, but the average grain size is preferably 0.01 to 0.75 μm, particularly preferably 0.05 to 0.6 μm. The grain shape is not particularly limited, and may be regular grains or polydisperse emulsion, but monodisperse grains may be used.
(A silver halide grain weight or number of grains of at least 95
% Having a particle size within ± 40% of the average particle size).

In the present invention, it is preferable to use a non-photosensitive fine grain silver halide. Non-photosensitive fine grain silver halide is silver halide fine grains that are not exposed during imagewise exposure to obtain a dye image and are not substantially developed in the developing process, and are preferably not fogged in advance. . The fine grain silver halide has a silver bromide content of 0 to 100 mol%, and may contain silver chloride and / or silver iodide, if necessary. Preferred is one containing 0.5 to 10 mol% of silver iodide. Fine grain silver halide has an average grain size (average value of circle equivalent diameter of projected area)
Is preferably 0.01 to 0.5 μm, more preferably 0.02 to 0.2 μm. The fine grain silver halide can be prepared by a method similar to that for ordinary photosensitive silver halide. In this case, the surface of the silver halide grain does not need to be chemically sensitized nor spectral sensitization. However, prior to adding this to the coating liquid, it is preferable to add a known stabilizer such as a triazole-based, azaindene-based, benzothiazolium-based, mercapto-based compound or zinc compound in advance. Colloidal silver can be preferably contained in this fine grain silver halide grain-containing layer.

The light-sensitive material of the present invention preferably contains colloidal silver between the support and the emulsion layer as an antihalation layer. As colloidal silver, Japanese Patent Laid-Open No. 5-13
Thickness 0.02, as described in Japanese Patent No. 4358.
It is preferable to use colloidal silver having a size of μm or less. The colloidal silver preferably has an edge length not less than twice its thickness, an average edge length of 0.04 μm or less, and a thickness of 0.005 to 0.02 μm.
Further, it is more preferable that the average edge length is 0.02 to 0.04 μm and the thickness is 0.005 to 0.012 μm. The coating amount of colloidal silver for the antihalation layer is 1 m
200 mg or less per ^{2 and} more preferably 50 to 100 mg. Coated silver amount of the light-sensitive material of the present invention is preferably 6.0 g / m ² or less, 4.5 g / m ² or less is most preferred.

The dry film thickness of the photographic material, that is, the dry film thickness of the support and all the constituent layers except the undercoat layer and the back layer of the support is from 12.0 to 20.0 μm. More preferably 1
2.0 to 17.0 μ is preferable. More preferably 13.
It is 0 to 16.0 μ.

The film thickness of the photosensitive material is 2 for the photosensitive material to be measured.
The photosensitive material was stored under the conditions of 5 ° C. and 50% RH for 7 days after the preparation. First, the total thickness of the photosensitive material was measured, and then the coating layer on the support was removed, and then the thickness was measured again. The thickness of the entire coating layer excluding the support of the photosensitive material is defined by the difference. The thickness is measured by, for example, a film thickness measuring device (Anritus Electric Co.
Ltd., K-402B Stand.). The coating layer on the support can be removed by using an aqueous solution of sodium hypozincate. Also,
It is also possible to use a scanning electron microscope to take a photograph of a cross section of the above-mentioned light-sensitive material (the magnification is preferably 3,000 times or more) to measure the total thickness on the support.

Swelling rate of the light-sensitive material of the present invention [{(2
5 ° C., the equilibrium swollen film thickness -25 ° C. in in H ₂ O, 55% RH
Dry total film thickness at 25/25 ° C. and 55% RH} × 100] is preferably 50 to 200%, 70 to 1
50% is more preferable. If the swelling ratio deviates from the above value, the residual amount of the color developing agent increases, and the photographic performance,
Image quality such as desilvering and film physical properties such as film strength are adversely affected. Further, the film swelling speed of the light-sensitive material in the present invention is 90% of the maximum swollen film thickness reached when processed in a color developing solution (38 ° C., 3 minutes 15 seconds), and the saturated swollen film thickness is defined as 1 / When the time required to reach the film thickness of 2 is defined as the swelling speed T1 / 2, T1 / 2 is preferably 15 seconds or less. It is more preferably 9 seconds or less.

Known photographic additives that can be used in the present invention are also described in the above-mentioned three Research Disclosures, and the relevant portions are shown in the following table. Types of additives RD17643 RD18716 RD307105 1. Chemical sensitizer, page 23, page 648, right column, page 866 2. Sensitivity enhancer, page 648, right column 3. Spectral sensitizer, page 23 to 24, page 648, right column 866 to 868 Color sensitizer: page 649, right column 4. Whitening agent: page 24, page 647, right column 868, page 5, fogging prevention, page 24-25, page 649, right column, page 868-870, stabilizer, light absorber, 25- Page 26 Page 649 Right column Page 873 Filter ~ Page 650 Left column Dye, UV absorber 7. Stain 25 Page Right column 650 Page Left column 872 Inhibitor ~ Right column 8. Dye image Page 25 650 Page Left column 872 Stabilizer 9. Hardener 26 pages 651 left column 874 to 875 pages 10. Binder page 26 651 pages left column 873 to 874 pages 11. Plasticizer, page 27 650 pages right column 876 lubricants 12. Coating aids , Pages 26 to 27, page 650, right column, pages 875 to 876, surfactant 13. static, page 27, page 650, right column, pages 876 to 877, inhibitors 14. matting agents, pages 878 to 879

Further, in order to prevent deterioration of photographic performance due to formaldehyde gas, it is preferable to add to the light-sensitive material a compound capable of immobilizing by reacting with formaldehyde described in US Pat. Nos. 4,411,987 and 4,435,503. . In the light-sensitive material of the present invention, US Pat.
It is preferable that the mercapto compounds described in JP-A Nos. 0,454, 4,788,132, JP-A-62-18539, and JP-A 1-283551 are contained. The light-sensitive material of the present invention is described in JP-A 1-10
It is preferable to include a compound described in No. 6052, which releases a fogging agent, a development accelerator, a silver halide solvent or a precursor thereof regardless of the amount of developed silver produced by the development processing. International publication WO
88/04794, Dyes dispersed by the method described in JP-A-1-502912 or EP 317,308A, U.S. Pat.
And the dyes described in JP-A 1-259358 are preferably contained.

Various color couplers can be used in the color light-sensitive material applied to the processing according to the present invention. Specific examples thereof are RD No. 17643, VII-C.
To G, the same No. 307105, VII-C to G, JP-A-62-215272, JP-A-3-338.
No. 47, No. 2-333144, European Patent Publication No. 4479.
69A, 482552A and the like. Yellow couplers include, for example, US Pat.
No. 3,501, No. 4,022,620, No. 4,3
No. 26,024, No. 4,401,752, No. 4,
No. 248,961, Japanese Patent Publication No. 58-10739, British Patent Nos. 1,425,020 and 1,476,760.
U.S. Pat. Nos. 3,973,968 and 4,31
No. 4,023, No. 4,511,649, No. 5,1
18,599, European Patents 249,473A, 0,447,969, JP-A-63-23145, JP-A-63-123047, JP-A-1-250944, 1-213648 and the like. They can be used in combination as long as they do not impair the effects of the present invention.

Particularly preferred yellow couplers are yellow couplers represented by the general formula (Y) described in JP-A-2-139544, page 18, upper left column to page 22, lower left column, Japanese Patent Application No. 3-179042, European Patent. Published 044796
No. 9, an acylacetamide yellow coupler characterized by an acyl group, and a general formula (Cp-
2) Yellow coupler.

As the magenta coupler, 5-pyrazolone compounds and pyrazoloazole compounds are preferable, and US Pat. Nos. 4,310,619 and 4,351,897 are preferred.
No. 3,073,636; U.S. Pat.
No. 1,432, No. 3,725,067, Research
Disclosure Magazine No. 24220 (6 June 1984)
JP, 60-33552, Research Disclosure No. 24230 (June 1984), JP, 60-43659, 61-72238, 60.
-35730, 55-118034, 60-1
More preferred are those described in US Pat. No. 8,5951, U.S. Pat. Nos. 4,500,630, 4,540,654, 4,556,630, and International Publication WO88 / 04795. Particularly preferred magenta couplers are pyrazoloazole-based magenta couplers of the general formula (I) on page 3, lower right column to page 10, lower right column of JP-A-2-139544 and JP-A-2-135944. Examples include 5-pyrazolone magenta couplers represented by the general formula (M-1) on page 17, lower left column to page 21, upper left column. Most preferable are the above-mentioned pyrazoloazole-based magenta couplers.

Examples of cyan couplers include phenol-type and naphthol-type couplers, and US Pat.
No. 52,212, No. 4,146,396, No. 4,
Nos. 228,233, 4,296,200, 2,369,929, 2,801,171, 2,772,162, 2,895,826,
No. 3,772,002, No. 3,758,308
No. 4,334,011, No. 4,327,17
3, West German Patent Publication No. 3,329,729, European Patent Nos. 0,121,365A and 0,249,453A.
U.S. Pat. Nos. 3,446,622 and 4,33.
No. 3,999, No. 4,775,616, No. 4,4
No. 51,559, No. 4,427,767, No. 4,
Those described in 690,889, 4,254,212, 4,296,199, JP-A-61-42658 and the like are preferable. Furthermore, JP-A-64-553
No. 64, No. 554, No. 64-555, No. 64-5
No. 56, pyrazoloazole couplers, and European Patent Publication Nos. 0,488,248 and 0,491,197.
No. 4,456,226A, a pyrrolo imidazole coupler described in EP-A-0,456,226A, a pyrazolopyrimidine coupler described in JP-A-64-46753, and a U.S. Pat. No. 4,818,672.
No. 2, JP-A-2-33144, imidazole couplers, JP-A-4-204730, pyrrolotriazine couplers, JP-A-64-32260, cyclic active methylene cyan couplers, JP-A-1- 183
No. 658, No. 2-262655, No. 2-85851.
The couplers described in JP-A No. 3-48243 can also be used.

