JPH0250152A - Method of processing silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To decrease the volume of a waste liquid and to allow a rapid desilvering processing by executing the processing while bringing a fixing processing soln. into contact with an anion exchange resin and specifying the amt. of the fixing processing soln. to be used per 1l anion exchange resin to 20-2,000l. CONSTITUTION:The processing is executed while the processing soln. having fixability (fixing processing soln.) is brought into contact with the anion exchange resin and the amt. of the fixing processing soln. to be used per 1l anion exchange resin is specified to 20-2,000l. The processing can be executed continuously by exchanging the anion exchange resin with a fresh resin when or before the cumulative amt. of the processing soln. used attains 2,000l. The volume of the waste liquid is decreased in this way and the rapid desilvering processing is executed.

Description

DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to a method for processing silver halide photographic light-sensitive materials, and more specifically, to a method for processing silver halide photographic light-sensitive materials quickly and reducing the amount of waste liquid of a processing solution capable of fixing the photographic light-sensitive materials. This invention relates to a processing method for reducing and desilvering.

(Prior Art) The basic steps in the processing of silver halide photosensitive materials, such as color photosensitive materials, are a color development step and a desilvering step. In the color development step, the exposed silver halide is reduced by a color developing agent to produce silver, and the oxidized color developing agent reacts with a color former (coupler) to provide a dye image. In the next desilvering step, the silver produced in the color development step is oxidized by the action of an oxidizing agent (commonly called a bleaching agent), and then dissolved by a silver ion complexing agent, commonly called a fixing agent. Ru. By going through this desilvering step, only a dye image is created on the color photosensitive material.

The above desilvering process is carried out in two baths, a bleaching bath containing a bleaching agent and a fixing bath containing a fixing agent, or in one bath using a bleach-fixing bath containing both a bleaching agent and a fixing agent. There is.

Furthermore, in addition to the above-mentioned basic steps, the actual development process includes various auxiliary steps for maintaining the photographic and physical quality of the image or for improving the storage stability of the image. Examples include a hardening bath, a stop bath, an image stabilization bath, and a water washing bath.

It takes a long time to desilver a light-sensitive material made of an emulsion containing silver iodide, such as a color negative light-sensitive material for photography, and there is a strong desire to shorten the time required for the fixing process.

In addition, from the perspective of pollution prevention, there is a strong desire to reduce the amount of photographic waste liquid, and reducing the amount of fixing solution waste, for example, reducing the amount of replenishment, is an important issue in the desilvering process. .

By the way, a number of methods have been studied to recover silver, a valuable precious metal, from bleach-fix solutions or fixing solutions. These methods include collecting the dissolved carbon as a precipitate, adding sodium sulfide to recover silver sulfide, and using a large amount of ion exchange resin to recover silver in the form of ions. Regarding these silver recovery methods, for example, "Kodak Publication J-10 (Recovering Silver Frame Photographic Material)" (Published by Kodak Industrial Division), Special Publication No. 58-2252
Specification No. 8, JP-A-54-19496, Belgian Patent No. 869087, West German Published Patent No. 263
It is described in the specification of No. 0661, etc.

However, these silver recovery methods were originally intended to recover silver from the bleach-fix solution, and are not necessarily intended for reusing the bleach-fix solution after silver recovery processing. Therefore, the bleach-fix solution after the above silver recovery process cannot be reused, or in order to reuse it, it is necessary to add the components lost during the silver recovery process (addition of a regenerating agent). There were various obstacles to reusing the bleach-fix solution after silver recovery.Therefore, it was decided to use silver recovery methods to reduce the amount of waste solution and perform quick desilvering. was not necessarily realized.

(Problems to be Solved by the Invention) Therefore, the present invention provides a method for processing a silver halide photographic light-sensitive material that has rapid fixing ability and reduces the amount of waste liquid of a processing solution that has fixing ability. There is a particular thing.

