JPH095965A - Method for processing silver halide color photographic sensitive material - Google Patents

Abstract

PURPOSE: To suppress staining and to improve the picture preservability, especially the increase in magenta stain with time, by agitating a bleaching fixer under specified conditions and incorporating a specified compd. into the fixer. CONSTITUTION: An image-wise exposed silver halide color photographic sensitive material is color-developed and then desilverized with a bleaching fixer. In this case, the fixer is agitated at 1.5<=S/V<=10 (where V is the tank volume in liter, and S is the circulation in liter/min), and at least one kind shown by RSO2 M is incorporated into the fixer. In the formula, R is an alkyl, cycloalkyl, alkenyl, alkynyl, aralkyl or aryl, M is hydrogen atom, alkali metal atom, ammonium or quaternary ammonium. Further, the bleaching fixation is conducted at pH4-5.5.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for processing a silver halide color photographic light-sensitive material, and particularly to provide a rapid processing method excellent in desilvering performance.

[0002]

2. Description of the Related Art In a method of processing a silver halide color photographic light-sensitive material, color development, desilvering, washing with water and stabilization are generally carried out. In particular, in the desilvering process, a bleach-fixing solution has come to be used from the viewpoint of simplifying and accelerating the processing. However, it is a well known fact that the bleach-fixing solution is a system in which an oxidizing agent and a reducing agent coexist, so that its oxidizing power is lower than that of the bleaching solution and the desilvering rate is slow.

Further, if the processing time of the bleach-fixing solution is shortened or the replenishing amount is reduced, not only the desilvering delay but also the post-processing stain is increased or the image storability is deteriorated (especially with time). It was found that a rise in Dmin) was observed. Analysis of the cause revealed that the color developing agent impregnated in the light-sensitive material during color development was not sufficiently oxidatively decomposed in the bleach-fixing bath, which had a weak oxidizing power, and remained in the light-sensitive material during the processing step. It is thought that this is due to the termination. Furthermore, with the low replenishment of the bleach-fix solution, the oxides of the main agents and dyes accumulated in the bleach-fix solution adhere to the photosensitive material, resulting in undesired stains and stains on the photosensitive material. In the case of a light-sensitive material having a layer, the problem that the reading accuracy is deteriorated may occur.

The above problems have been particularly noticeable in the silver halide color photographic light-sensitive materials used for photographing. It is considered that this is because the coating amount and the film thickness are larger than those of the printing material system, and in particular, the load on the desilvering process becomes large. Further, a method of improving stirring conditions to aim at various promoting effects such as desilvering is disclosed in JP-A-62-183460 and JP-A-62-18346.
It is described in No. 1 etc. However, as a general circulation amount, the S / V value is about 0.1 to 1.0, and violently stirring the bleach-fixing solution unlike the bleaching solution and the fixing solution causes oxidative deterioration of the solution. In order to promote the above phenomenon and become one of the factors of undesired stain, it has not been conventionally done, and the solution of the above problems has been desired.

[0005]

SUMMARY OF THE INVENTION Therefore, an object of the present invention is to provide a method for processing a silver halide color photographic light-sensitive material in which generation of stains is suppressed and image storability, particularly magenta stains with time, is remarkably improved. To provide.

[0006]

It has been found that the above problems can be solved by the following processing method. (1) In a processing method in which an image-exposed silver halide color photographic light-sensitive material is color-developed and then desilvered with a bleach-fixing solution, the bleach-fixing solution satisfies 1.5 ≤ S / V ≦ 10 Here, V = tank volume (liter), S = circulation amount (liter / min) are stirred, and the bleach-fixing solution contains at least one compound represented by the following general formula (I). A method for processing a silver halide color photographic light-sensitive material characterized by: General formula (I)

[0007]

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(In the formula, R represents an alkyl group, a cycloalkyl group, an alkenyl group, an alkynyl group, an aralkyl group, or an aryl group. M represents a hydrogen atom, an alkali metal atom, ammonium, or a quaternary amine. (2) The method for processing a silver halide color photographic light-sensitive material as described in (1) above, wherein the bleach-fixing process is performed at a pH of 4 to 5.5. (3) The silver halide color photographic material as described in (1) above, wherein the silver halide color photographic light-sensitive material has a magnetic recording layer containing magnetic particles on the side opposite to the photosensitive layer with respect to the support. Method of processing photosensitive material. The compound of the general formula (I) is a compound known as a sulfinic acid, and is disclosed in JP-A-1-224762,
No. 2-91643 and the like are known to be used in a bleach-fixing solution, but when used in a bleach-fixing solution under specific stirring conditions as in the present invention, stain is remarkably suppressed, and image storability is improved. It was never known to improve.

The compound of the general formula (I) of the present invention will be described in detail below. When R is an alkyl group, it preferably has 1 to 10 carbon atoms, and more preferably 1 to 3 carbon atoms. Also,
The cycloalkyl group has 6 to 10 carbon atoms, and the case of 6 is most preferable. In the case of an alkenyl group and an alkynyl group, it preferably has 3 to 10 carbon atoms, and more preferably 3 to 6 carbon atoms. In the case of an aralkyl group, it has 7 to 10 carbon atoms.
Is preferred. The aryl group preferably has 6 to 10 carbon atoms, and most preferably 6 carbon atoms. These groups may be substituted with various substituents, and preferable substituents are hydroxyl group, amino group, sulfonic acid group, carboxylic acid group, nitro group, phosphoric acid group, halogen atom, alkoxy group, mercapto. Group, cyano group, alkylthio group, sulfonyl group, carbamoyl group, carbonamido group, sulfonamide group, acyloxy group, sulfonyloxy group,
Examples thereof include ureido group and thioureido group.

Of the above, R is most preferably an alkyl group having 1 to 3 carbon atoms or a phenyl group,
Examples of preferable substitution include an amino group, a carboxylic acid group and a hydroxyl group. Most preferably, M is a hydrogen atom, a sodium atom, a potassium atom, an ammonium ion, or trimethylammonium. Specific compounds represented by formula (I) are shown below, but the invention is not limited thereto.

[0011]

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[0012]

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[0013]

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[0014]

[Chemical 6]

[0015]

[Chemical 7]

[0016]

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The amount of the compound of the general formula (I) added is preferably 0.001 to 1 mol, more preferably 0.01 to 0.5 mol, per liter of the bleach-fixing solution. The above compounds are disclosed in, for example, JP-A-62-1430.
It can be synthesized by the method described in No. 48 or a method similar thereto. Further, some of them are commercially available. Other details of the bleach-fixing solution of the present invention will be described later.

Next, the processing method of the present invention will be described in detail. The color developing solution (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 a typical example thereof is 3-methyl-4-amino.
-N, N diethylaniline, 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-
Examples include N, N-bis (5-hydroxypentyl) aniline, 4-amino-3-propyl-N- (4-hydroxybutyl) aniline, and their sulfates, hydrochlorides or p-toluenesulfonates. . Among these, especially 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.

The amount of the aromatic primary amine developing agent used is preferably 0.002 mol to 0.5 mol, and more preferably 0.005 mol to 0.
It is 4 mol. In particular, the effect of the present invention is remarkably obtained under the use condition of high concentration of 0.15 to 0.30 mol. The color developer includes hydroxylamine, diethylhydroxylamine, N, N-bis (sulphonatoethyl) hydroxylamine, hydroxylamines represented by the general formula (I) of JP-A-3-144446, and sulfites. Hydrazines such as N, N-biscarboxymethylhydrazine, phenylsemicarbazides, triethanolamine, various preservatives such as 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, competitive couplers, auxiliary developing agents such as 1-phenyl-3-pyrazolidone, tackifiers, aminopolycarboxylic acids, aminopolyphosphonic acids, alkyls Phosphonic acid, various chelating agents represented by phosphonocarboxylic acid, for example, ethylenediaminetetraacetic acid, nitrilotriacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, hydroxyethyliminodiacetic acid, 1-hydroxyethylidene-1,1 -Diphosphonic acid, Nitrilo-N, N, N-
Trimethylenephosphonic acid, ethylenediamine-N, N, N, N-
Tetramethylenephosphonic acid, ethylenediamine-di (o
-Hydroxyphenylacetic acid), β-alanine diacetic acid and salts thereof can be mentioned as typical examples.

Among the above, substituted hydroxylamine is most preferable as a preservative, and among them, diethylhydroxylamine, monomethylhydroxylamine or an alkyl group substituted with a water-soluble group such as a sulfo group, a carboxy group or a hydroxyl group is used as a substituent. Those having are preferred. The most preferable examples include N, N-bis (2-sulfonateethyl) hydroxylamine, monomethylhydroxylamine, diethylhydroxylamine and the like. It can be said that it is also a preferable specification to use triethanolamine, diethanolamine, catechol-3,5-disulphonate, catechol trisulphonate, etc. in combination as necessary. For the purpose of reducing the stain of the present invention, hydroxylamine sulfate gives better results when not used.

If desired, any antifoggant can be added to the color developer used in the present invention. As the antifoggant, alkali metal halides such as sodium chloride, potassium bromide and potassium iodide and organic antifoggants can be used. Examples of the organic antifoggants include benzotriazole, 6-nitrobenzimidazole,
5-nitroisoindazole, 5-methylbenzotriazole, 5-nitrobenzotriazole, 5-chloro-
Representative examples thereof include nitrogen-containing heterocyclic compounds such as benzotriazole, 2-thiazolyl-benzimidazole, 2-thiazolylmethyl-benzimidazole, indazole, hydroxyazaindolizine and adenine.