Typical examples of polymerized dye-forming couplers are shown in US Pat. Nos. 3,451,820 and 4,08.
No. 0,211, No. 4,367,282, No. 4,4
09,320, 4,576,910, British Patent 2,102,137, European Patent 341,188A.
No. etc. Examples of couplers in which the color forming dye has an appropriate diffusibility include US Pat. No. 4,366,237.
No., British Patent No. 2,125,570, European Patent No. 9
No. 6,570, West German Patent (Publication) No. 3,234,533
Those described in the above item are preferred. Couplers that release a photographically useful residue upon coupling can also be used in the present invention. DIR couplers releasing a development inhibitor are disclosed in the above-mentioned RD magazine No. 17643, VII to F, JP-A Nos. 57-151944 and 57-15423.
No. 4, No. 60-184248, No. 63-37346.
U.S. Pat. Nos. 4,248,962 and 4,782.
Those described in No. 012 are preferable. Examples of couplers that release a nucleating agent or a development accelerator imagewise during development include British Patents 2,097,140 and 2,131,
188, JP-A-59-157638 and JP-A-59-17.
Those described in No. 0840 are preferable.

Other couplers that can be used in the color photographic element of the present invention are described in US Pat.
Competitive couplers described in U.S. Pat.
No. 3,472, No. 4,338,393, No. 4,31
Multiequivalent couplers described in JP-A No. 0,618, JP-A-60-
DI described in No. 185950, No. 62-24252, etc.
R redox compound-releasing coupler, DIR coupler-releasing coupler, DIR coupler-releasing redox compound or DIR redox-releasing redox compound, coupler releasing a dye that recolors after release described in European Patent 173,302A, RD magazine No. 11449. , The same magazine No. 24
No. 241, a bleaching accelerator releasing coupler described in JP-A No. 61-201247, a ligand-releasing coupler described in US Pat. No. 4,553,477, and the like, JP-A-63-757.
Examples thereof include a coupler releasing a leuco dye described in US Pat. No. 47, and a coupler releasing a fluorescent dye described in US Pat. No. 4,774,181.

The standard amount of the coupler used is in the range of 0.001 to 1 mol per mol of the photosensitive silver halide,
Preferably 0.01 to 0.5 mol for the yellow coupler, 0.003 to 0.3 mol for the magenta coupler,
For cyan couplers, it is 0.002-0.3 mol.

The coupler used in the present invention can be introduced into the light-sensitive material by various known dispersion methods. Examples of the high boiling point solvent used in the oil-in-water dispersion method are described in US Pat. No. 2,322,027. Specific examples of the high-boiling organic solvent having a boiling point of 175 ° C. or higher at atmospheric pressure used in the oil-in-water dispersion method include phthalic acid esters (dibutyl phthalate, dicyclohexyl phthalate, di-2-ethylhexyl phthalate, decyl phthalate, bis phthalate (2,4-di-t-amylphenyl) phthalate, bis (2,4-di-t-amylphenyl)
Isophthalate, bis (1,1-diethylpropyl) phthalate, etc.), phosphoric acid or phosphonic acid esters (triphenyl phosphate, tricresyl phosphate,
2-ethylhexyl diphenyl phosphate, tricyclohexyl phosphate, tri-2-ethylhexyl phosphate, tridodecyl phosphate, tributoxyethyl phosphate, trichloropropyl phosphate, di
-2-Ethylhexylphenylphosphonate, etc., Benzoic acid esters (2-ethylhexylbenzoate, dodecylbenzoate, 2-ethylhexyl-p-hydroxybenzoate, etc.), Amides (N, N-diethyldodecane amide, N, N-diethyllauryl) Amides, N-tetradecylpyrrolidone, etc.), alcohols or phenols (isostearyl alcohol, 2,4-di-tert-amylphenol, etc.), aliphatic carboxylic acid esters (bis (2-ethylhexyl) sebacate, dioctylazese) Rate, glycerol tributyrate, isostearyl lactate,
Trioctyl citrate, etc., aniline derivatives (N, N-
Dibutyl-2-butoxy-5-tert-octylaniline, etc.), hydrocarbons (paraffin, dodecylbenzene, diisopropylnaphthalene, etc.) and the like. The auxiliary solvent has a boiling point of about 30 ° C or higher, preferably 50 ° C.
Organic solvents above 160 ° C can be used. Typical examples are ethyl acetate, butyl acetate, ethyl propionate,
Methyl ethyl ketone, cyclohexanone, 2-ethoxyethyl acetate, dimethylformamide and the like can be mentioned. The steps and effects of the latex dispersion method and specific examples of the latex for impregnation are described in US Pat. No. 4,199,363, West German Patent Application (OLS) Nos. 2,541,274 and 2,541,230.

In the light-sensitive material of the present invention, a dye preservability improving compound as described in European Patent EP 0,277,589A2 can be used together with a coupler. Particularly, it is preferable in combination with a pyrazoloazole-based magenta coupler. Various anti-fading agents can be used in combination with the light-sensitive material of the present invention. Organic fading inhibitors include hydroquinones, 6-hydroxychromans, 5-hydroxycoumarans, spirochromans, p-alkoxyphenols, hindered phenols centering on bisphenols, gallic acid derivatives, methylenedioxybenzene. Typical examples thereof include ethers or ester derivatives in which the phenolic hydroxyl groups of these compounds, aminophenols, hindered amines and these compounds are silylated or alkylated.

The light-sensitive material of the present invention contains a hydroquinone derivative, an aminophenol derivative,
It may contain a gallic acid derivative, an ascorbic acid derivative or the like. In order to prevent the cyan dye image from being deteriorated by heat and especially light, the benzotriazole-based ultraviolet absorbers described in, for example, U.S. Pat. No. 3,533,794 are provided in the cyan color forming layer and the layers on both sides adjacent thereto. It is more effective to introduce. In the color light-sensitive material of the present invention, phenethyl alcohol or JP-A-63-257747 is used.
No. 62-272248, and JP-A No. 1-80941.
Various antiseptics such as 1,2-benzisothiazolin-3-one, n-butyl p-hydroxybenzoate, phenol, 4-chloro-3,5-dimethylphenol, 2-phenoxyethanol, 2- (4-thiazolyl) benzimidazole It is preferable to add an agent or an antifungal agent.

The silver halide color light-sensitive material of the present invention may contain a color developing agent for the purpose of simplifying and accelerating the processing. For incorporation, it is preferable to use various precursors of color developing agents. For example, indoaniline compounds described in U.S. Pat.
3,342,599, Research Disclosure No.14,85
0 and the Schiff base type compound described in No. 15,159, the same 13,
Aldol compounds described in US Pat. No. 3,719,492
The metal salt complexes described in JP-A No. 53-135628 and the urethane compounds described in JP-A No. 53-135628 can be mentioned. The silver halide color light-sensitive material of the present invention may contain various 1-phenyl-3-pyrazolidones in order to accelerate color development, if necessary. A typical compound is described in JP-A-56-64339.
No. 57-144547 and No. 58-115438.

Suitable supports which can be used in the light-sensitive material of the present invention are described in, for example, RD. No.17643, page 28, same
No. 18716, page 647, right column to page 648, left column, and ibid. No. 307
105, p. 879.

In the silver halide color photographic light-sensitive material used in the present invention, a magnetic recording layer can be provided on the side opposite to the side coated with the silver halide emulsion layer with the support interposed therebetween. The ferromagnetic fine powder used in the magnetic recording layer in the present invention includes ferromagnetic iron oxide fine powder, Co-doped ferromagnetic iron oxide fine powder, ferromagnetic chromium dioxide fine powder, ferromagnetic metal powder,
Ferromagnetic alloy powder, barium ferrite, etc. can be used. As an example of the ferromagnetic alloy powder, the metal content is 75 wt%
80% by weight or more of the metal content is at least one kind of ferromagnetic metal or alloy (Fe, Co, Ni, Fe).
-Co, Fe-Ni, Co-Ni, Co-Fe-Ni, etc.) and other components (A
l, Si, S, Sc, Ti, V, Cr, Mn, Cu, Z
n, Y, Mo, Rh, Pd, Ag, Sn, Sb, B, B
a, Ta, W, Re, Au, Hg, Pb, P, La, C
e, Pr, Nb, Te, Bi and the like). Further, the ferromagnetic metal component may contain a small amount of water, hydroxide or oxide. The method for producing these ferromagnetic powders is known, and the ferromagnetic powder used in the present invention can also be produced according to known methods.

The shape and size of the ferromagnetic powder can be widely used without any particular limitation. As the shape, needle shape, rice grain,
It may have a spherical shape, a cubic shape, a plate shape, or the like, but a needle shape or a plate shape is preferable in terms of electromagnetic conversion characteristics. The crystallite size and non-surface area are not particularly limited, but the crystallite size is 400 Å or less, S
_{The BET} is preferably 20 m ² / g or more, and more preferably 30 m ² / g or more. The pH and surface treatment of the ferromagnetic powder can be used without particular limitation (the surface may be treated with a substance containing an element such as titanium, silicon or aluminum,
Carboxylic acid, sulfonic acid, sulfuric ester, phosphonic acid,
It may be treated with an organic compound such as an adsorptive compound having a nitrogen-containing heterocycle such as a phosphoric acid ester or benzotriazole). The preferred pH range is 5-10. In the case of ferromagnetic iron oxide fine powder, it can be used without any particular limitation on the ratio of divalent iron / trivalent iron. These magnetic recording layers are described in JP-A-47-32812 and 53.
-109604. The content of ferromagnetic fine powder per 1 m ^{2 of the} transparent support is 4 × 10 ⁻⁴ g to 3 g,
Preferably 10 ⁻³ g to 1 g, more preferably 4 × 10 ⁻³
g to 4 × 10 ⁻¹ g.