(Means for Solving the Problems) An object of the present invention is to process a silver halide photographic material having at least one silver iodobromide emulsion layer on a support with a processing solution having fixing ability. In the processing method for photographic light-sensitive materials, a processing liquid having the fixing ability (fixing processing liquid)
A silver halide photographic light-sensitive material, characterized in that the processing is carried out while contacting with an anion exchange resin, and the amount of the processing liquid having the fixing ability used is 201 to 200 (l) per 1 liter of the anion exchange resin. This was achieved using the following processing method.

Here, when or before the cumulative amount of processing liquid used reaches 200 liters, the processing can be continued by replacing the anion exchange resin with a new one. The liquid processing may be so-called continuous processing or batch processing. In order to easily process a large amount of photosensitive material, continuous processing using an automatic developing device is preferable.

As a result of cutting-edge research, the present inventors have found that a processing solution (fixing processing solution) whose fixing ability is fatigued due to the processing of photosensitive materials containing silver iodide contains a large amount of silver ions. Contains a small amount of iodide ions,
It has become clear that the fixing ability is significantly reduced by the effects of both.

In an attempt to recover silver ions from a processing solution with such fatigued fixing ability, when the various silver recovery methods described above are carried out, thiosulfate, which is a fixing agent, or sulfite ions, which are its preservative, are decomposed or This will have the negative effect of removing it.

In contrast, the present inventors have discovered that by removing iodide ions from a processing solution that has fixing ability, it is possible to sufficiently recover the fixing ability even if silver ions remain. Moreover, it has been discovered that by treating a processing solution with a tired fixing ability with an anion exchange resin, iodide ions can be removed very selectively among the inorganic ions in the solution. In addition, when processing a processing liquid having fixing ability with a unit volume of the above-mentioned anion exchange resin,
It has also become clear that there is a certain appropriate amount range for the cumulative amount of processing liquid used.

Furthermore, if the processing time of the bath with fixing ability and the subsequent washing and/or stabilization process is shortened (e.g. 5 minutes or less), the magenta stain (D
However, when the anion exchange resin of the present invention is used, this problem does not occur and it can be said that the treatment method is very suitable for rapid treatment. It is assumed that this is due to the anion exchange resin removing colored contaminants such as dyes.

In other words, when attempting to process a fixer with an anion exchange resin IIt exceeding 20,004 ml, the iodide ions will not be removed sufficiently by the resin, and 1 liter of resin
When processing a fixing solution with a concentration of 2ON or less, a large amount of thiosulfate, which is a fixing agent, is removed in addition to iodide ions, and it becomes necessary to add thiosulfate as a regenerating agent.

In addition, in the latter case, the amount of resin used increases, which is undesirable from a cost standpoint.
Because it is removed by ion exchange resin in the form of thiosulfate,
Resin II! The amount of fixer to be processed per treatment is about 5 to 15 Il.

The photosensitive material to be processed in the present invention contains at least one silver halide emulsion layer containing silver iodide in an amount of 1 mol % or more, preferably 5 mol % to 25 mol %, more preferably 7 to 20 mol %. It is characterized by having a layer.

Therefore, one or more silver iodides selected from silver iodide, silver iodobromide, silver chloride iodobromide, and silver chloroiodide are used to form one or more emulsion layers. is applied onto a support to form a color photosensitive material. At this time, in addition to silver iodide, silver chloride, silver bromide, etc. can be optionally used.

The silver halide grains in the photographic emulsion used in the color photographic light-sensitive material of the present invention are cubic, octahedral, rhombidodecahedral, and monododecahedral.
It may have a regular crystal shape such as a tetrahedron, or it may have an irregular crystal shape such as a spherical shape or a plate shape, or a composite shape of these crystal shapes. Research Disclosure (Research Disclosure)
closure) Vol. 225, pp. 20-58 (1983
The grains may be tabular grains having an aspect ratio of 5 or more as described in (January 2013). Further, the particles may have an epitaxial structure, or may have a multilayer structure in which the inside and the surface of the particle have different compositions (for example, halogen composition).

Further, the average size of the particles is preferably 0°5μ or more. More preferably, the average size is 0°7μ or more and 5.0
It is less than μ.