The color developing solution used in the present invention preferably has a pH range of about 9.5 to 10.5. If the developing activity can be maintained, it is preferable that the pH of the developing tank liquid is low also in the sense of preventing the generation of ammonia gas from the waste liquid. The most preferable pH of the tank liquid is 9.9 to 1
It is about 0.4. In order to maintain the above pH, it is preferable to use various buffers. As the buffer, carbonate,
Phosphate, borate, tetraborate, hydroxybenzoate, glycyl salt, N, N-dimethylglycine salt, leucine salt, norleucine salt, guanine salt, 3,4-dihydroxyphenylalanine salt, alanine salt, amino Butyrate,
2-amino-2-methyl-1,3-propanediol salt, valine salt, proline salt, trishydroxyaminomethane salt, lysine salt and the like can be used. Particularly, use of a carbonate is preferred. The amount of the buffer added to the developer is
It is preferably 0.1 mol / liter or more, and particularly
It is particularly preferably from 0.1 mol / liter to 0.4 mol / liter. Further, a compound having biodegradability is preferable as the chelating agent. An example of this is Japanese Patent Laid-Open No. 63-
146998, JP-A-63-199295, JP-A-63-267750, JP-A-63-267751,
JP-A-2-229146, JP-A-3-186841
Examples thereof include chelating agents described in German Patent No. 3739610, European Patent No. 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 preferred as the liquid shielding agent. It is particularly preferable to use it as a replenisher. The processing temperature of the color developer in the present invention is 3
The temperature is 0 to 55 ° C, preferably 35 to 55 ° C. The processing time is 20 seconds to 5 minutes, preferably 30 for the photographic light-sensitive material.
Second to 3 minutes and 20 seconds. Most preferably, it is 30 seconds to 2 minutes. In addition, the replenishment amount is 30 per square meter of sensitive material.
~ 800 ml, preferably about 50-500 ml.

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. Any development accelerator can be added to the developer used in the present invention, if necessary. As development accelerators, JP-B-37-16088, JP-B-37-5987, JP-B-38-7826
Nos. 44-12380, 45-9919 and U.S. Pat.
Thioether compounds represented by JP-A No. 247, etc.
-49829 and 50-15554, p-phenylenediamine compounds, JP-A-50-137726, JP-B-44-300
74, quaternary ammonium salts represented by JP-A-56-156826 and JP-A-52-43429, U.S. Pat. No. 2,494,903,
No. 3,128,182, No. 4,230,796, No. 3,253,919, Japanese Patent Publication No. 41-11431, U.S. Patent No. 2,482,546, No. 2,596,92
6 and 3,582,346, etc., amine compounds, JP-B-37-16088, JP-B-42-25201, U.S. Pat.
No. 4, Japanese Patent Publication Nos. 41-11431 and 42-23883, and U.S. Pat.
Polyalkylene oxides represented by 532,501 and the like,
In addition, 1-phenyl-3-pyrazolidones, imidazoles, and the like can be added as needed. next,
The desilvering process of the present invention will be described in detail. The desilvering step generally has a bleaching step, a bleach-fixing step, and a fixing step, and there are various steps. However, in the present invention, it is necessary to have the bleach-fixing step. Specific steps are shown below, but are not limited thereto.

(Step 1) Bleach-fixing (step 2) Bleach-bleach-fixing (step 3) Bleach-bleach-fixing-fixing (step 4) Fixing-bleach-fixing In the present invention, a bleach-fixing solution is immediately added after color development. The case of step 1 used is most preferable. Further, the bleach-fixing step may be a plurality of steps, and a multistage countercurrent method may be adopted.

As the bleaching agent used in the bleaching or bleach-fixing solution, aminopolycarboxylic acid iron (III) complexes, persulfates,
Bromate, hydrogen peroxide, and red blood salt are used,
The aminopolycarboxylic acid (III) complex can be most preferably used. The ferric complex salt used in the present invention may be added as a complexed complex iron salt in advance and dissolved,
Also, complexing compounds and ferric salts (eg ferric sulfate,
Ferric chloride, ferric bromide, iron nitrate (III), iron sulfate (III)
Complex salt may be formed in a liquid having a bleaching ability by coexisting with ammonium). The complex-forming compound may be slightly in excess of the amount required for complex formation with ferric ion, and when it is added in excess, it is usually preferably in the range of 0.01 to 10%.

In the present invention, as the compound forming the ferric complex salt in the liquid having bleaching ability, ethylenediaminetetraacetic acid (EDTA), 1,3-propanediaminetetraacetic acid (1,3-PDTA), Diethylenetriaminepentaacetic acid, 1,2-cyclohexanediaminetetraacetic acid, iminodiacetic acid, methyliminodiacetic acid, N- (2-acetamido) iminodiacetic acid, nitrilotriacetic acid, N- (2-carboxyethyl) iminodiacetic acid, N- (2-carboxymethyl) iminodipropionic acid, β-alanine diacetic acid, α-methyl-nitrilotriacetic acid, 1,4-diaminobutanetetraacetic acid, glycol ether diaminetetraacetic acid, N- (2-carboxyphenyl) iminodiacetic acid, Ethylenediamine
N- (2-carboxyphenyl) -N, N ', N'-triacetic acid, ethylenediamine-N, N'-disuccinic acid, 1,
Examples thereof include 3-diaminopropane-N, N'-disuccinic acid, ethylenediamine-N, N'-dimalonic acid, and 1,3-diaminopropane-N, N'-dimalonic acid, but are particularly limited to these. is not.

In order to form an iron (III) complex of these compounds, the iron (III) complex may be isolated and used,
The organic acid and iron (III) salt (for example, iron chloride, iron sulfate, iron nitrate, iron oxalate, etc.) may be mixed in an aqueous solution and used as they are. Further, it is preferable to add an excess amount of organic acid to stabilize the iron chelate. Specifically, the molar ratio is about 1.01 to 1.2 times.

The concentration of the ferric complex salt in the bleach-fixing solution of the present invention is appropriately in the range of 0.005 to 1.0 mol / liter, preferably 0.01 to 0.50 mol / liter. , And more preferably 0.02 to 0.30
It is in the range of mol / liter. The concentration of the ferric complex salt in the replenisher for the bleach-fixing solution is preferably 0.00
5 to 2 mol / liter, more preferably 0.01 to 1.
It is 0 mol / liter.

Various compounds can be used as a bleaching accelerator in the bleach-fixing solution or the pre-bath thereof. For example, U.S. Pat.No. 3,893,858, German Patent 1,29
0,812, JP-A-53-95630, Research Disclosure No. 17129 (July 1978), compounds having a mercapto group or a disulfide bond,
JP-B-45-8506, JP-A-52-20832, JP-A-53-32735,
Thiourea compounds described in U.S. Pat. No. 3,706,561 and halides such as iodine and bromine ions are preferable because of their excellent bleaching power.

Other bleach-fixing solutions applicable to the present invention include bromide (eg potassium bromide, sodium bromide, ammonium bromide) or chloride (eg potassium chloride, sodium chloride, ammonium chloride) or iodine. Rehalogenating agents such as halides (eg, ammonium iodide) can be included. PH of borax, sodium metaborate, acetic acid, sodium acetate, sodium carbonate, potassium carbonate, phosphorous acid, phosphoric acid, sodium phosphate, citric acid, sodium citrate, tartaric acid, malonic acid, succinic acid, glutaric acid, etc. One or more inorganic acids with buffering capacity,
Organic acids and their alkali metal or ammonium salts, or corrosion inhibitors such as ammonium nitrate and guanidine can be added. Further, the bath having a bleaching ability may contain various other fluorescent whitening agents, antifoaming agents or surfactants, polyvinylpyrrolidone, organic solvents such as methanol.

A thiosulfate can be used as the fixing agent component in the bleach-fixing solution. Examples of the thiosulfate include sodium thiosulfate, potassium thiosulfate, and ammonium thiosulfate. Other known fixing agents, thiocyanates such as sodium thiocyanate and ammonium thiocyanate; ethylenebisthioglycolic acid, thioether compounds such as 3,6-dithia-1,8-octanediol, mesoionic compounds, and thioureas It is also possible to use the water-soluble silver halide dissolving agent. In the present invention, the use of thiosulfates, particularly ammonium thiosulfate and sodium thiosulfate, is preferred. The total amount of the fixing agent per liter is preferably 0.3 to 3 mol, more preferably 0.5 to 2.0 mol.

The bleach-fixing solution of the present invention may contain a sulfite (or bisulfite or metabisulfite) as a preservative. Specifically, 0.01 to 0.5 mol /
The content is preferably 0.02 to 0.3 mol / l. In addition, as preservatives, aldehydes (benzaldide, acetaldehyde, etc.), ketones (acetone, etc.), ascorbic acids, hydroxylamines, etc. can be added as necessary.

Furthermore, buffers, optical brighteners, chelating agents,
A defoaming agent, an antifungal agent, etc. may be added as necessary. In the bleach-fixing solution used in the present invention, the pH can be set in the range of 2 to 9, but particularly in the stain and image storability improving effects of the present invention, the preferred pH range is 4 to 9.
It is 5.5, and most preferably 4.5 to 5.5.
In order to maintain the above pH, it is preferable that the bleach-fixing solution contains an organic acid represented by the following general formula (II), which is also a preferable embodiment from the viewpoint of improving stain and image storability.

[0034]

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In the formula, when n = 1, A represents an alkyl group or a phenyl group, when n = 2, A represents a single bond divalent linking group, and when n = 3, A represents a trivalent group. Represent M represents a hydrogen atom, an alkali metal or an ammonium salt.

Next, details of the compound represented by formula (II) will be described. When n = 1, the alkylene group of A preferably has 1 to 10 carbon atoms, and more preferably 2 to 5 carbon atoms.
It is. The alkylene group and the phenyl group may have a substituent, and as the substituent, a hydroxy group, a halogen atom,
Examples thereof include an amino group, a sulfo group and an acylamino group, and a hydroxy group is particularly preferable.

When n = 2, A is specifically a substituted or unsubstituted alkylene group, alkenyl group, phenyl group, cyclohexyl group or heterocyclic group (for example, N as a hetero atom,
A 5- to 8-membered ring compound containing at least one of O and S is preferable, and a 5- to 6-membered ring compound containing N is particularly preferable. For example, pyrrole, pyridine, pyrrolidine, piperidine, etc. can be mentioned. ) Etc. n = 3
In this case, A represents a trivalent linking group, specifically, a phenyl group, a cyclohexyl group, a heterocyclic group (for example, a 5- to 8-membered ring containing at least one hetero atom, N, O, S, etc.). Is preferable, and a 5- or 6-membered ring compound containing N is particularly preferable, and examples thereof include pyrrole, pyridine, pyrrolidine, and piperidine). The carbon number of the group represented by A in the case of n = 2 and n = 3 is preferably 10 or less. The n M's may be the same or different. Specific examples are shown below, but the present invention is not limited to these.