The binder of the magnetic recording layer used in the present invention is a known thermoplastic resin, thermosetting resin, radiation curable resin, or the like which has been conventionally used as a binder for magnetic recording media.
Reactive resins and mixtures thereof can be used. The Tg of the resin is −40 ° C. to 150 ° C., and the weight average molecular weight is 10,000 to 300,000, preferably 10,000 to 100,000.
Examples of the thermoplastic resin include vinyl chloride / vinyl acetate copolymer, vinyl chloride, vinyl acetate and vinyl alcohol,
Copolymers with maleic acid and / or acrylic acid, vinyl chloride / vinylidene chloride copolymers, vinyl chloride / acrylonitrile copolymers, vinyl copolymers such as ethylene / vinyl acetate copolymers, nitrocellulose, cellulose acetate Cellulose derivatives such as propionate and cellulose acetate butyrate resin, acrylic resin,
Polyvinyl acetal resin, polyvinyl butyral resin, polyester polyurethane resin, polyether polyurethane resin, polycarbonate polyurethane resin, polyester resin, polyether resin, polyamide resin,
Amino resin, styrene butadiene resin, rubber resin such as butadiene acrylonitrile resin, silicone resin,
Fluorine-based resins may be mentioned. Of these, vinyl chloride resins are preferred because of their high dispersibility in ferromagnetic fine powder. As the radiation curable resin, the above-mentioned thermoplastic resin to which a group having a carbon-carbon unsaturated bond is bonded as a radiation curable functional group is used. Preferred functional groups include an acryloyl group and a methacryloyl group. In the binder molecules listed above, polar groups (epoxy group, -CO _{2
M, -OH, -NR 2, -NR} 3 X, -SO 3 M, -OS
_{O 3 M, -PO 3 M 2} , -OPO 3 M 2, wherein M is hydrogen,
It is an alkali metal or ammonium, and when there are a plurality of M's in one group, they may be different from each other. R
Is hydrogen or an alkyl group, and X is an anion)
May be introduced. The polymer binders listed above are used alone or in a mixture of several kinds, and can be cured by adding a known isocyanate-based crosslinking agent and / or a radiation-curable vinyl-based monomer.

Further, a hydrophilic binder may be used in the magnetic recording layer of the present invention. The hydrophilic binder used is Research Disclosure (R
D) No. 17643, page 26, and the same No. 1871
6, pages 651, and water-soluble polymers, cellulose esters, latex polymers, water-soluble polymer esters, etc. are exemplified. Water-soluble polymers include gelatin, gelatin derivatives, casein, agar, sodium alginate, starch, polyvinyl alcohol, polyacrylic acid copolymers, maleic anhydride copolymers, etc., and cellulose esters such as carboxymethyl cellulose and hydroxyethyl cellulose. Is. Examples of the latex polymer include vinyl chloride-containing copolymers, vinylidene chloride-containing copolymers, acrylic acid ester-containing copolymers, vinyl acetate-containing copolymers and butadiene-containing copolymers. Of these, gelatin is the most preferable. Gelatin is a so-called alkali-processed (lime-processed) gelatin that is immersed in an alkali bath before extraction of gelatin, an acid-processed gelatin that is immersed in an acid bath, and a double-immersed gelatin that has been subjected to both of these processes in the manufacturing process. Any of gelatin may be used. If necessary, a part thereof may be colloidal albumin, casein, carboxymethyl cellulose, cellulose derivative such as hydroxyethyl cellulose, agar, sodium alginate, starch derivative, sugar derivative such as dextran, synthetic hydrophilic colloid such as polyvinyl alcohol, poly N- Vinylpyrrolidone, polyacrylic acid copolymer, polyacrylamide or derivatives thereof, partial hydrolysates, gelatin derivatives and the like may be used in combination with gelatin.

It is preferable to harden the magnetic recording layer containing gelatin, and as a hardener that can be used in the magnetic recording layer,
For example, aldehyde compounds such as formaldehyde and glutaraldehyde, ketone compounds such as diacetyl and cyclopentanedione, bis (2-chloroethylurea), 2-hydroxy-4,6-dichloro-1,3,3.
5-triazine and others U.S. Pat. No. 3,288,77
5, 2,732,303, British Patent 974,7
23, 1,167,207 and the like, compounds having a reactive halogen, divinyl sulfone, 5-acetyl-1,3-diacryloylhexahydro-1,3,5-triazine, and others. US Patent No. 3,
Compounds having a reactive olefin described in 635,718, 3,232,763, British Patent 994,869, etc., N-hydroxymethylphthalimide, and other U.S. Pat. No. 2,732,316. Issue 2
N-methylol compounds described in US Pat. No. 586,168, isocyanates described in US Pat. No. 3,103,437, and US Pat. No. 3,017,28.
0, 2,983,611 and the like, aziridine compounds, US Pat. Nos. 2,725,294 and 2,725,295 and the like, acid derivatives,
Examples thereof include epoxy compounds described in US Pat. No. 3,091,537 and halogen carboxaldehydes such as mucochloric acid. Alternatively, as an inorganic compound hardening agent, chrome alum, zirconium sulfate, JP-B-56-12853, JP-A-58-32699.
No., Belgian Patent No. 825,726, JP-A-60-22
5148, JP-A-51-126125, JP-B-58
Examples include carboxyl group-activating type hardeners described in JP-A-50699, JP-A-52-54427, US Pat. No. 3,321,313 and the like.

The amount of the hardener used is usually 0.01 to 30% by weight, preferably 0.05 to 20% by weight based on dry gelatin.
% By weight. The thickness of the magnetic recording layer is 0.1 μm to 10 μm
m, preferably 0.2 μm to 5 μm, more preferably 0.5 μm to 3 μm.

It is preferable that the magnetic recording layer in the present invention is substantially transparent and is provided on the back surface of the photosensitive material almost all over. The magnetic recording layer can be provided by coating, printing or adhering on the back surface of the transparent support. It is also preferable to co-cast a solution of a polymer in which magnetized particles are dispersed and a solution of a polymer for preparing a transparent support to prepare a transparent support having a magnetic recording layer. In this case, it is preferable that the compositions of the two types of polymers are substantially the same. The magnetic recording layer may have functions such as lubricity improvement, curl control, antistatic and adhesion prevention, or may be provided with another functional layer to impart these functions.
If necessary, a protective layer adjacent to the magnetic recording layer may be provided to improve the scratch resistance. The back surface of the transparent support having a magnetic recording layer can be subjected to calendering to improve smoothness and improve the S / N ratio of magnetic signals. In this case, it is preferable to apply the photosensitive layer on the transparent support after the calendering treatment.

Next, the support of the light-sensitive material of the present invention will be described. The material of the support of the light-sensitive material used in the present invention is not particularly limited, but it is disclosed in JP-A-4-124.
Various plastic films described in No. 636, page 5, upper right column, line 1 to page 6, upper right column, line 5 can be used, and preferred are cellulose derivatives (for example, diacetyl,
Triacetyl, propionyl, butanoyl, acetylpropionyl-acetate, etc., polyamides, polycarbonates described in US Pat. No. 3,023,101, polyesters described in Japanese Patent Publication No. 4040414 and the like (eg polyethylene terephthalate, poly-1,4). -Cyclohexane dimethylene terephthalate, polyethylene naphthalate, etc.), polystyrene, polypropylene, polyethylene, polysulfone, polyarylate, polyetherimide, etc., and particularly preferred are triacetyl cellulose, polyethylene terephthalate, and polyethylene naphthalate. Polar groups in these films _{(epoxy, -COO 2 M, -OH, -NR} 2, -NR 3
_{X, -SO 3 M, -OSO 3} M, -PO 3 M 2, -OP
₃ M ₂ , provided that M is hydrogen, an alcar metal or ammonia, R is hydrogen or an alkyl group having 1 to 20 carbon atoms, and X is an anion). Particularly preferred supports are polyethylene terephthalate, functional materials, polyethylene naphthalate and polyarylate described in February 1991, pp. 20-28, and copolymers and polymer blends using these as raw materials. These supports are preferably used after being heat-set after biaxial stretching, and may be heat-relaxed if necessary. In addition, these supports have previously had their Tg in order to reduce their curl.
The heat treatment is preferably performed at the following temperature. For example, in the case of polyethylene naphthalate, Tg is about 120 ° C. Therefore, it is preferable to perform heat treatment at a temperature of 119 ° C. or lower for 0.2 to 48 hours, more preferably 115 ° C.
That is, heat treatment is performed for 24 hours. In particular, in order to perform the heat treatment in a short time, it is preferable to raise the temperature once to Tg or more and gradually cool it in the vicinity of Tg because the efficiency is greatly improved. In the case of polyethylene naphthalate, the heat treatment time can be remarkably shortened by once maintaining the temperature between 130 ° C. and 200 ° C., cooling to 125 ° C., and then gradually cooling to 100 ° C. for 40 minutes. When the support subjected to such heat treatment is measured by a differential thermal analyzer, an endothermic peak appears in the vicinity of Tg, and the larger the endothermic peak, the more the winding tendency is less likely to occur, and 100 mcal / g or more, more preferably 200 mcal / g. It is preferable that the heat treatment is performed so that the amount becomes g or more.