Also, the particle size distribution may be broad or narrow. The latter is known as a so-called monodisperse emulsion, and its dispersion coefficient is preferably 20% or less, more preferably 15% or less (here, the dispersion coefficient is the standard deviation divided by the average grain size). The coating silver amount of the photosensitive material of the present invention is 1 to 2
It is preferably 0 g/rd, especially 2 to 10 g/rd, and the total iodine amount (A
ge) is preferably 4 x 10 mol/d or more, more preferably 6 x 10-' mol/d or more and 4
X1'0-''mol/ffr or less.

Cadmium salts, zinc salts, lead salts, thallium salts, iridium salts, or complex salts thereof, rhodium salts or complex salts thereof, iron salts or complex salts thereof, etc. may be present in the stage of silver halide grain formation or physical ripening. .

The processing liquid having fixing ability (fixing processing liquid) of the present invention means a bleach-fixing liquid or a fixing liquid.

When the processing solution having fixing ability of the present invention is a bleach-fix solution, a bleach accelerator can also be used.

As a result of the method of the present invention making it possible to reduce iodine ions, it is possible to reduce the amount of replenishment of the fixing treatment liquid, and at the same time, the amount of waste liquid can be reduced. Therefore, a low-cost, low-pollution, and quick fixing method has become possible.

The basic anion exchange resin used in the present invention is preferably represented by the following general formula (■).

−Maximum (■) R.I.S. ÷l-, +B÷, ÷CH, -C+.

The person in the formula represents a monomer unit copolymerized with a copolymerizable monomer having at least two copolymerizable ethylenically unsaturated groups and at least one of which is included in the side chain.
B represents a monomer unit copolymerized with a copolymerizable ethylenically unsaturated monomer, and R1 represents a hydrogen atom, a lower alkyl group, or an aralkyl group.

Q represents a single bond or a group represented by an alkylene group, a phenylene group, an aralkylene group, -C-0-L, C-NH-L-, or -C-NR-L-, where L is an alkylene group, an arylene group, group or an aralkylene group, and R represents an alkyl group.

Rras R1s% R16% Rtt, Rr
as R+? , R16sR1l represents a hydrogen atom, an alkyl group, an aryl group, or an aralkyl group, which may be the same or different from each other, and may be substituted.

Xe represents an anion, and Q, RIa, RIS,
RIa or Q, Rty, R1l, R1l, Rto,
Two or more arbitrary groups of R2° may be bonded to each other to form a ring structure together with the nitrogen atom.

X%y1 and 2 represent mole percentage, X is 0 to 6
0 to 0, y represents a value from O to 60.2 represents a value from 30 to 100.

In the method of the present invention, continuous processing means that the processing solution is replenished and the processing is carried out continuously or intermittently over a long period of time. The amount of processing liquid (replenisher) to be replenished is determined depending on, for example, the area of the photosensitive material to be processed and the processing time.

Generally, replenishment of a processing solution with fixing ability is carried out according to the area of the photosensitive material being processed.If the amount of replenishment is reduced, the desilvering rate is thought to be due to the accumulation of eluates from the photosensitive material. Desilvering failure occurs at a certain processing time.

By using the compound of the present invention, it is possible to prevent the delay in derailment due to the delay in fixing, and it is possible to achieve a quick fixing process with a low replenishment amount.

To explain the maximum (■) above in more detail, examples of monomers in A are divinylbenzene, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate,
Ethylene glycol diacrylate, diethylene glycol diacrylate, 1,6-hexanediol diacrylate, neopentyl glycol dimethacrylate,
Ants such as tetramethylene glycol dimethacrylate,
Among these, divinylbenzene and ethylene glycol diacrylate are particularly preferred.

A may contain two or more types of the above monomer units.