[0038]

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[0039]

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[0040]

[Chemical 12]

[0041]

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Among the above compounds, in the present invention, n = 2
Dicarboxylic acids of are preferred. Specifically, II-20, II-
21, II-22, II-23, II-24, II-26, II-
27, II-28, and II-29 can be mentioned. The amount of these organic acids added is 0.0 per 1 liter of the final bath.
05 to 0.5 mol, preferably 0.005 to 0.1 mol. If the pH of the membrane can be maintained, it is preferable that the added amount be small. If necessary, two or more kinds may be used in combination. The compound of the general formula (II) is known, and a commercially available product can be easily purchased.

The replenishing amount of the bleach-fixing solution used in the present invention is ²⁰ to 2000 ml per 1 m ² of the light-sensitive material, and the effect of the present invention is remarkably exhibited when the amount is 30 to 300 ml. Further, washing water as a post-bath or overflow solution of a stabilizing bath may be replenished as necessary. The processing temperature of the bleach-fixing solution is 20 to 50 ° C, preferably 30 to 45 ° C. Processing time is 10 seconds to 6
Minutes, preferably 20 seconds to 3 minutes.

The circulating amount of the bleach-fixing solution of the present invention must be 1.5 ≦ S / V ≦ 10, where V = tank volume (liter) and S = circulating amount (liter / min). That is, in the conventional processing machine, the tank capacity is within the range of 5 liters to 500 liters, and the S / V value is within the range of 0.1 to 1.0. Was the amount. That is, with a tank capacity of 10 liters, circulation was performed at 1.0 to 10 liters / minute. This is because if the circulation is further strengthened, the desilvering rate and the like will be advantageous, but the oxidative deterioration of the solution will be accelerated, and this will be a factor in the generation of stains. In the present invention, it is preferable to apply it to a relatively small processing tank of about 1 to 10 liters. Further, by strengthening stirring in such a processing tank, rather than causing stain, it is rather good. It has been found that it will turn. A preferable S / V value is about 2.0 to 8.0. If the S / V value is smaller than that of the present invention, the effect of the present invention cannot be obtained,
If the value is too large, stains will still be generated, so
Not preferable. Such stirring is disclosed in JP-A-62-183.
The most preferable embodiment is the so-called jet agitation method described in JP-A No. 460, in which a jet flow is made to collide with the emulsion surface of a light-sensitive material. In addition, JP-A-62-183461
As described in No. 3, a method of increasing the stirring efficiency by using a rotating means may be used in combination.

The bleach-fixing solution of the present invention may be aerated during processing. Any means known in the art can be used for aeration, and air can be blown into a processing solution having bleaching ability, or air can be absorbed using an ejector. When blowing air,
Air is preferably released 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 the aeration, the matters described on pages BL-1 to BL-2 of Z-121, Eusing Process C-41 3rd edition (1982), published by Eastman Kodak Company can be used. In the treatment using the treatment liquid having the bleaching ability of the present invention, it is preferable that stirring is strengthened,
The contents described in JP-A-3-33847, page 8, upper right column, line 6 to lower left column, line 2 can be used as they are.

The automatic processors used in the light-sensitive material of the present invention are disclosed in JP-A-60-191257, JP-A-60-191258 and JP-A-60-1912.
It is preferable to have a photosensitive material conveying means described in No. 59. 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 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 amount of water in the multi-stage countercurrent method is described in the Journal of the
Society of Motion Pictureand Television Engineers
Vol. 64, pp. 248-253 (May, 1955). 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
No. -8,542, isothiazolone compounds, thiabendazoles, chlorinated fungicides such as chlorinated sodium isocyanurate, and other benzotriazoles, etc., written by Hiroshi Horiguchi, "Chemistry of Fungicides and Fungicides" (1986) Sankyo Publishing Co., Ltd. "Sterilization, Sterilization, and Mold Prevention Techniques of Microorganisms" edited by the Sanitation Technology Society (1982), Japan Society of Industrial Technology, "The Encyclopedia of Bactericidal and Antifungal Agents" (ed. 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, Examples include N-methylol compounds such as dimethylol urea and N-methylol pyrazole, organic acids and pH buffering agents. The preferable addition amount of these compounds is from 0.001 to 0.02 mol per liter of the stabilizing solution. However, the lower the concentration of free formaldehyde in the stabilizing solution, the less the formaldehyde gas is scattered. From these viewpoints, examples of the dye image stabilizer include N-methylolazoles such as m-hydroxybenzaldehyde, hexamethylenetetramine and N-methylolpyrazole described in JP-A-4-270344, and N, N'-bis (1 4,3,4-triazol-1-ylmethyl) piperazine and the like.
Azolylmethylamines described in 13753 are preferred. In particular, azoles such as 1,2,4-triazole and 1,4-bis (1,2,4) described in JP-A-4-359249 (corresponding to EP-A-519190A2).
A combination of azolylmethylamine and its derivative such as (-triazol-1-ylmethyl) piperazine is preferable because of high image stability and low formaldehyde vapor pressure. Further, if necessary, ammonium compounds such as ammonium chloride and ammonium sulfite, metal compounds such as Bi and Al, a fluorescent brightener, a hardener, and US Pat.
No. 86,583, and a preservative which can be contained in the above-mentioned fixing solution or bleach-fixing solution, for example, a sulfinic acid compound described in JP-A-1-231105 is also preferable. .

In the present invention, after the bleach-fixing step,
Processing in a stabilizing bath having a pH of 3 to 6 is desirable for reducing stains and stabilizing the image storability after processing.
Particularly, the range of pH 4 to 5.5 is preferable. In order to set the pH within the above range, it is desirable to use various organic acids. Specific examples thereof include acetic acid, oxalic acid, malonic acid, succinic acid, glutaric acid, malic acid, citric acid, maleic acid, and phthalic acid. This low pH stabilizer is
A multi-stage countercurrent method may be adopted, or a final bath may be adopted after a water washing process. In order to prevent unevenness of water droplets when the photosensitive material after processing is dried,
Various surfactants can be included. 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. It is preferable to add various chelating agents to the wash water and / or the stabilizing solution. Preferred chelating agents include aminopolycarboxylic acids such as ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, β-alaninediacetic acid, α-methyl-nitrilotriacetic acid and 1-hydroxyethylidene-1,1-diphosphonic acid, N, N, N. ′
-Trimethylene phosphonic acid, diethylene triamine-
Organic phosphonic acids such as N, N, N ', N'-tetramethylenephosphonic acid or EP 345,172A
Examples thereof include the hydrolyzate of the maleic anhydride polymer described in No. 1 and the like. The replenishing amount of the washing water and / or the stabilizing solution of the present invention may be in the range of about 1 to 1000 times the carry-in amount of the pre-fixing bath having fixing ability, but in the water saving specification of about 3 to 30 times. In this case, the effect of the present invention can be remarkably obtained.

The overflow solution accompanying the above washing with water and / or supplementation of the stabilizing solution can be reused in other steps such as the desilvering step. In the processing using an automatic developing machine or the like, when each of the above processing solutions is 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 replenisher. There is no particular limitation on a specific method for performing water replenishment. Among them, a monitor water tank separate from the bleaching tank described in JP-A Nos. 1-254959 and 1-254960 is installed, and water in the monitor water tank is provided. The amount of evaporation of water is calculated, the amount of evaporation of water in the bleaching tank is calculated from the amount of evaporation of water, and water is supplied to the bleaching tank in proportion to the amount of evaporation.
Nos. 3,249,644, 3,249,645, and 3,249,646, the evaporation correction method using a liquid level sensor and an overflow sensor are preferable.
Tap water may be used as water for correcting the evaporation of each processing solution, but it is preferable to use deionized water or sterilized water which is preferably used in the above-mentioned washing step. In the present invention, the replenishment amount means a processing liquid replenished per unit area of the light-sensitive material in order to obtain stable finishing performance (to suppress fluctuations in photographic characteristics) even when the light-sensitive material is continuously processed ( (E.g. color developing solution, bleach-fixing solution). This amount means the amount of all the liquids and solids added per unit area, and the solid + liquid replenishment means the arithmetic total value. Here, even if the treatment liquid to be replenished is one liquid, even if it is divided into two or more liquids due to the stability of the liquid itself and the necessity of dividing the replenishment function (eg, treatment replenishment and aging replenishment). Good. In addition, when replenishing in divided portions, it may be divided into concentrated liquid and diluted water. In this case, the former may be a concentrated solution or a solid agent (eg, powder, granules, tablets, etc., solid, paste, jelly, etc.). As a method of replenishing, the treatment tank may be directly replenished in a state of being divided into two or more liquids, or two or more liquids may be mixed before replenishing.

Next, the light-sensitive material of the present invention will be described.
The present invention can be applied to any photosensitive material, but is preferably applied to a color paper, a color negative film, a color reversal film, and the like.
Application to color negative films is preferred. The silver halide emulsion and other materials (additives, etc.) and photographic constituent layers (layer arrangement, etc.) applied in the present invention, and the processing method and processing additive applied for processing the light-sensitive material are , The following patent publications, in particular European patent EP 0,35
Those described in 5,660A2 (Japanese Patent Application No. 1-107011) are preferably used.