These supports of the present invention have a thickness of 6
0 μm or more and 300 μm, more preferably 70 μm
Is about 200 μm. When the thickness is less than 60 μm, the toy-like curl generated by the shrinkage stress of the emulsion layer during drying becomes remarkable and the flatness is easily deteriorated. A plasticizer may be added to these supports for the purpose of imparting flexibility and the like. Particularly in the case of cellulose ester, a plasticizer-containing material such as triphenyl phosphate, biphenyl diphenyl phosphate, dimethyl ethyl phosphate, etc. is preferable. Chemical treatment, mechanical treatment, corona discharge treatment, flame treatment for firmly adhering a photographic layer (for example, a photosensitive silver halide emulsion layer, an intermediate layer, a filter layer or a layer having conductivity) on these supports. , UV treatment, high frequency treatment, glow discharge treatment, active plasma treatment, laser treatment, mixed acid treatment, ozone oxidation treatment, etc., may be followed by direct photographic emulsion coating to obtain adhesive strength. Alternatively, a method may be used in which after these surface treatments are carried out once or without a surface treatment, an undercoat layer is provided and a photographic emulsion layer is coated thereon. Of these, corona discharge treatment, flame treatment, ultraviolet treatment, and glow discharge treatment are particularly preferable, and the treatment is performed at a high temperature (for example, 10
0 ° C or higher, preferably 200 ° C, and preferably several seconds to several minutes). For the cellulose derivative, a single layer of gelatin solution dispersed in a methylene chloride / ketone / alcohol mixed organic solvent is applied to form an undercoat layer. Gelatin hardeners include chromium salts (chrome alum, etc.), aldehydes (formaldehyde,
Glutaraldehyde, etc., isocyanates, active halogen compounds (2,4-dichloro-6-hydroxy-
s-triazine), epichlorohydridone resin, vinyl sulfoalkyl-based curing agent, and the like. Various additives may be contained in these undercoat liquids, if necessary. For example, surfactants, antistatic agents, antihalation agents, coloring dyes, pigments, coating aids, antifoggants and the like. When the undercoating liquid is used, an etching agent such as resorcin, chloral hydrate, chlorophenol and the like can be contained in the undercoating liquid.

The light-sensitive material of the present invention preferably has a layer having conductivity, and the conductivity thereof has an electric resistance of 10 ¹² Ω / cm (25 ° C., 10% R at 25 ° C.) before and after development processing.
H) or less is preferable. The electric resistance of the light-sensitive material of the present invention when a conductive layer is not provided is 10 ¹⁵ to 10 ¹⁶ Ω / cm (25 ° C., 10% RH).
It is a degree. The conductive material used preferably is a crystalline metal oxide particle, and those containing oxygen vacancies and those containing a small amount of a foreign atom forming a donor with respect to the metal oxide used are generally conductive. In particular, the latter is particularly preferable because it does not give fog to the silver halide emulsion. ZnO as an example of a metal oxide,
TiO ₂ , SnO ₂ , Al ₂ O ₃ , In ₂ O ₃ , SiO ₂ , M
gO, BaO, MoO ₃ , V ₂ O _{5 and the} like, or composite oxides thereof are preferable, and ZnO, TiO ₂ and SnO ₂ are particularly preferable. Examples of containing different kinds of atoms include, for example, addition of Al, In, etc. to ZnO and S to SnO ₂ .
It is effective to add b, Nb, a halogen element, or the like, and to TiO ₂ , add Nb, Ta, or the like. The addition amount of these heteroatoms is preferably in the range of 0.01 mol% to 30 mol%, and particularly preferably 0.1 mol% to 10 mol%. Furthermore, in order to improve the dispersibility and transparency of the fine particles, a silicon compound may be added during the production of the fine particles. These metal oxide fine particles have conductivity, and their volume resistivity is 10 ⁷ Ω / cm or less, particularly 10 ⁵ Ω / cm or less. The lower limit of the volume resistivity is preferably 10 ⁻⁴ Ω
/ Cm. Regarding these oxides, JP-A-5
6-143431, 56-120519, 58
-62647 and the like.

Further, as described in JP-B-59-6235, a conductive material in which the above-mentioned metal oxide is attached to other crystalline metal oxide particles or fibrous material (for example, titanium oxide) is used. May be. The particle size that can be used is preferably 1 μm or less, but when it is 0.5 μm or less, stability after dispersion is good and it is easy to use. Further, in order to make the light scattering property as small as possible, it is very preferable to use conductive particles of 0.3 μm or less because a transparent photosensitive material can be formed. When the conductive material is needle-like or fibrous, the length is preferably 30 μm or less and the diameter is 1 μm or less,
Particularly preferred is a length of 10 μm or less and a diameter of 0.3 μm
And the length / diameter ratio is 3 or more.

These conductive metal oxides may be applied from a coating solution without a binder, and in that case, it is preferable to further apply a binder thereon.
It is further preferred that the metal oxide is coated with a binder. The binder is not particularly limited, but the binder used in the magnetic layer described above may be used. For example, a water-soluble binder such as gelatin, dextran, polyacrylamide, starch, or polyvinyl alcohol may be used, or a poly (meta) may be used. ) Acrylic ester, polyvinyl acetate, polyurethane, polyvinyl chloride, polyvinylidene chloride, styrene / butadiene copolymer, polystyrene, polyester, polyethylene,
Synthetic polymer binders such as polyethylene oxide, polypropylene and polycarbonate may be used in the organic solvent, and further these polymer binders may be used in the form of an aqueous dispersion. Further, these metal oxides may be used as a mixture of spherical and fibrous ones. In the present invention, the content of metal oxide is 0.0005 to 1 g
/ M ² is preferable, more preferably 0.0009 to 0.5
g / m ^2, particularly preferably 0.0012~0.3g / m ^2.

Further, a heat-resistant agent, a weather-resistant agent, inorganic particles, a water-soluble resin, an emulsion, etc. may be added to the layer made of a metal oxide for matting and improving the quality of the film, as long as the effect of the present invention is not impaired. good. For example, inorganic fine particles may be added to the layer made of a metal oxide. Examples of the inorganic fine particles to be added include silica, colloidal silica, alumina, alumina sol, kaolin, talc, mica, calcium carbonate and the like. The fine particles have an average particle size of 0.01 to
10 μm is preferable, and more preferably 0.01 to 5 μm.
m, 0.05 to 10 by weight ratio with respect to the solid content in the coating agent
Parts are preferred, and particularly preferred is 0.1 to 5 parts.

The additive layer of the conductive metal oxide used in the present invention is not particularly limited. Can be mentioned. Of these, preferred are a protective layer, an intermediate layer, an antihalation layer, an undercoat layer, a back layer, and a back protective layer,
More preferred are an undercoat layer, a back layer, an intermediate layer and an antihalation layer. More specifically, it is particularly preferable to add a conductive material to the back layer (in particular, the back first layer closest to the support). The light-sensitive material used in the present invention is disclosed in JIII Journal of Technical Disclosure No. 94-6023 (1994.3.
15 issue), the support is the material, heat treatment, surface treatment, and undercoat described in the above items 1 to 6, and the antistatic agent is the one described in item 7. preferable. In addition, the cartridge that stores the photosensitive material is the first
No. 9 and U.S. Pat. No. 4,834,306 are preferable, and those coated with the magnetic recording layer described in JP-A-4-124634 are also preferably used.

In addition, the contents described in JP-A-4-62543, page 6, upper right column, line 17 to page 10, upper right column, line 17 can be preferably applied to the light-sensitive material used in the present invention.

When the light-sensitive material according to the present invention is used as a color negative film, the package (patrone) for accommodating the color negative film may be any existing or known one, but especially US Pat. No. 4,834,34.
306, FIG. 1-FIG. 3 and U.S. Pat. No. 4,846,418, FIG. 1-F
IG. Those described in 3 are preferable.

The format of the color negative film used in the present invention is based on the Japanese Industrial Standard "JIS.K-7519".
(1982) ”, the 135 type,
In addition to the format described in -287040, any known format can be used. The present invention can be applied to various color light-sensitive materials. Typical examples include color negative films for general use or movies, color reversal films for slides or televisions, color papers, color positive films and color reversal papers.

The light-sensitive material of the present invention is described in Japanese Patent Publication No. 2-3261.
It is also effective when applied to the lens-fitted film unit described in No. 5, No. 3-39784, etc.

The following are examples of automatic processors that can perform the processing of the present invention. Fuji Photo Film Co., Ltd. FP560BAL, FP360BAL, FP92
0AL, FP900AL, FP550B, FP350,
FP230B, FNCP900III, FNCP600I
I, FNCP300. For details of the above-mentioned automatic processor (processor), refer to the attached manuals such as instruction manuals (for managers / operators), service manuals,
It is described in the parts list. The treatment agent applicable to the present invention may be supplied as a concentrated liquid having a single or plural parts, or may be supplied in the form of powder, tablets, granules, pastes and the like. Further, the liquid may be supplied in a use liquid state, and may be an arbitrary combination of a concentrated liquid, a powder, tablets, granules, a paste and a use liquid. For a single concentrate,
It is diluted and used as a replenisher. In this case, it is preferable to automatically dilute the concentrated liquid in the developing machine with water in the replenisher tank. It is preferable to use the water in the wash water replenishment tank as this water. Alternatively, the concentrated liquid may be directly replenished to the treatment tank, and water corresponding to the dilution rate may be directly replenished to the treatment tank. Especially, it is preferable in a compact developing machine having no replenishing tank. The same applies to the concentrated solution having a plurality of parts, and it is preferable to automatically dilute the concentrated solution in the replenisher tank with water by setting the concentrated solution in the developing machine. It is preferable to use the water in the wash water replenishment tank as this water. Further, the treatment tank may be directly replenished for each part, and water corresponding to the dilution rate may be directly replenished to the treatment tank. In addition, in the case of powders, tablets, granules, and paste-like treatment agents, as well as directly adding the chemicals to the treatment tank,
It is also preferable to add water corresponding to the dilution rate to the treatment tank.
It is also preferable that the solution is automatically dissolved and diluted in the replenishment tank and used as a replenisher. In the present invention, the replenishment amount means the total amount of the liquid replenished per unit area (for example, 1 m ² ) of the light-sensitive material, and when the concentrated liquid (the total amount in the case of plural parts) and water are replenished separately. Means the total volume of the powder, tablets, granules, paste-like treatment agent and water when mixed and dissolved.