Examples of ethylenically unsaturated monomers in B are ethylene, propylene, 1-butene, isobutyne, styrene, α
- methylstyrene, vinyltoluene, monoethylenically unsaturated esters of aliphatic acids (e.g. vinyl acetate, allyl acetate), esters of ethylenically unsaturated monocarboxylic or dicarboxylic acids (e.g. methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, n-
hexyl methacrylate, cyclohexyl methacrylate, benzyl methacrylate, n-butyl acrylate, n-hexyl acrylate, 2-ethylhexyl acrylate) monoethylenically unsaturated compounds (e.g. acrylonitrile) or dienes (e.g. butadiene, isoprene), etc. Among these, styrene, n-butyl methacrylate, cyclohexyl methacrylate, etc. are particularly preferred. B may contain two or more types of the above monomer units.

R1 is a hydrogen atom or a lower alkyl group having 1 to 6 carbon atoms (e.g. methyl group, ethyl group, n-propyl group, n
-butyl group, n-amyl group, n-hexyl group), aralkyl group (eg benzyl group), and among these, hydrogen atom or methyl group is particularly preferred.

Q is preferably a divalent optionally substituted alkylene group having 1 to 12 carbon atoms (e.g., methylene group, ethylene group, hexamethylene group), an optionally substituted arylene group (e.g., phenylene group), or a carbon atom. An optionally substituted aralkylene group having 7 to 12 carbon atoms (for example, L is an optionally substituted alkylene group having 1 to 6 carbon atoms, an optionally substituted arylene group having 7 to 12 carbon atoms, or an optionally substituted arylene group having 7 to 12 carbon atoms) An optionally substituted aralkylene group is preferred, and an optionally substituted alkylene group having 1 to 6 carbon atoms is more preferred.

R is preferably an alkyl group having 1 to 6 carbon atoms.

A group represented by the following formula is also preferred.

R1, R15% R16% R1? , R1l%
RIq and RZ@5R1l are preferably a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or an aralkyl group having 7 to 20 carbon atoms, and each is the same. It may be different or different. These alkyl groups, aryl groups, and aralkyl groups include substituted alkyl groups, substituent groups, and substituted aralkyl groups.

Examples of the alkyl group include unsubstituted alkyl groups such as methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, t-butyl group, n-amyl group,
Isoamyl group, n-hexyl group, cyclohexyl group, n
-hebutyl group, n-octyl group, 2-ethylhexyl group, n-nonyl group, n-decyl group, n-dodecyl group, etc.; the alkyl group preferably has 1 to 16 carbon atoms.

More preferably, the number of carbon atoms is 4 to 10.

Examples of substituted alkyl groups include alkoxyalkyl groups (e.g., methoxymethyl, methoxyethyl, methoxybutyl, ethoxyethyl, ethoxypropyl, ethoxybutyl, butoxyethyl, butoxypropyl, butoxybutyl, vinyloxyethyl), cyanoalkyl groups (e.g., 2-cyanoethyl, 3-cyanopropyl, 4-cyanobutyl), halogenated alkyl groups (e.g. 2-fluoroethyl, 2-chloroethyl, 3-fluoropropyl), alkoxycarbonylalkyl groups (e.g. ethoxycarbonylmethyl), allyl groups, 2 -butenyl group, propargyl group, etc.

Examples of the aryl group include unsubstituted aryl groups (e.g. phenyl, naphthyl); examples of substituted aryl groups include alkylaryl groups (e.g. 2-methylphenyl, 3-methylphenyl, 4-methylphenyl, 4-ethylphenyl, 4
-isopropylphenyl% 4-tert-butylphenyl), alkoxyaryl groups (e.g. 4-methoxyphenyl, 3methoxyphenyl group, 4-ethoxyphenyl)
, aryloxyaryl group (eg, 4-phenoxyphenyl), and the like. The aryl group preferably has 6 to 14 carbon atoms, more preferably 6 to 10 carbon atoms. Particularly preferred is a phenyl group.