[0053]

[Table 1]

[0054]

[Table 2]

[0055]

[Table 3]

[0056]

[Table 4]

[0057]

[Table 5]

The silver halide emulsion used in the present invention is:
Silver iodobromide, silver iodochloride, silver iodochlorobromide, silver chlorobromide, silver bromide,
Emulsions of various halogen compositions such as silver chloride can be used. In particular, the present invention preferably has a layer containing a silver iodobromide emulsion and has an iodine content of 1.0 to 10
It is preferable to use an emulsion containing about mol%. As the coating amount of silver is not particularly limited, 2g~8g / m ² approximately, and more preferably may contain about 3 to 6 g / m ^2. If it is less than the main coating silver amount, the image quality is deteriorated, which is not preferable, and if it is more than the coating silver amount, the stain is deteriorated, which is not preferable. The light-sensitive material used in the present invention may contain various couplers, but the details are as shown in Table 2. Further, as a cyan coupler, JP-A-2-
In addition to the diphenylimidazole-based cyan couplers described in 33144, 3-hydroxypyridine-based cyan couplers described in European Patent EP0,333,185A2 (among others, the 4-equivalent couplers of couplers (42) listed as specific examples are chlorine-containing couplers). Two equivalents with a leaving group or coupler (6)
And (9) are particularly preferable) and the cyclic active methylene cyan couplers described in JP-A 64-32260 (coupler examples 3, 8, and 34 listed as specific examples are particularly preferable) are also preferably used. .

Further, in the light-sensitive material according to the present invention, a hydrophilic colloid layer can be decolorized by a treatment described in European Patent EP 0,337,490A2, pages 27 to 76 for the purpose of improving image sharpness and the like. Such dyes (among others, oxonol dyes) can be added so that the optical reflection density at 680 nm of the photosensitive material becomes 0.70 or more. In the color photographic light-sensitive material according to the present invention, it is preferable to use a color image storability-improving compound as described in European Patent EP 0,277,589A2 together with a coupler. In particular, it is preferably used in combination with a pyrazoloazole coupler.

That is, a compound (F) and / or a compound which chemically bonds with the aromatic amine developing agent remaining after the color development processing to form a chemically inactive and substantially colorless compound.
Alternatively, the compound (G) which chemically bonds with an oxidized product of an aromatic amine color developing agent remaining after the color developing treatment to form a chemically inactive and substantially colorless compound is used simultaneously or alone. However, it is preferable to prevent the occurrence of stains and other side effects due to the formation of a coloring dye due to the reaction of the residual color developing agent in the film or the oxidant thereof with the coupler during storage after processing. Further, to the light-sensitive material according to the present invention, a fungicide such as that described in JP-A-63-271247 is added in order to prevent various molds and bacteria that propagate in the hydrophilic colloid layer and deteriorate the image. Preferably. In the present invention, it is preferable that the dry film thickness of the silver halide color photographic light-sensitive material excluding the support is 25 μm or less in order to reduce the carryover amount and increase the silver recovery rate. Particularly, it is preferably about 13 to 23 μm, more preferably about 9 to 19 μm. These film thicknesses can be reduced by reducing the gelatin amount, silver amount, oil amount, coupler amount, etc., but it is most preferable to reduce the gelatin amount. Here, the film thickness is 25 ° C. for the sample,
After being left at 60 RH% for 2 weeks, it can be measured by a conventional method.

When the silver halide color photographic light-sensitive material of the present invention has a magnetic recording layer, the magnetic reading accuracy is improved, which is a desirable mode. The silver halide photographic material carrying magnetic recording preferably used in the present invention is a thin film of preheated polyester described in detail in JP-A-6-35118, JP-A-6-17528, and JIII Journal of Technical Disclosure No. 94-6023. Layer support, eg, polyethylene aromatic dicarboxylate based polyester support, 5
0 μm to 300 μm, preferably 50 μm to 200 μm
m, more preferably 80 to 115 μm, and particularly preferably 85 to 105 μm, is heat-treated (annealed) at a temperature of 40 ° C. or higher and a glass transition point temperature or lower for 1 to 1500 hours to obtain Japanese Patent Publication Nos. 43-2603 and 43-2604, Japanese Patent Sho 45
UV irradiation described in -3828, JP-B-48-5043,
Surface treatment such as corona discharge described in JP-A-51-131576 and glow discharge described in JP-B-35-7578 and JP-B-46-43480, and undercoating as described in USP 5,326,689 are performed. 761, 791
The undercoat layer described in JP-A-59-2350 is provided.
5, the ferromagnetic particles described in JP-A-4-195726 and JP-A-6-59357 may be applied. The above-mentioned magnetic layer is disclosed in JP-A-4-124642 and JP-A-4-124464.
The stripe shape described in 5 may be used. Further, if necessary, an antistatic treatment described in JP-A-4-62543 is used, and a product coated with a silver halide emulsion is finally used. The silver halide emulsion used here is disclosed in JP-A-4-166932 and JP-A-316932.
-41436 and JP-A-3-41437 are used. It is preferable that the photosensitive material thus produced is manufactured by the manufacturing management method described in Japanese Patent Publication No. 4-86817, and the manufacturing data is recorded by the method described in Japanese Patent Publication No. 6-87146. After that, or before that,
According to the method described in Japanese Patent Application Laid-Open No. 4-125560, a film having a width smaller than that of the conventional 135 size is cut, and perforations are provided on each side of the small format screen to match the small format screen smaller than the conventional one.
Make a hole. The film thus produced is disclosed in JP-A-4-1.
57459 cartridge package and Japanese Patent Laid-Open No. 5-2102
02 cartridge or USP shown in FIG.
4, 221, 479 film patrones and USP4,
834, 306, US4, 834, 366, USP5
226, 613, USP 4, 846, 418 are used by being put in the cartridge described. The film cartridge or film cartridge used here is USP 4,84
A type capable of accommodating a tongue, such as No. 8,693, USP5, 317, and 355, is preferable from the viewpoint of light shielding properties. Further, a cartridge having a lock mechanism such as USP5, 296, 886, a cartridge displaying a usage state described in USP5, 347, 334, or a cartridge having a double exposure preventing function is preferable. In addition, Japanese Unexamined Patent Publication No.
As described in 85128, a cartridge in which the film is easily attached by simply inserting the film into the cartridge may be used.

The film cartridge thus produced can be used for the purpose of photographing, developing, and enjoying various photographs by using a camera, a developing machine, and a laboratory device described below.
For example, a simple loading camera described in JP-A-6-8886 and JP-A-6-99908, an automatic winding camera described in JP-A-6-57398 and JP-A-6-101135, and a photographing camera described in JP-A-6-205690 are disclosed. Camera that can take out and replace the type of film with
8. A camera capable of magnetically recording information on photographing, for example, panoramic photographing, high-definition photographing, and normal photographing (magnetic recording capable of selecting print aspect ratio) described in JP-A-5-283382 or JP-A-6-101194.
Camera having a double exposure prevention function described in
If a camera or the like having a function of displaying the use state of the film described in 150577 is used, the function of the film cartridge (patrone) can be sufficiently exhibited. Films photographed in this manner are disclosed in JP-A-6-222514 and JP-A-6-222514.
Japanese Patent Application Laid-Open Nos. Hei 6-95265, Hei 4-95265, and
The method of utilizing magnetic recording on a film described in No. 123054 may be used, or the aspect ratio selection function described in JP-A-5-19364 may be used. In the case of cine-type development, the film is spliced and processed according to the method described in JP-A-5-119461. Also, during or after the development process, the attach and detach processes described in JP-A-6-148805 are performed. After processing in this manner, see JP-A-2-1848.
35, JP-A-4-186335, JP-A-6-79968
The film information may be converted into a print through back printing and front printing on color paper by the method described in (1). Further, Japanese Patent Application Laid-Open Nos.
It may be returned to the customer together with the index print and return cartridge described in 232594.

Cartridges used in the present invention include US Pat. Nos. 4,848,893 and 5,317,
No. 355, No. 5,347,334, No. 5,296,886
And JP-A-6-85128 are preferable. Particularly, in the thrust type in which the tongue is not exposed, the effect of the present invention becomes closer to the closed chamber state in the cartridge, and the effect of the present invention becomes more remarkable.

A preferred embodiment of a camera for photographing the light-sensitive material of the present invention will be described. JP-A-6-888 for simple loading
No. 6, No. 6-99908, No. 6-57398, No. 6-101135 as automatic winding, No. 6-205690 as taking out during photographing, and No. 5-293138 as print aspect ratio selective recording function.
No. 5-283382, JP-A No. 6-101194 as a double exposure prevention function, and JP-A No. 5-150577 as a use state display function are preferable. The preferred embodiments of the laboratory processing and equipment used in the present invention will be described. Regarding the use of magnetic recording, JP-A-6-95265 and 4-
123054, US Pat. Nos. 5,034,838 and 5,
No. 041,933, JP-A-5-19364 as a print aspect ratio selectable mechanism, and JP-A-2-184835 and 4-1863 as a function of printing information on a print.
No. 35, No. 6-79968, and No. 5-11353, No. 5-232594 as index print functions.
No. 6, attach and detach functions.
No. 05, JP-A-5-119461 as a splice function
As a cartridge magazine function
Aspects of Nos. 346 and 5-19439 are preferable.

Next, the magnetic recording layer used in the present invention will be described. The magnetic recording layer used in the present invention is obtained by coating a support with an aqueous or organic solvent-based coating solution in which magnetic particles are dispersed in a binder. The magnetic particles used in the present invention include ferromagnetic iron oxides such as γFe2O3, Co-deposited γFe2O3, Co-deposited magnetite, Co-containing magnetite, ferromagnetic chromium dioxide, ferromagnetic metals, ferromagnetic alloys, and hexagonal Ba. Ferrite, Sr ferrite, Pb ferrite, Ca ferrite, etc. can be used. Co deposition γFe2O3
Co-coated ferromagnetic iron oxides such as The shape may be needle-like, rice grain-like, spherical, cubic, plate-like or the like.
Preferably at least 20 m ² / g in SBET is the specific surface area, and particularly preferably equal to or greater than 30 m ² / g. The saturation magnetization (σs) of the ferromagnetic material is preferably 3.0 × 10 4 to 3.0 × 10 5 A / m, particularly preferably 4.0 × 10 4 to 2.5 × 10 5 A / m. Ferromagnetic particles,
Surface treatment with silica and / or alumina or an organic material may be performed. Further, magnetic particles are disclosed in JP-A-6-1610.
The surface may be treated with a silane coupling agent or a titanium coupling agent as described in 32. Also JP
The magnetic particles described in 4-259911 and 5-81652 whose surface is coated with an inorganic or organic substance can also be used.