Next, the processing liquid container used in the present invention will be described. As a conventional processing liquid container, high density polyethylene (HDPE), polyvinyl chloride resin (P
VC), polyethylene terephthalate (PET), etc. 1
A rigid container using a layer material or a multilayer material such as nylon / polyethylene (NY / PE) can be used. Further, it is possible to use a liquid container which has flexibility so that it is easy to reduce the volume of the container, that is, to reduce the required space after the contents are discharged and emptied. In the present invention, it is preferable to use the flexible container. As a specific example of the flexible container, a liquid container that is opened and closed by a lid member having a hard mouth protruding upward from a flexible container body,
The container body and the mouth are integrally molded, and the container body has a bellows part at least in the height direction (FIG. 1).
Can be raised.

The flexible container having the bellows portion will be described below. The container shape has a bellows portion, and has a horizontal cross section of a square shape, for example, a substantially square shape (FIG. 1), a substantially hexagonal shape, a substantially octagonal shape, a round shape (FIG. 2), an oval shape, or the like. The substantially square shape or the substantially hexagonal shape is preferable in that the required space is reduced in the presence of the contents. As for the number of bellows portions (uneven portions), the number of convex portions is preferably 2 to 20, more preferably 3 to 10, and particularly preferably 4 to 8. The degree of irregularity of the bellows part is not particularly limited, but the outer peripheral dimension of the concave portion is 85% or less, preferably 40 to 75%, more preferably 50 to 75% with respect to the outer peripheral dimension of the convex portion. The ratio of the total height of the container body with the bellows part completely compressed to the total height of the container body before the contraction of the bellows part is preferably 50% or less, more preferably 40% or less, and particularly preferably 10 to 3
It is 0%. This ratio is preferably 10% or more in terms of manufacturing and design.

The liquid container can have a necessary gas barrier property by changing the material and raw material used. For example, when a high oxygen barrier property is required such as in a developing solution, low density polyethylene / polyvinyl alcohol ethylene copolymer / low density polyethylene (LD
PE / EVOH / LDPE) and low density polyethylene / nylon / low density polyethylene (LDPE / NY / LDP)
E) and other three-layer structure, and low-density polyethylene / nylon (LDPE / NY) layer structure and other multi-layer structure mainly composed of low-density polyethylene, with a gas barrier property of 25 ml / m ² · day · atm (20 ° C 65%) or less, preferably 0.5 to 10 ml / m ² · day · atm (20 ° C 65%
%). For example, when oxygen barrier property is not required like bleaching solution, low density polyethylene (LDPE) alone or ethylene
It can be formed using a vinyl acetate copolymer resin (EVA). Here, the low-density polyethylene has a density of 0.940 g / cc or less, preferably 0.90 to 0.94.
g / cc, more preferably 0.905 to 0.925 g / cc
Can be used. In this case, gas barrier property ^{50ml / m 2 · day · atm} (20 ℃ 65%) or more, for example ^{100~5000ml / m 2 · day · atm} (20 ℃ 65
%).

The average wall thickness of the container mouth portion, the flange portion and their vicinity is preferably 1 to 4 mm, more preferably 1 to 4 mm.
The thickness of the container body is preferably 0.1 to 1.5 mm, and particularly preferably 1.2 to 2.5 mm.
mm, more preferably 0.2 to 1.0 mm, particularly preferably 0.3 to 0.7 mm, and the difference between the two is preferably 0.2 mm, more preferably about 0.5 mm. To be The ratio of the surface area (cm ² ) of the container to the internal volume (cm ³ ) of the container increases due to the bellows structure, but is preferably 0.3 to 1.5 cm ^-1 , more preferably 0.4 to 1.2.
cm ^-1, it is particularly preferably 0.5 to 1.0 cm ^-1.
When filling the above-mentioned container with liquid, it is preferable that the head space (the space of the space without the processing liquid in the upper part of the container) is small in terms of improving the liquid stability, but if the head space is too small, during filling or use Liquid overflow easily occurs.
The liquid filling rate in the container is preferably 65 to 95%, more preferably 70 to 90%.

It is preferable that the cap or the inner stopper of the container is made of the same material as that of the container body, since it is easy to sort the container after use for recycling and recycling. By changing the material and the raw material, it is possible to provide the necessary gas barrier property in the same manner as the main body described above. The internal volume of the container is not particularly limited, but is preferably 50 ml to 5 liters from the viewpoint of handleability.

The above container can be recycled for use by the following method. 1. At the user's end, the bellows part of the used container is compressed, the inner plug and cap are stored, and the container is stored. 2. When the user reaches a certain quantity, it is collected from the user. 3. With the cap still attached, the used container is hung on a shredder device and cut into a predetermined size. 4. The cut pieces are put into a water tank, washed for a predetermined time, dried and then used as a material for molding a resin product. 5. It is also possible to mix the regenerated material with the material for virgin, mold the above-mentioned container, and newly fill the processing liquid to obtain a product. Specific examples of the flexible processing liquid containers A and B having the bellows part will be given below.

Container name Container A Container B type Approximate square shape (Fig. 1) Approximate circle shape (Fig. 2) Outer circumference of bellows convex portion (cm) 24cm 24cm Outer circumference of bellows recessed portion (cm) 16cm 16cm Recessed outer circumference / Outer circumference of convex part (%) 67% 67% Height before shrinking bellows (cm) 18cm 18cm Height after shrinking bellows (cm) 4cm 4cm Reduction rate of height due to bellows contraction 22% 22% Contents (ml) 580ml 580ml Filling amount (ml) 500ml 500ml Filling rate (%) 86% 86% Container body material LDPE (density 0.91g / cc) LDPE (density 0.91g / cc) / NY / LDPE (density 0.91g / cc) Cap and inner plug material 〃 〃 Oxygen permeability (ml / m ²・ day ・ atm (20 ℃ 65%)) 100 1.0 Body wall thickness (mm) 0.5 0.5 Container surface area (cm ² ) 520 505

[0124]

The present invention will be described in more detail with reference to the following examples, but the present invention is not limited thereto. Example 1 On a subbed cellulose triacetate film support,
A multilayer color photographic light-sensitive material sample 101 composed of each layer having the composition shown below was prepared. (Photosensitive layer composition) The main materials used for each layer are classified as follows: ExC: Cyan coupler UV: UV absorber ExM: Magenta coupler HBS: High boiling organic solvent ExY: Yellow coupler H: Gelatin Curing agent ExS: Sensitizing dye The numbers corresponding to the respective components indicate the coating amount expressed in units of g / m ² , and for silver halide, the coating amount in terms of silver. However, with respect to the sensitizing dye, the coating amount is shown in mol unit per mol of silver halide in the same layer.

First Layer (Antihalation Layer) Black Colloidal Silver Silver 0.09 Gelatin 1.60 ExM-1 0.12 ExF-1 2.0 × 10 ^-3 Solid Disperse Dye ExF-2 0.030 Solid Disperse Dye ExF-3 0.040 HBS-1 0.15 HBS- 2 0.02

Second layer (intermediate layer) Silver iodobromide emulsion M Silver 0.065 ExC-2 0.04 Polyethyl acrylate latex 0.20 Gelatin 1.04

Third Layer (Low Sensitivity Red Sensitive Emulsion Layer) Silver Iodobromide Emulsion A Silver 0.25 Silver Iodobromide Emulsion B Silver 0.25 ExS-1 6.9 × 10 ^-5 ExS-2 1.8 × 10 ^-5 ExS-3 3.1 × 10 ^-4 ExC-1 0.17 ExC-3 0.030 ExC-4 0.10 ExC-5 0.020 ExC-6 0.010 Cpd-2 0.025 HBS-1 0.10 Gelatin 0.87

Fourth Layer (Medium-Sensitivity Red Sensitive Emulsion Layer) Silver Iodobromide Emulsion C Silver 0.70 ExS-1 3.5 × 10 ^-4 ExS-2 1.6 × 10 ^-5 ExS-3 5.1 × 10 ^-4 ExC-1 0.13 ExC-2 0.060 ExC-3 0.0070 ExC-4 0.090 ExC-5 0.015 ExC-6 0.0070 Cpd-2 0.023 HBS-1 0.10 Gelatin 0.75

Fifth layer (high-sensitivity red-sensitive emulsion layer) Silver iodobromide emulsion D Silver 1.40 ExS-1 2.4 × 10 ^-4 ExS-2 1.0 × 10 ^-4 ExS-3 3.4 × 10 ^-4 ExC-1 0.10 ExC-3 0.045 ExC-6 0.020 ExC-7 0.010 Cpd-2 0.050 HBS-1 0.22 HBS-2 0.050 Gelatin 1.10

Sixth layer (intermediate layer) Cpd-1 0.090 Solid disperse dye ExF-4 0.030 HBS-1 0.050 Polyethyl acrylate latex 0.15 Gelatin 1.10

Seventh Layer (Low-Sensitivity Green Sensitive Emulsion Layer) Silver iodobromide Emulsion E 0.15 Silver iodobromide Emulsion F Silver 0.10 Silver iodobromide Emulsion G Silver 0.10 ExS-4 3.0 × 10 ^-5 ExS-5 2.1 × 10 ^-4 ExS-6 8.0 × 10 ^-4 ExM-2 0.33 ExM-3 0.086 ExY-1 0.015 HBS-1 0.30 HBS-3 0.010 Gelatin 0.73