Examples of aralkyl groups include unsubstituted aralkyl groups (e.g. benzyl, phenethyl, diphenylmethyl, naphthylmethyl); substituted aralkyl groups such as alkylaralkyl groups (e.g. 4-methylbenzyl, 2,5-dimethylbenzyl, 4-isopropylbenzyl). , alkoxyaralkyl groups (e.g. 4-methoxybenzyl, 4-ethoxybenzyl), cyanoaralkyl groups (e.g. 4-cyanobenzyl), perfluoroalkoxyaralkyl groups (e.g. 4-pentafluoropropoxybenzyl, 4-undecafluoro) hexyloxybenzyl), halogenated aralkyl groups (for example, 4-chlorobenzyl, 4-bromobenzyl, 3-chlorobenzyl), and the number of carbon atoms in the aralkyl group is preferably 7 to 15, preferably 7 ~1l pieces. Among these, benzyl group and phenethyl group are particularly preferred.

Of R1 R+ss RI&, preferably an alkyl group,
It is an aralkyl group, and particularly preferably an alkyl group in which the total number of carbon atoms of R14, RIS, and Ro is 12 to 30.

Among R1ff, R11, R11, R8°, and R□, hydrogen atoms and alkyl groups are preferred.

Xe represents an anion, such as a hydroxide ion, a halogen ion (e.g., chlorine, bromine), an alkyl or aryl sulfonic acid ion (e.g., methanesulfonic acid, ethanesulfonic acid, benzenesulfonic acid, p-toluenesulfonic acid), an acetate ion, Examples include sulfate ions and nitrate ions, with chloride ions, acetate ions, and sulfate ions being particularly preferred.

Further, it is also preferable that two or more arbitrary groups of Q, R14, R+s, and R1& are bonded to each other to form a cyclic structure together with the nitrogen atom. The cyclic structure formed is preferably a pyrrolidine ring, piperidine ring, morpholine ring, pyridine ring, imidazole ring, quinuclidine ring, or the like. Particularly preferred are a pyrrolidine ring, a morpholine ring, a piperidine ring, an imidazole ring, and a pyridine ring.

Furthermore, any two or more groups of Q, R+ff, R1l, R19, R1°, and R21 may be bonded to each other to form a cyclic structure together with the nitrogen atom (the cyclic structure formed is a 6-membered cyclic structure). Rings or 5-membered rings are particularly preferred.

RIS The basic anion resin of the present invention has a general formula of 10HIC- (
IX) I3 may contain two or more types of the above monomer units.

X is from 0 to 60 mol%, preferably from 0 to 40 mol%, more preferably from 0 to 30 mol%. y is from 0 to 60 mol%, preferably from 0 to 40 mol%, more preferably from 0 to 30 mol%.

2 is 30 to 100 mol%, preferably 40
The amount is preferably from 50 to 95 mol%, more preferably from 50 to 85 mol%.

-a Among formulas (■), the following general formula (IX) is particularly preferred.

In the formula, A% B, x, y, z, R+s, RI4, R15%
R and xo have the same meaning as the above-mentioned -maximum (■).

- Among the maximum (IX), preferably R2, R1 and R4 are all alkyl groups and the total number of carbon atoms is 12 to 30.

Specific examples of the basic anion exchange resin represented by the general formula (■) of the present invention are shown below, but the compounds of the present invention are not limited thereto.

+01l□C1l-)i (-CH2Cl-)-.

x:z=lo:90 x:z=25: 31:69 tb +C1hC+- +CII□C1゜ CH0 C=O Hz CH2 N)I x:z=20:80 +C-Cl+,+ CH.

+CH, CI+.

+01l□C1l±1 CH.

20:80 CH0 +CIICIIg+ x:z=33:61 Z=30: CH.

x:z=10:90 X:V:z=20:20:60 CI(ff x:y:z=5:47:48 CH.

x:y:z=10:40:50 C=0 C=O H -O H Ht C=0 +ClIC1l□± X:f2=10:10:80 -(-CIICI+!+ 1,000CHt + CIl co HI 6HI2 HI CH2 H y: z=5: 25: 70 C=0 +C-Cur) C.I.

HI CI! 0 x:y:z=15:5:80 αη x: Z=36: 64 I x:y:z=10:20 near G 72m +C1hC)I÷ (-C1hC1l÷ C20 20: 80 C1].

+C++ZC+.

+01l□C+-8 C20 C20 Hzs Csll+s y:z=25 near 5 1e x:z=15:35 y: z=45: ! ＋：Yz・： 10:5:85 +CLCtl+ C20 CH.