Next, the binder used for the magnetic particles is
Thermoplastic resin described in JP-A-4-219569, thermosetting resin,
Radiation-curable resins, reactive resins, acids, alkalis or biodegradable polymers, natural polymers (cellulose derivatives, sugar derivatives, etc.) and mixtures thereof can be used. Tg of the above resin is -40 ℃ ~ 300 ℃, the weight average molecular weight is
It is 20,000 to 1 million. Examples thereof include vinyl copolymers, cellulose diacetate, cellulose triacetate, cellulose derivatives such as cellulose acetate propionate, cellulose acetate butyrate, and cellulose tripropionate, acrylic resins and polyvinyl acetal resins, and gelatin is also preferable. Particularly, cellulose di (tri) acetate is preferable. The binder can be cured by adding an epoxy-based, aziridine-based, or isocyanate-based crosslinking agent. As the isocyanate-based cross-linking agent, tolylene diisocyanate,
Isocyanates such as 4,4′-diphenylmethane diisocyanate, hexamethylene diisocyanate and xylylene diisocyanate, and reaction products of these isocyanates and polyalcohols (for example, a reaction product of 3 mol of tolylene diisocyanate and 1 mol of trimethylolpropane). ), And polyisocyanates produced by condensation of these isocyanates, and are described in, for example, JP-A-6-59357.

As a method for dispersing the above-mentioned magnetic material in the binder, a kneader, a pin type mill, an annular type mill or the like is preferable and a combination thereof is also preferable, as in the method described in JP-A-6-35092. Dispersants described in JP-A-5-088283 and other known dispersants can be used. The thickness of the magnetic recording layer is 0.1 μm to 10 μm, preferably 0.2 μm to 5 μm.
m, more preferably 0.3 μm to 3 μm. The weight ratio between the magnetic particles and the binder is preferably 0.5: 100 to 60: 100.
And more preferably from 1: 100 to 30: 100. The coating amount of the magnetic particles 0.005~ 3g / m ^2, preferably from 0.01 to 2
g / m ² , more preferably 0.02 to 0.5 g / m ² . The transmission yellow density of the magnetic recording layer is preferably 0.01 to 0.50,
03 to 0.20 is more preferable, and 0.04 to 0.15 is particularly preferable.
The magnetic recording layer can be provided on the entire back surface of the photographic support by coating or printing, or in a stripe shape. As a method of applying the magnetic recording layer, an air doctor, a blade, an air knife, a squeeze, an impregnation, a reverse roll,
Transfer rolls, gravure, kisses, casts, sprays, dips, bars, extrusions and the like can be used, and the coating solutions described in JP-A-5-341436 are preferred.

The magnetic recording layer has improved lubricity, curl adjustment,
It may have functions such as antistatic, anti-adhesion and head polishing, or may be provided with another functional layer to impart these functions, and at least one kind of particles has a Mohs hardness of 5 or more. The above-mentioned non-spherical inorganic particle abrasives are preferable. As the composition of the non-spherical inorganic particles, oxides such as aluminum oxide, chromium oxide, silicon dioxide, titanium dioxide and silicon carbide, carbides such as silicon carbide and titanium carbide, and fine powders such as diamond are preferable. These abrasives may have their surfaces treated with a silane coupling agent or a titanium coupling agent. These particles may be added to the magnetic recording layer, or may be overcoated (for example, a protective layer, a lubricant layer, etc.) on the magnetic recording layer. As the binder used at this time, the above-mentioned binders can be used, and the same binder as the binder for the magnetic recording layer is preferable. For photosensitive materials having a magnetic recording layer, see US Pat.
5,229,259, 5,215,874 and EP 466,130.

Next, the film support used in the present invention will be described. In the present invention, any film support can be used, but in the sense that the effect of the present invention is more exerted, a polyester support (PEN) is used.
Is preferred. Details of the polyester support will be described, but details such as a photosensitive material, a treatment, a cartridge and an example described later are described in Public Technical Report No. 94-6023 (Invention Society; 1994.3.15.). There is. The polyester used in the present invention is formed by using a diol and an aromatic dicarboxylic acid as essential components.
6-, 1,5-, 1,4-, and 2,7-naphthalenedicarboxylic acid, terephthalic acid, isophthalic acid, phthalic acid,
Examples of the diol include diethylene glycol, triethylene glycol, cyclohexanedimethanol, bisphenol A and bisphenol. Examples of the polymerized polymer include homopolymers such as polyethylene terephthalate, polyethylene naphthalate, and polycyclohexanedimethanol terephthalate. Particularly preferred is a polyester containing 50 to 100 mol% of 2,6-naphthalenedicarboxylic acid. Among them, polyethylene 2,6-naphthalate is particularly preferable.
The average molecular weight ranges from about 5,000 to 200,000. The polyester of the present invention has a Tg of 50 ° C or higher, and further 90 ° C.
The above is preferable.

The polyester support is preferably heat-treated at a heat treatment temperature of 40 ° C. or higher and lower than Tg, more preferably Tg-20 ° C. or higher and lower than Tg (APEN) in order to prevent curling habit. The heat treatment may be performed at a constant temperature within this temperature range, or may be performed while cooling. The heat treatment time is 0.1 hours or more and 1500 hours or less, more preferably 0.5 hours or more and 200 hours or less. The heat treatment of the support may be performed in the form of a roll, or may be performed while transporting the support in the form of a web. Give unevenness to the surface (for example, apply conductive inorganic fine particles such as SnO2 or Sb2O5),
The surface condition may be improved. It is also desirable to take measures such as applying knurls to the ends and raising the ends only slightly to prevent cut-out of the core. These heat treatments may be performed at any stage after the formation of the support, after the surface treatment, after the application of the back layer (antistatic agent, slip agent, etc.), and after the application of the undercoat. Preferably after application of the antistatic agent. An ultraviolet absorber may be incorporated into this polyester. To prevent light piping, Mitsubishi Kasei's Diaresin,
The object can be achieved by kneading a commercially available dye or pigment for polyester such as Kayaset manufactured by Nippon Kayaku.

Next, in the present invention, it is preferable to carry out a surface treatment in order to bond the support and the light-sensitive material constituting layer. Chemical treatment, mechanical treatment, corona discharge treatment, flame treatment, ultraviolet treatment, high frequency treatment, glow discharge treatment, active plasma treatment,
Surface activation treatments such as laser treatment, mixed acid treatment, ozone oxidation treatment and the like can be mentioned. Among the surface treatments, ultraviolet irradiation treatment, flame treatment, corona treatment, and glow treatment are preferable. Next, the undercoating method will be described. It may be a single layer or two or more layers. As the binder for the undercoat layer, vinyl chloride, vinylidene chloride, butadiene, methacrylic acid,
Examples include a copolymer using a monomer selected from acrylic acid, itaconic acid, maleic anhydride and the like as a starting material, polyethylene imine, epoxy resin, grafted gelatin, nitrocellulose, and gelatin. Compounds that swell the support include resorcin and p-chlorophenol. As a gelatin hardening agent for the undercoat layer, chromium salts (chrome alum, etc.), aldehydes (formaldehyde, glutaraldehyde, etc.), isocyanates, active halogen compounds (2,4-dichloro-6-) are used.
Hydroxy-S-triazine, etc.), epichlorohydrin resin, active vinyl sulfone compound and the like. SiO2, TiO2, inorganic fine particles or polymethylmethacrylate copolymer fine particles (0.01 to 10 μm) may be contained as a matting agent.

In the present invention, an antistatic agent is preferably used. Examples of these antistatic agents include carboxylic acids and carboxylates, polymers containing sulfonates, cationic polymers, and ionic surfactant compounds. The most preferred antistatic agent is Z
nO, TiO2, SnO2, Al2O3, In2O3, SiO2, MgO, BaO,
At least one selected from MoO3 and V2O5 has a volume resistivity of 107 Ω · cm or less, more preferably 105 Ω · cm or less. Particle size 0.001 to 1.0 μm crystalline metal oxide or a composite thereof. Fine particles of oxides (Sb, P, B, In, S, Si, C, etc.), and further fine particles of sol-like metal oxides or composite oxides thereof. The content in the photosensitive material should be between 5 and
500 mg / m ² are preferred and particularly preferably 10 to 350 mg / m ^2. The ratio of the amount of the conductive crystalline oxide or its composite oxide to the binder is preferably from 1/300 to 100/1, more preferably from 1/100 to 100/5.

The light-sensitive material of the present invention preferably has a slip property. The slip agent-containing layer is preferably used on both the photosensitive layer surface and the back surface. A preferable slip property is a dynamic friction coefficient of 0.
It is 25 or less and 0.01 or more. The measurement at this time represents the value when the stainless steel ball with a diameter of 5 mm is transported at 60 cm / min (25
℃, 60% RH). In this evaluation, even when the surface of the photosensitive layer is replaced as the partner material, the values are almost the same level. Examples of the slip agent usable in the present invention include polyorganosiloxanes, higher fatty acid amides, higher fatty acid metal salts, esters of higher fatty acids and higher alcohols, and polyorganosiloxanes such as polydimethyl siloxane, polydiethyl siloxane, poly Styrylmethylsiloxane, polymethylphenylsiloxane, or the like can be used. The additional layer is preferably the outermost layer of the emulsion layer or the back layer. Particularly, polydimethylsiloxane or an ester having a long-chain alkyl group is preferable.

The sensitive material of the present invention preferably contains a matting agent. The matting agent may be on either the emulsion side or the back side, but is particularly preferably added to the outermost layer on the emulsion side.
The matting agent may be soluble in the processing solution or insoluble in the processing solution, and preferably both are used in combination. For example, polymethylmethacrylate, poly (methylmethacrylate / methacrylic acid = 9/1 or 5/5 (molar ratio)), polystyrene particles and the like are preferable. The particle size is preferably 0.8 to 10 μm, and the particle size distribution is preferably narrow, and the average particle size is 0.9 to 1.
It is preferable that 90% or more of the total number of particles be contained in one time. It is also preferable to simultaneously add fine particles having a size of 0.8 μm or less in order to enhance the matting property. For example, polymethyl methacrylate (0.2 μm), poly (methyl methacrylate /
Methacrylic acid = 9/1 (molar ratio, 0.3 µm)), polystyrene particles (0.25 µm), colloidal silica (0.03 µm).