Eighth Layer (Medium-Sensitivity Green Sensitive Emulsion Layer) Silver Iodobromide Emulsion H Silver 0.80 ExS-4 3.2 × 10 ^-5 ExS-5 2.2 × 10 ^-4 ExS-6 8.4 × 10 ^-4 ExC-8 0.010 ExM-2 0.10 ExM-3 0.025 ExY-1 0.018 ExY-4 0.010 ExY-5 0.040 HBS-1 0.13 HBS-3 4.0 × 10 ^-3 Gelatin 0.80

Ninth layer (high-sensitivity green-sensitive emulsion layer) Silver iodobromide emulsion I Silver 1.25 ExS-4 3.7 × 10 ^-5 ExS-5 8.1 × 10 ^-5 ExS-6 3.2 × 10 ^-4 ExC-1 0.010 ExM-1 0.020 ExM-4 0.025 ExM-5 0.040 Cpd-3 0.040 HBS-1 0.25 Polyethyl acrylate latex 0.15 Gelatin 1.33

10th layer (yellow filter layer) Yellow colloidal silver Silver 0.015 Cpd-1 0.16 Solid disperse dye ExF-5 0.060 Solid disperse dye ExF-6 0.060 Oil-soluble dye ExF-7 0.010 HBS-1 0.60 Gelatin 0.60

11th layer (low-sensitivity blue-sensitive emulsion layer) Silver iodobromide emulsion J Silver 0.09 Silver iodobromide emulsion K Silver 0.09 ExS-7 8.6 × 10 ^-4 ExC-8 7.0 × 10 ^-3 ExY-1 0.050 ExY-2 0.22 ExY-3 0.50 ExY-4 0.020 Cpd-2 0.10 Cpd-3 4.0 × 10 ^-3 HBS-1 0.28 Gelatin 1.20

12th layer (high-sensitivity blue-sensitive emulsion layer) Silver iodobromide emulsion L Silver 1.00 ExS-7 4.0 × 10 ^-4 ExY-2 0.10 ExY-3 0.10 ExY-4 0.010 Cpd-2 0.10 Cpd-3 1.0 × 10 ^-3 HBS-1 0.070 Gelatin 0.70

Thirteenth layer (first protective layer) UV-1 0.19 UV-2 0.075 UV-3 0.065 HBS-1 5.0 × 10 ^-2 HBS-4 5.0 × 10 ^-2 gelatin 1.8

14th layer (second protective layer) Silver iodobromide emulsion M Silver 0.10 H-1 0.40 B-1 (diameter 1.7 μm) 5.0 × 10 ^-2 B-2 (diameter 1.7 μm) 0.15 B-3 0.05 S-1 0.20 Gelatin 70

Further, in order to improve the storability, processability, pressure resistance, antifungal / antibacterial property, antistatic property and coating property of each layer, W-1 to W-3, B-4 to B- may be used. 6, F
-1 to F-17 and iron salt, lead salt, gold salt, platinum salt,
It contains a palladium salt, an iridium salt, and a rhodium salt. F-10 was added to the 13th layer in an amount of 10 mg / m ² to obtain F-
11 was added to the fifth layer at 10 mg / m ² (note that F-10
Is the above compound A-3, and F-11 is the above compound A-4.
Is the same compound).

[0140]

[Table 6]

In Table B, (1) Emulsions J to L were prepared according to the examples of JP-A-2-91938.
It is reduction-sensitized during grain preparation using thiourea dioxide and thiosulfonic acid. (2) Emulsions A to I were prepared according to the examples of JP-A-3-237450.
Gold sensitization, sulfur sensitization and selenium sensitization are performed in the presence of the spectral sensitizing dye described in each photosensitive layer and sodium thiocyanate. (3) For the preparation of tabular grains, low molecular weight gelatin is used according to the examples of JP-A 1-158426. (4) Dislocation lines as described in JP-A-3-237450 are observed in the tabular grains by using a high voltage electron microscope. (5) Emulsion L is a double structure grain containing an internal high iodine core described in JP-A-60-143331.

Preparation of Dispersion of Organic Solid Disperse Dye ExF-2 shown below was dispersed by the following method. That is, water 21.7
3 ml of 5% sodium p-octylphenoxyethoxyethoxyethane sulfonate and 5% aqueous solution
0.5 g of an aqueous solution of p-octylphenoxypolyoxyethylene ether (degree of polymerization: 10) was put in a 700 ml pot mill, and 5.0 g of dye ExF-2 and 500 ml of zirconium oxide beads (diameter 1 mm) were added. The contents were dispersed for 2 hours. A BO type vibrating ball mill manufactured by Chuo Koki was used for this dispersion. After the dispersion, the contents were taken out, added to 8 g of a 12.5% gelatin aqueous solution, and the beads were removed by filtration to obtain a gelatin dispersion of the dye. The average particle size of the dye particles is 0.44
μm.

Similarly, solid dispersions of ExF-3, ExF-4 and ExF-6 were obtained. The average particle diameters of the dye fine particles were 0.24 μm, 0.45 μm and 0.52 μm, respectively.
ExF-5 is a microprecipitation described in Example 1 of European Patent Application Publication (EP) 549,489A.
It was dispersed by the dispersion method. The average particle size was 0.06 μm.

[0144]

[Chemical 13]

[0145]

Embedded image

[0146]

[Chemical 15]

[0147]

Embedded image

[0148]

[Chemical 17]

[0149]

Embedded image

[0150]

[Chemical 19]

[0151]

Embedded image

[0152]

[Chemical 21]

[0153]

[Chemical formula 22]

[0154]

[Chemical formula 23]

[0155]

[Chemical formula 24]

[0156]

[Chemical 25]

[0157]

[Chemical formula 26]

[0158]

[Chemical 27]

[0159]

[Chemical 28]

The sample 101 was cut into a width of 35 mm and photographed by a camera, and the following treatment was carried out for 1 m ² per day for 15 days. (Running process) Each process is an automatic processor FP-3 manufactured by Fuji Photo Film Co., Ltd.
The following was performed using 60B. The overflow solution of the bleaching bath was reflowed to the waste solution tank without flowing into the post-bath. This FP360B is equipped with the evaporation correction means described in JIII Journal of Technical Disclosure No. 94-4992. The treatment process and the treatment liquid composition are shown below.

(Processing step) Processing time Processing temperature Replenishment amount ^* Tank capacity Color development 3 minutes 5 seconds 37.8 ° C 20 ml 11.5 l Bleaching 50 seconds 38.0 ° c 5 ml 5 l Fixing (1) 50 seconds 38.0 ° c −5 l Fixing (2) 50 seconds 38.0 ℃ 8 ml 5 liters Water wash 30 seconds 38.0 ℃ 17 ml 3 liters Stable (1) 20 seconds 38.0 ℃ −3 liters Stable (2) 20 seconds 38.0 ℃ 15 ml 3 liters Dry 1 minute 30 60 ℃ per second * Replenishment amount per 35m width of photosensitive material 1.1m (equivalent to 24Ex. 1) Stabilizer and fixer are countercurrent system from (2) to (1),
The overflow of washing water was introduced into the fixing bath (2). The amount of developing solution brought into the bleaching process, the amount of bleaching solution brought into the fixing process, and the amount of fixing solution brought into the washing process were 2.
It was 5 ml, 2.0 ml, and 2.0 ml. The crossover time is 6 seconds in all cases, and this time is included in the processing time of the previous step. The opening area of the above processor is 100 cm ^{2 with the} color developer,
The bleaching solution had a volume of 120 cm ² , and the other processing solutions had a volume of approximately 100 cm ² .

The composition of the processing liquid is shown below. (Color developer) Tank liquid (g) Replenisher (g) Diethylenetriaminepentaacetic acid 3.0 3.0 Catechol-3,5-disulfonate disodium salt 0.3 0.3 Sodium sulfite 3.9 5.3 Potassium carbonate 39.0 39.0 Compound of general formula (I) (Table- See C) See Table-C See Table-C Potassium bromide 1.3 0.3 Potassium iodide 1.3 mg-4-Hydroxy-6-methyl-1,3,0.05-3a, 7-tetrazaindene hydroxylamine sulfate 2.4 3.3 2 -Methyl-4- [N-ethyl-N- (β-hydroxyethyl) amino] aniline sulfate 4.5 6.5 Water was added to 1.0 liter 1.0 liter pH (adjusted with potassium hydroxide and sulfuric acid) 10.05 10.18

(Bleaching Solution) Tank Solution (g) Replenishing Solution (g) 1,3-Diaminopropanetetraacetic Acid Ferric Ammonium Monohydrate 113 170 Ammonium Bromide 70 105 Ammonium Nitrate 14 21 Dicarboxylic Acid (See Table-C) 0.8 times the replenisher See Table C. Add water 1.0 liter 1.0 liter pH [Prepared with ammonia water] 4.6 4.0

(Fixing (1) Tank Liquid) A 5:95 (volume ratio) mixture of the above bleaching tank liquid and the following fixing tank liquid. (PH 6.8) (Fixer solution (2)) Tank solution (g) Replenisher solution (g) Ammonium thiosulfate aqueous solution 240 ml 720 ml (750 g / l) Imidazole 7 21 Ammonium methanethiosulfonate 5 15 Ammonium methanesulfinate 10 30 Ethylenediaminetetraacetic acid 13 39 Add water 1.0 liter 1.0 liter pH [Prepared with ammonia water and acetic acid] 7.4 7.45

(Washing water) Tap water was used as an H-type strongly acidic cation exchange resin (Amberlite IR-produced by Rohm and Haas).
120B) and OH-type strongly basic anion exchange resin (Amberlite IR-400) were passed through a mixed bed column to adjust the concentration of calcium and magnesium ions to 3 mg.
/ Liter or less, followed by sodium diisocyanurate dichloride 20 mg / liter and sodium sulfate 150
mg / l was added. The pH of this liquid is 6.5 to 7.
It was in the range of 5.