In the silver halide color photographic light-sensitive material used in the present invention, the film swelling degree of the photographic layer is 1.5 to.
A value of 4.0 is preferable from the viewpoint of improving stain and improving image storability. Particularly, in the range of 1.5 to 3.0, a further effect can be obtained. The swelling degree of the present invention means a value obtained by dividing the film thickness of the photographic layer after dipping the color light-sensitive material in distilled water at 33 ° C. for 2 minutes by the film thickness of the dried photographic layer.

The term "photographic layer" as used herein refers to a laminated hydrophilic colloid group layer containing at least one photosensitive silver halide emulsion layer and having a water-permeable relationship with this layer. The back layer provided on the opposite side of the support from the photographic photosensitive layer is not included. The photographic layer is usually formed of a plurality of layers involved in photographic image formation, and includes an intermediate layer, a filter layer, an antihalation layer, a protective layer and the like in addition to the silver halide emulsion layer.

Any method may be used to adjust the degree of swelling. For example, the amount and type of gelatin used in the photographic film, the amount and type of hardener, or the drying conditions after coating the photographic layer. And can be adjusted by changing the aging condition. It is advantageous to use gelatin for the photographic layer, but other hydrophilic colloids can also be used. For example, gelatin derivatives, graft polymers of gelatin and other polymers, proteins such as albumin and casein, cellulose derivatives such as hydroxyethylcellulose, carboxymethylcellulose and cellulose sulfates, sugar derivatives such as sodium alginate and starch derivatives; polyvinyl alcohol Use of various kinds of synthetic hydrophilic high-molecular substances such as mono- or copolymers such as polyvinyl alcohol partial acetal, poly-N-vinylpyrrolidone, polyacrylic acid, polymethacrylic acid, polyacrylamide, polyvinylimidazole and polyvinylpyrazole Can be. As the gelatin, acid-treated gelatin may be used in addition to lime-treated gelatin, and gelatin hydrolyzate and gelatin enzyme-decomposed product may also be used. Examples of the gelatin derivative include gelatin such as acid halide,
Those obtained by reacting various compounds such as acid anhydrides, isocyanates, bromoacetic acid, alkane sultones, vinylsulfonamides, maleimide compounds, polyalkylene oxides and epoxy compounds are used.

As the gelatin graft polymer, a homopolymer or copolymer of vinyl monomers such as acrylic acid, methacrylic acid, derivatives thereof such as esters and amides, acrylonitrile and styrene are grafted onto gelatin. What was made to use can be used. In particular, a graft polymer with a polymer having a certain degree of compatibility with gelatin, for example, a polymer such as acrylic acid, methacrylic acid, acrylamide, methacrylamide, or hydroxyacryl methacrylate is preferable.
Examples of these are disclosed in U.S. Pat.
31, 767 and 2,956,884. Representative synthetic hydrophilic polymeric substances are described, for example, in West German Patent Application (OLS) 2,312,708, U.S. Pat.
No. 620, 751, No. 3, 879, 205;
No. 3-7561.

Examples of hardening agents include chromium salts (chromium alum, chromium acetate, etc.), aldehydes (formaldehyde, glyoxal, glital aldehyde, etc.), N-methylol compounds (dimethylol urea, methylol dimethylhydantoin, etc.), dioxane. Derivatives (2,3-dihydroxydioxane, etc.), active vinyl compounds (1,3,5-triacryloyl-hexahydro-s-triazine, bis (vinylsulfonyl) methyl ether, N, N'-methylenebis- [β- (vinyl Sulfonyl) propionamide] etc.), active halogen compounds (2,4-dichloro-6-hydroxy-s-triazine etc.), mucohalogen acids (mucochloric acid, mucophenoxycycloric acid etc.), isoxazoles, dialdehyde starch, 2-black And 6-hydroxy-triazinyl gelatin can be used alone or in combination. Particularly preferred hardeners are aldehydes,
They are active vinyl compounds and active halogen compounds.

The light-sensitive material according to the present invention may be exposed to visible light or infrared light. The exposure method may be low-illuminance exposure or high-illuminance short-time exposure, and in the latter case, a laser scanning exposure method in which the exposure time per pixel is shorter than 10 ⁻⁴ seconds is preferable. Further, it is preferable to use the band stop filter described in U.S. Pat. No. 4,880,726 upon exposure. As a result, light color mixture is removed, and color reproducibility is significantly improved.

[0081]

EXAMPLES The present invention will be described in more detail with reference to Examples below.
The present invention is not limited to these. Embodiment 1 FIG. (1) Material of Support, etc. Each support used in this example was prepared by the following method. PEN: 100 parts by weight of commercially available poly (ethylene-2,6-naphthalate) polymer and Tinuvi as an ultraviolet absorber
n 2 parts by weight of P.326 (manufactured by Geigy) were dried by a conventional method, melted at 300 ° C., and extruded from a T-die.
The film was longitudinally stretched 3.3 times at 0 ° C, and then 3.3 times at 130 ° C.
Double stretching was performed, and heat setting was further performed at 250 ° C. for 6 seconds. The glass transition temperature was 120 ° C. -TAC: methylene chloride / methanol = 82/8 wt.
Ratio, TAC concentration 13%, plasticizer TPP / BDP = 2/1
(Here, TPP; triphenyl phosphate, BD
P; biphenyl diphenyl phosphate) 15 wt%
Produced by the band method described above. As described above, PEN (APEN) heat-treated on the support
101 using the sample, and PEN without heat treatment
Was designated as Sample 103. Also, 1 sample using TAC
02.

(2) Coating of Undercoat Layer Each of the above supports is subjected to corona discharge treatment on both sides thereof, and then an undercoat solution having the following composition is applied to provide the undercoat layer on the high temperature surface side during stretching. It was For the corona discharge treatment, a solid state corona treatment machine 6KVA model manufactured by Pillar Co. is used, and a 30 cm width support is treated at 20 m / min. 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 processing is 9.6KHz,
The gap clearance between the electrode and the dielectric roll is 1.6.
It was mm.

Gelatin 3 g Distilled water 250 ml Sodium-α-sulfodi-2-ethylhexyl succinate 0.05 g Formaldehyde 0.02 g Further, an undercoat layer having the following composition was provided on the support TAC. Gelatin 0.2 g Salicylic acid 0.1 g Methanol 15 ml Acetone 85 ml Formaldehyde 0.01 g (3) Coating of back layer On one side of the undercoated support prepared in (2), the following back layers 1 to 3 are formed. The layers were applied. A) Back first layer Co-containing acicular γ-iron oxide fine powder (containing as gelatin dispersion; average particle size 0.08 μm) 0.2 g / m ² gelatin 3 g / m ² described in the following chemical formula 14. 0.1 g / m ² Compound described in Chemical formula 15 below 0.02 g / m ² Poly (ethyl acrylate) (average diameter 0.08 μm) 1 g / m ²

[0084]

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[0085]

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(B) Second layer of back gelatin 0.05 g / m ² conductive material [S _n O ₂ / Sb ₂ O ₃ (9: 1), particle size 0.15 μm] 0.16 mg / m ² dodecylbenzenesulfone Acid soda 0.05 g / m ² c) Back third layer Gelatin 0.5 g / m ² polymethylmethacrylate (average particle size 1.5 μm) 0.02 g / m ² cetyl stearate (sodium dodecylbenzenesulfonate dispersion) 0.01 g / m ² Sodium di (2-ethylhexyl) sulfosuccinate 0.01 g / m ² Compound described in the following chemical formula 16 0.01 g / m ²

[0087]

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The coercive force of the obtained back layer is 960 Oe.
Met. (4) Heat Treatment of Support After the undercoat layer and the back layer were applied and dried and wound by the above method, heat treatment was performed at 110 ° C. for 48 hours. The photosensitive layer shown in (5) was coated on the two types of supports prepared by the above method to prepare a photosensitive material. The PEN support was used as sample 101, and the TAC support was used as sample 102. A sample 103 was the PEN support that had not been subjected to the heat treatment (4). (5) Preparation of photosensitive layer 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 hardening agent ExS: Sensitizing dye The numeral corresponding to each component indicates the coating amount expressed in 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 Silver 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 x 10 ^-2 HBS-4 5.0 x 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 0.70

Further, in order to improve storage stability, processability, pressure resistance, antifungal / antibacterial property, antistatic property and coating property, W-1 to W-3, B-4 to B- may be appropriately added to each layer. 6, F
-1 to F-17, and iron salts, lead salts, gold salts, platinum salts,
It contains a palladium salt, an iridium salt, and a rhodium salt.

[0104]

[Table 6]

In Table 6, (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 were performed in the presence of the spectral sensitizing dye and sodium thiocyanate described in each photosensitive layer. (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 described in JP-A-3-237450 are observed in the tabular grains using a high-pressure electron microscope. (5) Emulsion L is a double-structured 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
Milliliter and 3% of a 5% aqueous solution of sodium p-octylphenoxyethoxyethoxyethoxyethanesulfonate and 0.5 g of a 5% aqueous solution of p-octylphenoxypolyoxyethylene ether (degree of polymerization: 10) were placed in a 700 milliliter pot mill, followed by dyeing. 5.0 g of ExF-2 and 500 ml of zirconium oxide beads (diameter 1 mm) were added, and the contents were dispersed for 2 hours. For this dispersion, a BO type vibration ball mill manufactured by Chuo Koki was used. After 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 fine dye particles was 0.44 μm.

Similarly, solid dispersions of ExF-3, ExF-4 and ExF-6 were obtained. The average particle diameters of the fine dye 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.
Dispersed by a dispersion method. The average particle size was 0.06 μm.