(Stabilizing Solution) Common to Tank Solution and Replenishing Solution (unit: g) Sodium p-toluenesulfinate 0.03 Polyoxyethylene-p-monononylphenyl ether (Average degree of polymerization: 10) 0.2 1,2-Benzisothiazoline-3- on. Sodium 0.10 Ethylenediaminetetraacetic acid disodium salt 0.05 1,2,4-triazole 1.3 1,4-bis (1,2,4-triazol-1-ylmethyl) piperazine 0.75 Water was added to 1.0 liter pH 8.5

In the above running treatment, each replenisher was prepared in the following manner, filled in a container in advance, and left for 6 months at room temperature using a kit (some of which is a concentrated kit). Disappears (alarm goes out)
Each was placed in each replenishment tank.

(Color Developer) A Part Hydroxylamine Sulfate 17.0 g Addition of ion-exchanged water to 2.5 L pH 4.1 B Part Diethylenetriaminepentaacetic acid 14.0 g Catechol-3,5-disulfonate disodium 1.5 g Sodium sulfite 26.5 g Odor Potassium iodide 1.5 g Potassium carbonate 195.0 g Compound of general formula (I) (see Table-C) Concentration 5 times that of the above replenisher 2-methyl-4- [ethyl-N- (β-hydroxyethyl) amino] aniline sulfate 32.5g Add both ion-exchanged water to 2.5 liter pH (adjust with potassium hydroxide) 10.55 Addition method to the replenishment tank After inserting 2 parts of A part, insert 2 parts of B part. (No agitation) (Bleaching solution), (Fixing solution) Replenisher as they are (Complete solution kit) (Stable solution concentration kit) 100 times concentrated solution of stable solution Preparation method After adding 8 liters of tap water, Insert one kit (80 ml). (No stirring)

Container Color developing solution Bleaching solution / Fixing solution Stabilizer A Part B Part Shape Approximate square type Approximate square type Approximate square type Approximately circular type Internal volume 2.8 liters 2.8 liters 2.2 liters 280 milliliters Filling amount 2.5 liters 2.5 liters 2.0 liters 250 ml Container body material LDPE ^* LDPE / NY / LDPE LDPE ^* HDPE * Density 0.91 g / cc Other materials of cap and inner plug, height reduction rate due to contraction of bellows, oxygen permeability, wall thickness are approximately circle The mold is the same as the container B described in the text, and the substantially square shape is the same as the container A described in the text. In addition, the surface area of the container is 300 cm ² if it is approximately circular, and 2 in a 2.2 liter container if it is approximately square.
100 cm ^2, is 2500 cm ² in 2.8 l vessel.

After the completion of each running process, the sample 101 which was not exposed and photographed with a camera was further processed, and this sample was used to evaluate the process unevenness and the density increase in the minimum density part. The evaluation method is shown below. Irregularity of treatment The sample 101 photographed with a camera was visually observed for 1000 frames, and the occurrence frequency of irregularity was compared. 2 per frame
If unevenness was observed, it was treated as if there were two unevennesses. Occurrence frequency = (number of irregularities / 1000) x 100 (percentage) Increase in density in the minimum density part The yellow transmission density of the unexposed sample after the new solution and the running process was measured by the Fuji Photo Film Co., Ltd. photographic densitometer FSD.
The difference between the fresh solution and the unexposed yellow density after the running treatment was calculated and compared. The results of unevenness in processing and increase in density in the minimum density area are shown in Table-C.

[0171]

[Table 7]

As can be seen from Table-C, in the embodiment of the present invention, good results were obtained without unevenness in processing and increase in density in the minimum density area.

Example 2 A photosensitive material prepared by excluding F-10 and F-11 of the photosensitive material used in Example 1 will be referred to as Sample 201. In addition, this sample 201 includes compounds A-3, A-8, A-9 in the text.
Samples 202, 203 and 204 were prepared by adding 5 mg / m ² to the 13th layer. The treatment unevenness was compared in the same manner as in Example 1. The results are shown in Table-D.
It was shown to.

[0174]

[Table 8]

By using the preferred radical scavenger of the present invention in a light-sensitive material as shown in Table-D,
It can be seen that the occurrence of processing unevenness can be sufficiently suppressed.

Example 3 Preparation of Sample 301 1) Support The support used in this example was prepared by the following method. 100 parts by weight of commercially available polyethylene-2,6-naphthalate polymer and Tinuvin as an ultraviolet absorber
P. 2 parts by weight of 326 (manufactured by Ciba-Geigy Ciba-Geigy) were dried by a conventional method, dissolved at 300 ° C., extruded from a T-type die, and longitudinally stretched 3.0 times at 140 ° C. The film was transversely stretched 3.0 times at 130 ° C. and further heat-set at 250 ° C. for 6 seconds to obtain a PEN film having a thickness of 90 μm. Furthermore, a part of it has a diameter of 20c.
It was wound around a stainless steel core of m and subjected to a heat history of 110 ° C. for 48 hours.

2) Coating of undercoat layer The above-mentioned support was subjected to corona discharge treatment, UV discharge treatment, glow discharge treatment, and flame treatment on both sides,
An undercoat liquid having the following composition was applied to each surface, and an undercoat layer was provided on the high temperature surface side during stretching. Pillar Pi for corona discharge treatment
A 30 cm wide support is treated at 20 m / min using a llar solid state corona processor 6KVA model. At this time, the object to be treated was treated at 0.375 KV · A · min / m ^{2 based on} the current / voltage readings. The discharge frequency during the treatment was 9.6 KHz, and the gap clearance between the electrode and the dielectric roll was 1.6 mm. The UV discharge treatment was performed while heating at 75 ° C.
Furthermore, the glow discharge treatment was performed with a cylindrical electrode at 3000 W for 30
Irradiated for seconds.

Gelatin 3 g Distilled water 25 ml Sodium α-sulfo-di-2-0.05 g Ethylhexyl succinate formaldehyde 0.02 g Salicylic acid 0.1 g Diacetyl cellulose 0.5 g p-Chlorophenol 0.5 g Resorcin 0.5 g Cresol 0. _{5g (CH 2 = CHSO 2 CH} 2 CH 2 NHCO) 2 CH 2 0.2g 3 -fold molar adduct aziridine of trimethylolpropane 0.2g trimethylolpropane - 3 fold molar adduct of methanol-toluene diisocyanate 0.2g 15 ml Acetone 85 ml Formaldehyde 0.01 g Acetic acid 0.01 g Concentrated hydrochloric acid 0.01 g

3) Coating of Back Layer On one surface of the above-mentioned support after undercoating, an antistatic layer, a magnetic recording layer and a sliding layer having the following compositions were coated as back layers. 3-1) Coating of antistatic layer 3-1-1) Preparation of conductive fine particle dispersion liquid (tin oxide-antimony oxide composite dispersion liquid) 230 parts by weight of stannic chloride hydrate and antimony trichloride 2
3 parts by weight was dissolved in 3000 parts by weight of ethanol to obtain a uniform solution. A 1N sodium hydroxide aqueous solution was added dropwise to this solution until the pH of the solution reached 3, to obtain a coprecipitate of colloidal stannic oxide and antimony oxide. The obtained coprecipitate was left at 50 ° C. for 24 hours to obtain a reddish brown colloidal precipitate. The reddish brown colloidal precipitate was separated by centrifugation. To remove excess ions, water was added to the precipitate and washed by centrifugation. This operation was repeated 3 times to remove excess ions. 200 parts by weight of the colloidal precipitate from which excess ions have been removed is redispersed in 1500 parts by weight of water, and 650
The powder was sprayed in a firing furnace heated to 0 ° C. to obtain a bluish tin oxide-antimony oxide composite fine particle powder having an average particle size of 0.005 μm. The specific resistance of this fine particle powder is 5 Ω · cm
Met. A mixed solution of 40 parts by weight of the above-mentioned fine particle powder and 60 parts by weight of water was adjusted to pH 7.0, and after roughly dispersing with a stirrer,
Horizontal sand mill (trade name: Dyno Mill; WILLYA.B
It was prepared by dispersing with ACHOFENAG) until the residence time reached 30 minutes. At this time, the average particle size of the secondary aggregate was about 0.04 μm.

3-1-2) Coating of Conductive Layer A conductive layer having the following formulation was coated so that the dry film thickness would be 0.2 μm, and dried at 115 ° C. for 60 seconds. Conductive fine particle dispersion prepared in 3-1-1) 20 parts by weight Gelatin 2 parts by weight Water 27 parts by weight Methanol 60 parts by weight p-Chlorophenol 0.5 parts by weight Resorcinol 2 parts by weight Polyoxyethylene nonylphenyl ether 0. 01 parts by weight

The resistance of the obtained conductive film was 10 ^8.0 (1
00V) and had excellent antistatic performance. 3-2) Coating of magnetic recording layer Magnetic substance Co-coated γ-Fe ₂ O ₃ (long axis 0.14 μm,
Uniaxial 0.03 μm needle-shaped, specific surface area 41 m ² / g, saturation magnetization 89 emu / g, surface treated with 2% by weight of Fe ₂ O ₃ each with aluminum oxide and silicon oxide, coercive force 930 Oe , Fe ^{+ 2} / Fe ⁺³ ratio is 6/94) 110
220 g of water and 150 g of a silane coupling agent of poly (polymerization degree 16) oxyethylenepropyltrimethoxysilane were added to 0 g, and kneaded well in an open kneader for 3 hours. The roughly dispersed viscous liquid was dried at 70 ° C. for one day and night to remove water, and then heated at 110 ° C. for 1 hour to prepare surface-treated magnetic particles. Further, the following formulation was used, and the mixture was kneaded again in an open kneader.

Surface-treated magnetic particles 1000 g Diacetyl cellulose 17 g Methyl ethyl ketone 100 g Cyclohexanone 100 g

[0183] Furthermore, a sand mill (1/4
G) was finely dispersed at 200 rpm for 4 hours. Kneaded product 100 g Diacetyl cellulose 60 g Methyl ethyl ketone 300 g Cyclohexanone 300 g

Further, 20 wt% of diacetyl cellulose and a 3-fold molar adduct of trimethylolpropane-toluene diisocyanate as a curing agent were added to the binder. So that the viscosity of the obtained liquid is about 80 cp,
Diluted with equal amounts of methyl ethyl ketone and cyclohexanone. The coating was performed on the above conductive layer with a bar coater so that the film thickness would be 1.2 μm. The amount of the magnetic substance was applied so as to be 0.6 g / m ² . Further, silica particles (0.3 μm) as a matting agent and aluminum oxide (0.5 μm) as an abrasive were added so as to be 10 mg / m ² . Drying was performed at 115 ° C. for 6 minutes (the temperature of the rollers and the conveying device in the drying zone are 115 ° C.). When using a blue filter in Status M of X- write, increment of the color density of D ^B of the magnetic recording layer was about 0.1. The saturation magnetization moment of the magnetic recording layer was 4.2 emu / m ² , the coercive force was 923 Oe, and the squareness ratio was 65%.

3-3) Preparation of Sliding Layer The following formulation liquid was applied so that the solid coating amount of the compound was as follows, and dried at 110 ° C. for 5 minutes to obtain a sliding layer. Diacetyl cellulose 25 mg / m ² C ₆ H ₁₃ CH (OH) C ₁₀ H ₂₀ COOC ₄₀ H ₈₁ (Compound a) 6 mg / m ² C ₅₀ H ₁₀₁ O (CH ₂ CH ₂ O) ₁₆ H (Compound b) 9 mg / m ²

Compound a / compound b (6: 9) is
It was heated and dissolved at 105 ° C. in a solvent of xylene and propylene glycol monomethyl ether (volume ratio 1: 1), and this solution was poured into 10 times amount of propylene glycol monomethyl ether (25 ° C.) to obtain a fine dispersion liquid. 5 more
After diluting in twice the amount of acetone, redispersion with a high pressure homogenizer (200 atm) gives a dispersion (average particle size 0.01
μm) and then added and used. The performance of the obtained sliding layer was as follows: dynamic friction coefficient 0.06 (5 mmφ stainless hard ball, load 100 g, speed 6 cm / minute),
It has a coefficient of static friction of 0.07 (clip method) and excellent characteristics. The sliding property with respect to the emulsion surface, which will be described later, also had a dynamic friction coefficient of 0.12.

(4) Preparation of photosensitive layer On the opposite side of the back surface prepared in (3) and the support,
The photosensitive layers described on page 116, left column, to page 133 of Kokai Giho, Kogi Gi No. 94-6023 (published by the Institute of Invention and Innovation, 1994) were coated.

The photosensitive material prepared as described above is used for 24 mm
The width is cut into 160 cm, and two perforations of 2 mm square are provided at a distance of 5.8 mm at a position 0.7 mm from one side width direction of the photosensitive material. A device in which these two sets are provided at intervals of 32 mm is prepared, and is shown in US Pat. No. 5,296,887, FIG. 1-FIG. The sample 301 was stored in the plastic film cartridge described in No. 7. This sample had a head gap of 5 μm and a turn number of 20 from the coated surface side of the magnetic recording layer.
00 input / output head is used, and F at a feed rate of 100 mm / s is applied during the perforation of the photosensitive material.
The M signal was recorded. This sample was treated with each of the continuous treatment solutions used in Example 1 and then stored again in the original plastic film cartridge.

The film thus stored is pulled out, and the first embodiment is shown.
When the unevenness of treatment and the increase in density of the minimum density part were compared in the same manner as in (1), these were improved by the method of the present invention. Also, when the stored film was pulled out and the signal was read at the same speed as when the signal was recorded by the above head, it was confirmed that the signal was correctly output, and the photosensitive material having the magnetic recording layer was processed. In this case, the recorded signal can be processed without being damaged.

Example 4 When the following color negative film was processed after completion of the running process of the process No. 17 of Example 1, there was no particular increase in the density in the minimum density part, and the result was good. Fuji Photo Film Co., Ltd. SUPER G100 (serial number 918821) 〃 SUPER G400 (serial number V21856) 〃 SUPER G ACE 400 (serial number V53534) 〃 SUPER G800 (serial number M04507) 〃 SUPER G ACE 800 (serial number M09542) 〃 SUPER HG1600 (Production number 767006) 〃 REALA (Production number 881002) 〃 160NS (Production number 401092) 〃 160S (Production number 090101) Eastman Kodak Co., Ltd. SUPER Gold100 (Emulsion number 028L17A) 〃 SUPER Gold200 (Emulsion number 022LO66A) ) 〃 SUPER Gold 400 (Emulsion number 263L11A) 〃 SUPER Gold 1600 (Emulsion number 103L116C) 〃 Vericolor III (Emulsion number 799130G067B)

Example 5 In Example 1, the replenisher for the color developing solution was used as a concentration kit having the following three-part structure and left at room temperature for 6 months.
When the same treatment as in Example 1 was performed using the replenisher prepared, the same results as in Example 1 were obtained. Part A Diethylenetriamine pentaacetic acid 14 g Sodium sulfite 51 g Potassium bromide 3 g Potassium carbonate 390 g Both ion-exchanged water are added 1000 ml pH (adjusted with potassium hydroxide) 13.8

Part B Diethylenetriaminepentaacetic acid 8 g Hydroxylamine sulfate 34 g N, N-bis (2-sulfoethyl) hydroxylamine disodium 20 g Both ion-exchanged water are added 500 ml pH (adjusted with potassium hydroxide) 3.5

Part C 2-Methyl-4- [N-ethyl-N- (βhydroxyethyl) amino] aniline sulphate 65 g Catechol-3,5-disulphonic acid disodium 3 g Sodium sulphite 2 g Both ion-exchanged water were added. 500 ml pH 2.25 The container used was as follows. Part A = Container A (filling amount 500 ml) Part B = Container A (〃) Part C = Container B (〃) Preparation method of replenisher solution 2 parts A (1 liter) and 1 part B in 8 liters of water (500 milliliters) and one part C (500 milliliters) are sequentially added and well stirred. In this way, 10 liters of the replenisher solution is prepared.

Embodiment 6 Processing No. 1 of Embodiment 1 In Example 17, the same process as in Example 1 was performed except for the following changes. The color developer was changed to the following, and the replenishing amount of the color developer was set to 7.5 ml per 35 mm width 1.1 m, and separate washing water was added to the color developing tank to 7.5 ml per 35 mm width 1.1 m. did. The composition of the treatment liquid is shown below.

(Color developer) Tank liquid (g) Replenisher (g) Diethylenetriaminepentaacetic acid 3.0 8.0 p-Toluenesulfonic acid 5.0 18.0 Catechol-3,5-disulfonic acid disodium 0. 3 0.6 Sodium sulfite 3.9 11.0 Potassium carbonate 39.0 78.0 Compound (17) 6.3 18.0 Potassium bromide 1.3-Potassium iodide 1.3 mg-4-hydroxy-6- Methyl-1,3,3a, 7-tetrazaindene 0.05-2-methyl-4- [N-ethyl-N- (β-hydroxyethyl) amino] aniline sulfate 4.7 14.0 Water was added. 1.0 liter 1.0 liter pH (adjusted with potassium hydroxide and sulfuric acid) 10.05 10.27

Further, the stabilizing solution is the same as the stabilizing replenisher of Example 1 (10).
Replenish the double concentrate with 1.5 ml per 1.1 m of 35 mm width, and separately stabilize (2) 35 m of wash water supplement
13.5 ml was replenished per 1.1 m of m width.

The color developing replenisher was filled in the container B, and the stable replenisher was filled in the container A, which was stored at room temperature for 3 months. When evaluated in the same manner as in Example 1, both the occurrence frequency of processing unevenness and the increase in density in the minimum density part were almost 0, and very good results were obtained.

[0198]

The silver halide color photographic light-sensitive material containing silver iodide is treated with a color developer containing hydroxylamines having an alkyl group or a heterocyclic aromatic group,
After that, by performing treatment with a solution having a bleaching ability containing a dicarboxylic acid, it is possible to prevent uneven treatment and an increase in density in the minimum density part.

[Brief description of drawings]

FIG. 1 is a perspective view of a substantially rectangular container for a flexible processing liquid having a bellows portion.

FIG. 2 is a front view of a substantially round container for a flexible processing liquid having a bellows portion.

[Explanation of symbols]

 1 Kip 2 Inner plug 3 Mouth 4 Label 5 Bellows

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Internal reference number FI technical indication G03C 7/42

Claims (3)

[Claims] 1. A method of processing a silver halide color photographic light-sensitive material with a color developing solution and then processing it with a processing solution having a bleaching ability, wherein the light-sensitive material has at least one emulsion layer containing silver iodide. A silver halide color photographic light-sensitive material characterized in that the color developing solution contains at least one compound represented by the following general formula (I), and the processing solution having a bleaching ability contains a dicarboxylic acid. Processing method. General formula (I) (In the formula, R ¹ and R ² each independently represent a hydrogen atom, an alkyl group, or a heteroaromatic group, and R ¹ and R ² may be linked to form a heterocycle together with a nitrogen atom. .
However, R ¹ and R ² are not hydrogen atoms at the same time. ) 2. The method of processing a silver halide color photographic light-sensitive material according to claim 1, wherein the light-sensitive material contains at least one radical scavenger. 3. The method of processing a silver halide color photographic light-sensitive material according to claim 1, wherein the light-sensitive material has a transparent magnetic recording layer.