[0108]

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[0109]

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[0110]

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[0111]

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[0112]

[Chemical 21]

[0113]

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[0114]

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[0115]

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[0116]

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[0117]

[Chemical formula 26]

[0118]

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[0119]

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[0120]

[Chemical 29]

[0121]

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[0122]

[Chemical 31]

[0123]

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The photosensitive material 101 prepared as described above
The width of the photosensitive material 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. This 2
Two sets were provided at intervals of 32 mm, and FIG. 1 to FIG. 7
In a plastic film cartridge described in (1). An FM signal was recorded on this sample at a feed rate of 100 mm / s during the above-mentioned perforation of the photosensitive material by using a head gap of 5 μm from the coated surface side of the magnetic recording layer and a turnable number of 2000.

After recording the FM signal, 1000 cms on the emulsion surface
After uniform exposure of the entire surface of the above-mentioned item 1 and each processing by the method described below, the film was stored again in the original plastic film cartridge. Next, 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, and it was examined whether or not the signal was correctly output.
Table 6 shows the ratio of the number of error bits to the number of input bits. If this error rate is 0.01% or less, there is no practical problem, but if it is 0.1% or more, it is NG. Also,
For the processed photosensitive material, the minimum yellow density (DBmi
n) was measured with a Macbeth densitometer. Further, the processed photosensitive material was evaluated for the increase in magenta stain after 1 week under the condition of 60 ° C. and 70% RH. (ΔDGmin) Next, the details of the processing performed will be described. The sample described above has a color temperature of 4800K.
At 20 cms for gray exposure through a wedge wedge, and processing was performed with the cine type automatic processor with the following processing steps and processing solutions. As shown in Table 7, the bleach-fixing solution was changed in circulation amount and pH, and each of them was sequentially processed.

(Treatment Process) Treatment Process Temperature Time Tank Capacity Circulation Volume Color development 42 ° C. 90 seconds 4 liters 4 liters / min Bleach fixing 40 ° C. 60 seconds 3 Table 7 stability (1) 40 ° C. 15 seconds 22 liters / min Stability (2) 40 ℃ 15 seconds 2 2 〃 Stability (3) 40 ℃ 15 seconds 2 2 〃 Dry 75 ℃ 30 seconds (Stable with 3 tank countercurrent method from (3) to (1) The circulation was such that the processing liquid hits the emulsion surface perpendicularly through multiple slits with a width of 1 mm. The bleach-fix solution was prepared by inserting a flow meter into the circulation system and using a pinch cock so that the flow rate would be a predetermined value.

The composition of each processing liquid is as follows. (Color developer) (Unit: g) Tank solution Diethylenetriaminepentaacetic acid 4.0 4,5-Dihydroxybenzene-1,3-disulfonic acid disodium salt 0.5 Sodium sulfite 4.0 Potassium carbonate 38.0 Potassium bromide 4.0 Potassium iodide 1.3 mg Hydroxylamine sulfate Salt 4.8 2-Methyl-4- [N-ethyl-N- (β-hydroxyethyl) amino] aniline sulfate 10.0 Water was added to 1.0 liter pH (adjusted with potassium hydroxide and sulfuric acid) 10.25

(Bleach-fixing solution) (Unit: g) Tank solution 200 ml of the above color developer Ethylenediamine- (2-carboxyphenyl) -N, N ', N'-triacetic acid 0.10 mol Ethylenediaminetetraacetic acid 0.08 mol Ferric chloride 0.16 mol Ammonium thiosulfate aqueous solution (700 g / l) (ATS) 300 ml Ammonium iodide 1.0 g Ammonium sulfite 15.0 g Compound of general formula (I) 0.2 mol Succinic acid 10.0 g Water added 1.0 liter pH (adjusted with nitric acid and aqueous ammonia) ) See Table 7

(Stabilizing Solution) The tank solution and the replenishing solution have the same formulation (unit: g) sodium p-toluenesulfinate 0.03 polyoxyethylene-p-monononylphenyl ether (average degree of polymerization: 10) 0.2 sodium chlorinated isocyanurate 0.02 Deionized water (conductivity 5 μs / cm or less) 1000 ml pH 6.5 bleach-fix solution was processed for each of which the formulation was changed. The results are shown in Table 7.

[0130]

[Table 7]

As is clear from the results of Table 7, in the present invention, the increase in stain due to the passage of time of yellow stain and magenta is improved, and the reading accuracy of magnetic recording is also improved. Especially, the pH of the bleach-fixing solution is 4.0.
The most favorable result was shown in .about.5.5.

Example 2 No. 1 of the first example. In the treatment of 9, instead of the compound I-9, I-1, I-3, I-18, I-26, I-2
When 8 and I-34 were used, almost the same excellent results were obtained.

Example 3. No. 1 of the first embodiment. Under the processing conditions 1 to 12, samples 102 and 103 having different supports from the sample 101 of Example 1
Was used to evaluate the magnetic reading accuracy in the same manner. The results are shown in Table 8.

[0134]

[Table 8]

In the present invention, the magnetic reading accuracy was improved, and in particular, the sample 10 using the heat-treated PEN support was used.
1 showed the most preferable result.

Example 4. Sample 101 of Example 1 was imagewise exposed and then continuously processed in the following processing steps until the replenishing amount of the bleach-fixing solution was replenished to twice the tank volume. (Processing process) Processing process Temperature Time Replenishment amount Tank capacity Color development 45 ℃ 60 seconds 260 (ml / m ² ) 2 (liter) Bleach fixing 40 ℃ 60 seconds 260 2 stability (1) 40 ℃ 15 seconds − 0.7 stability (2) 40 ° C for 15 seconds-0.7 stability (3) 40 ° C for 15 seconds 390 0.7 Dry 75 ° C for 60 seconds (Stability is a 3-tank countercurrent system from (3) to (1).) Bleach-fixer In the same manner as in Example 1, the circulating amount was changed as shown in Table 9 and the running test was performed for each of them. Further, using an electrolytic silver recovery device BF-12 manufactured by Mazda Sangyo, the silver concentration was controlled so as to be kept at 2 to 5 g / liter while desilvering.

The composition of the processing liquid is shown below. As the bleach-fixing solution, the compound of the general formula (II) was changed, and running was performed for each of them, and DBmin and ΔDG were changed in the same manner as in Example 1.
min, magnetic reading accuracy was obtained. (Color developer) Tank liquid (g) Replenisher (g) Diethylenetriaminepentaacetic acid 2.0 2.0 1-Hydroxyethylidene-1,1-diphosphonic acid 2.0 2.0 Sodium sulfite 3.9 5.1 Potassium carbonate 37.5 39.0 Potassium bromide 1.5-Potassium iodide 1.3 mg-N-hydroxy- (N, N-bissulfonate methyl) hydroxylamine 5.0 10.0 2-Methyl-4- [N-ethyl-N- (β-hydroxyethyl) amino] aniline sulfate 6.0 10.0 Add water 1.0 liter 1.0 liter pH (adjusted with potassium hydroxide and sulfuric acid) 10.15 10.25

(Bleach-fixing solution) Tank solution (g) Replenishing solution (g) Ethylenediamine- (2-carboxyphenyl) -N, N ', N'-triacetic acid 0.16 mol 0.25 mol Ethylenediaminetetraacetic acid 0.03 mol 0.05 mol Chloride chloride Diiron 0.16 mol 0.27 mol Ammonium bromide 70 105 Ammonium nitrate 14 21 Compound of general formula (II) (see Table 9) 0.15 mol 0.15 mol Ammonium sulfite 19 57 Ammonium thiosulfate aqueous solution (700 g / l) 280 ml 840 ml Imidazole 15 45 I -25 0.15 mol 0.20 mol Add water 1.0 liter 1.0 liter pH [Prepared with ammonia water and acetic acid] 4.5 4.0

(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 Ethylenediaminetetraacetic acid disodium salt 0.05 1, 2,4-triazole 1.3 1,4-bis (1,2,4-triazol-1-ylmethyl) piperazine 0.75 malonic acid 5.0 water added 1.0 liter pH 5.5

The composition of the bleach-fix solution was changed as shown in Table 9, and each of them was subjected to continuous processing until the tank capacity of the bleach-fix solution was doubled. The results are shown in Table 9.

[0141]

[Table 9]

From Table 9, according to the present invention, the stain was improved and the reading accuracy of magnetic recording was improved.

Example 5. Next, a color print material was prepared in the following manner. After the corona discharge treatment is applied to the surface of the paper support laminated with polyethylene on both sides, a gelatin subbing layer containing sodium dodecylbenzene sulfonate is provided, and various photographic constituent layers are further coated to form a multilayer color having the layer constitution shown below. A photographic printing paper (201) was produced. The coating solution was prepared as follows.

Preparation of coating solution for first layer Yellow coupler (ExY) 153.0 g, color image stabilizer (C
pd-1) 15.0 g, color image stabilizer (Cpd-2) 7.5 g,
16.0 g of color image stabilizer (Cpd-3) was used as a solvent (Solv-
1) 25 g, solvent (Solv-2) 25 g and ethyl acetate 1
This was dissolved in 80 cc, and this solution was emulsified and dispersed in 1000 g of a 10% gelatin aqueous solution containing 10 cc of 10% sodium dodecylbenzenesulfonate and 10 g of citric acid to prepare an emulsified dispersion A. On the other hand, silver chlorobromide emulsion A (cubic, average grain size of 0.
3: 7 mixture of large emulsion A of 88 μm and small emulsion A of 0.70 μm (silver molar ratio). Coefficients of variation of grain size distribution are 0.08 and 0.10 respectively, and silver bromide for each size emulsion
0.3 mol% was locally contained on a part of the surface of the grain based on silver chloride) was prepared. In this emulsion, the blue-sensitive sensitizing dyes A and B shown below are large-sized emulsions A per mol of silver.
For, 2.0 × 10 ^-4 mol, respectively, also to the small size emulsion A, are respectively 2.5 × 10 ^-4 mol per mol. The chemical ripening of this emulsion was performed by adding a sulfur sensitizer and a gold sensitizer. The above emulsified dispersion A and this silver chlorobromide emulsion A were mixed and dissolved to prepare a coating solution for the first layer having the following composition. The emulsion coating amount indicates a coating amount in terms of silver amount.

The coating solutions for the second to seventh layers were prepared in the same manner as the coating solution for the first layer. As the gelatin hardening agent for each layer, 1-oxy-3,5-dichloro-s-triazine sodium salt was used. Also, Cpd-14 and C are added to each layer.
total amount pd-15 were added to each so that 25.0 mg / m ² and 50.0 mg / m ^2. The following spectral sensitizing dyes were used for the silver chlorobromide emulsion of each photosensitive emulsion layer. Blue-sensitive emulsion layer

[0146]

[Chemical 33]

(2.0 × 10 ^-4 mol for large size emulsion and 2.5 × 10 ^-4 mol for small size emulsion, respectively, per mol of silver halide) Green-sensitive emulsion layer

[0148]

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(4.0 × 10 ^-4 mol per mol of silver halide for large size emulsions, and for small size emulsions)
5.6 × 10 ^-4 mol) and,

[0150]

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(7.0 × 10 ⁻⁵ mol for large size emulsion and 1.0 × 10 ⁻⁴ mol for small size emulsion per mol of silver halide) Red-sensitive emulsion layer

[0152]

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(0.9 × 10 ⁻⁴ mol for large size emulsion and 1.1 × 10 ⁻⁴ mol for small size emulsion per mol of silver halide)

Further, the following compounds were added in an amount of 2.6 × 10 ^-3 mol per mol of silver halide.

[0155]

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For the blue-sensitive emulsion layer, the green-sensitive emulsion layer and the red-sensitive emulsion layer, 1- (5-methylureidophenyl)-
5-mercaptotetrazole was replaced by silver halide 1
8.5 x 10 ^-5 mol, 7.7 x 10 ^-4 mol, 2.5 x 10 per mol
^-4 mol was added. Further, 4-hydroxy-6-methyl-1,3,3a, 7 was added to the blue-sensitive emulsion layer and the green-sensitive emulsion layer.
Tetrazaindene was added in an amount of 1 × 10 ^-4 mol and 2 × 10 ^-4 mol per mol of silver halide, respectively. Further, in order to prevent irradiation, the following dye (the amount in parentheses represents the coating amount) was added to the emulsion layer.

[0157]

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(Layer Structure) The composition of each layer is shown below. The numbers represent the coating amount (g / m ² ). The silver halide emulsion represents a coating amount in terms of silver. Support Polyethylene laminated paper [The first layer of polyethylene contains white pigment (TiO ₂ ) and bluish dye (ultra blue)]

First Layer (Blue Sensitive Emulsion Layer) Silver Chlorobromide Emulsion A 0.27 Gelatin 1.36 Yellow Coupler (ExY) 0.79 Color Image Stabilizer (Cpd-1) 0.08 Color Image Stabilizer (Cpd-2) 0.04 Color Image stabilizer (Cpd-3) 0.08 Solvent (Solv-1) 0.13 Solvent (Solv-2) 0.13

Second Layer (Color Mixing Prevention Layer) Gelatin 1.00 Color mixing inhibitor (Cpd-4) 0.06 Solvent (Solv-2) 0.25 Solvent (Solv-3) 0.25 Solvent (Solv-7) 0.03

Third Layer (Green Sensitive Emulsion Layer) Silver chlorobromide emulsion (cubic, 1: 3 mixture of large size emulsion B having an average grain size of 0.55 μm and small size emulsion B of 0.39 μm (Ag molar ratio)) The coefficient of variation of the grain size distribution is 0.10 and 0.08, respectively, and AgBr is 0.8 mol% for each size emulsion.
0.13 gelatin 1.45 magenta coupler (ExM) 0.16 color image stabilizer (Cpd-2) 0.03 color image stabilizer (Cpd-5) 0.15 color Image Stabilizer (Cpd-6) 0.01 Color Image Stabilizer (Cpd-7) 0.01 Color Image Stabilizer (Cpd-8) 0.08 Solvent (Solv-3) 0.50 Solvent (Solv-4) 0.15 Solvent (Solv-5) 0.15

Fourth Layer (Color Mixing Prevention Layer) Gelatin 0.70 Color mixing inhibitor (Cpd-4) 0.04 Solvent (Solv-2) 0.18 Solvent (Solv-3) 0.18 Solvent (Solv-7) 0.02

Fifth layer (red-sensitive emulsion layer) Silver chlorobromide emulsion (cubic, 1: 4 mixture of large size emulsion C having an average grain size of 0.50 μm and small size emulsion C of 0.41 μm (Ag mole ratio)) . Coefficient of variation of particle size distribution is 0.09
And 0.11, AgBr 0.8 mol% was locally contained in a part of the surface of the grain based on silver chloride in each size emulsion)
0.20 Gelatin 0.85 Cyan coupler (ExC) 0.33 Ultraviolet absorber (UV-2) 0.18 Color image stabilizer (Cpd-1) 0.33 Color image stabilizer (Cpd-6) 0.01 Color image stabilizer (Cpd-8) 0.01 Color image Stabilizer (Cpd-9) 0.01 Color image stabilizer (Cpd-10) 0.01 Color image stabilizer (Cpd-11) 0.01 Solvent (Solv-1) 0.01 Solvent (Solv-6) 0.22

Sixth layer (UV absorbing layer) Gelatin 0.55 UV absorbing agent (UV-1) 0.38 Color image stabilizer (Cpd-5) 0.02 Color image stabilizer (Cpd-12) 0.15

Seventh Layer (Protective Layer) Gelatin 0.13 Polyvinyl alcohol acrylic modified copolymer (degree of modification
17%) 0.05 Liquid paraffin 0.02 Surfactant (Cpd-13) 0.01

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[0167]

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[0168]

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[0169]

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[0170]

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[0171]

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The color paper (Sample 201) obtained as described above was processed into a roll having a width of 89 mm and exposed imagewise. Next, the exposed paper was continuously processed in the following processing steps. The bleach-fix solution has a formula and circulation amount of 10th.
Changes were made as shown in the table, each of which was treated continuously until replenishment of 3 times the tank volume. Process temperature Temperature Replenishment amount Tank volume Circulation amount (℃) (sec) (ml / m ² ) (L) (L / min) Color development 42.0 ℃ 25 40 3 2 Bleach fixing 38.0 ℃ 15 40 2 See Table 10 Water Wash (1) 38.0 ° C 3 − 0.5 1 Wash with water (2) 38.0 ° C 3 − 0.5 1 Wash with water (3) 38.0 ° C 3 − 0.5 1 Wash with water (4) 38.0 ° C 3 − 0.5 1 Wash with water (5) 38.0 ° C 5 70 0.7 1 Dry 90 ° C Washing with water is a countercurrent method from (5) to (1). The carry-over amount per 1 m ^{2 of} light-sensitive material is 35 in each bath.
ml.

The composition of each processing liquid is as follows. [Color developer] [Tank solution] [Replenisher] Water 800 ml 800 ml Ethylenediaminetetraacetic acid 3.0 g 3.0 g 4,5-dihydroxybenzene-1,3-disulfonic acid disodium salt 0.5 g 0.5 g Potassium chloride 7.5 g- Potassium bromide 0.03 g-potassium carbonate 27.0 g 27.0 g Diaminostilbene optical brightener (WHITEX 4 manufactured by Sumitomo Chemical Co., Ltd.) 1.0 g 3.0 g sodium sulfite 0.1 g 0.1 g disodium-N, N-bis (sulfonate ethyl) hydroxyl Amine 5.0 g 10.0 g Sodium triisopropylnaphthalene (β) sulfonate 0.1 g 0.1 g N-ethyl-N- (β-methanesulfonamidoethyl) -3-methyl-4-aminoaniline / 3/2 sulfuric acid monohydrate 6.0 g 13.5 g Add water 1000 ml 1000 ml pH (25 ° C / potassium hydroxide) Adjusted by the arm and sulfuric acid) 10.00 11.10

[Bleach-fixing solution] [Tank solution] [Replenishing solution] Water 600 ml 150 ml Ammonium thiosulfate (750 g / liter) 93 ml 230 ml Ammonium sulfite 40 g 100 g Ethylenediaminetetraacetic acid iron (III) ammonium 55 g 135 g Ethylenediaminetetraacetic acid 5 g 12.5 g Nitric acid (67%) 30 g 65 g General formula (I) compound 0.12 mol 0.15 mol Water added 1000 ml 1000 ml pH (25 ° C / adjusted with acetic acid and ammonia water) 5.2 4.8

[Rinse Solution] (The tank solution and the replenisher are the same) Sodium chlorinated isocyanurate O.02 g Deionized water (conductivity 5 μs / cm or less) 1000 ml pH 6.5

The unexposed sample 201 was treated with the equilibrium liquid for each running, and the minimum density (DBmin) of the treated yellow was measured. Further, the amount of increase in magenta stain (ΔDGmin) was measured after 10 days under the condition of 80C-70%. The above results are shown in Table 10.

[0177]

[Table 10]

From Table 10, in the present invention, the increase in yellow stain and magenta stain was greatly improved, and particularly the most preferable result was shown under the circulation condition where the S / V value was 2 or more and 8 or less.

[0179]

The good desilvering performance can be obtained even under rapid processing. It is possible to suppress the generation of stains and suppress the temporal stain of magenta.

Claims (3)

[Claims] 1. A processing method in which an image-exposed silver halide color photographic light-sensitive material is subjected to desilvering treatment with a bleach-fixing solution after color development, wherein the bleach-fixing solution satisfies 1.5 ≤ S / V ≦ 10 where V = tank volume (liter), S = circulation amount (liter / min), and the bleach-fixing solution contains at least one compound represented by the following general formula (I). A method for processing a silver halide color photographic light-sensitive material, which is characterized. General formula (I) (In the formula, R represents an alkyl group, a cycloalkyl group, an alkenyl group, an alkynyl group, an aralkyl group, or an aryl group. M represents a hydrogen atom, an alkali metal atom, ammonium, or a quaternary amine.) 2. The pH of the bleach-fixing treatment is 4 to 5.5.
2. The method for processing a silver halide color photographic light-sensitive material according to claim 1, wherein 3. The silver halide according to claim 1, wherein the silver halide color photographic light-sensitive material has a magnetic recording layer containing magnetic particles on the side opposite to the light-sensitive layer with respect to the support. Color photographic light-sensitive material processing method.