-(-CIl□C+ C=O Hz=10:90 x:z=25: CHl CHl CHl x:z=40:60 C!0 1,000CHGHz+ %co, co-) C&H x:z=lQ:9Q x:z=30:10 1l C=0 (-CIICH!-) X:y:z-15:15 near 0 x:y:z=15 : 25:60 x:z=30: X')'+ : yz:Z=20:5:25:50x:z
=30:10 x:y:z=1l:9:80%50. ! e x:z=25 near 5 z=30 (4B) C1゜p0 x:z, :zz=10:15 near 5 l x:z, :zz=20:30:50 xe Je x:z, :z , = 15:15 near 0 As the basic anion exchange resin used in the present invention, many commercially available resins can be used. As such a basic anion exchange resin, Amberlite ERA-410. Same rRA~41l, Same IRA-91
0. IRA-400, IRA-401, IRA-
402, IRA-430, IRA-458, I
RA-900, IRA-904, IRA-938 (
Manufactured by Rohm Amberhaas), DIAIONS Al
oA, 5A12A, 5A20A, 5A2IA, PA306, PA316, PA318, PA40
6. PA412, PA418 (hereinafter manufactured by Mitsubishi Chemical Corporation)
, Epolus -70 (manufactured by Yoshi Yushi Co., Ltd.).

It can also be synthesized by the following synthesis example.

One-Ship Synthesis Method The anion exchange resin of the present invention is produced by adding a tertiary amine or a tertiary phostuine to a substantially water-insoluble resin (hereinafter referred to as precursor resin) having a group that can undergo a quaternization reaction with a tertiary amine or a tertiary phostuine. It can be synthesized by subjecting an amine or tertiary phosphine to a quaternization reaction and introducing a cation. The precursor resin is disclosed in Japanese Patent Application Laid-open No. 59-39347, U.S. Patent No. 2,874,
No. 132, No. 3,297,648, No. 3,549,5
No. 62, No. 3,637.535, No. 3.817. 8
No. 78, No. 3,843,566, No. 2,630°42
No. 7, No. 2,630.429, West German Patent No. 1.151
, No. 127, Special Publication No. 32-4143, No. 46-190
No. 44, No. 46-20054, No. 53-5294,
It can be synthesized by the methods described in Japanese Patent Nos. 33-2796 and 33-7397, and methods similar thereto.

Introduction of a cationic group by a quaternization reaction of a precursor resin with a tertiary amine or a tertiary phosphine is carried out using a tertiary amine or a tertiary phosphine in the precursor resin, as described in JP-A-59-39347. , U.S. Patent 2,874.132
No. 3,297゜648, No. 3,549.562, No. 3,637.535, No. 3.817.878,
No. 3゜843.566, No. 2,630,427, No. 2.630.429, West German Patent No. 1,151゜127
No., Special Publication No. 32-4143, No. 46-19044,
No. 46-20054, No. 53-5294, No. 33-
Each method described in No. 2796 and No. 33-7397, and
It is possible to synthesize by a method similar to this.

In addition, the anion exchange resin of the present invention is produced by using a substantially water-insoluble monomer having a quaternary ammonium group or a quaternary phosphonium group and a copolymerizable ethylenically unsaturated group. It can also be synthesized by the synthesis method of a precursor resin or by converting it into a resin by the method I (II).

Furthermore, the anion exchange resin of the present invention has a quaternary ammonium group or a quaternary phosphonium group, and a substantially water-insoluble copolymerizable monomer having an ethylenically unsaturated group, an amine or a phosphine, and a quaternary using a monomer mixture of substantially water-insoluble electrostatically capable monomers having a group capable of reacting with chemical reaction and having an ethylenically unsaturated group, or according to the method for synthesizing the precursor resin described above. Resinization is carried out using a method similar to , and cations are introduced using a tertiary amine or tertiary phosphine according to or similar to the method for introducing cations into the precursor resin through quaternization reaction. It can also be synthesized by

Synthesis Example 1 (Synthesis of poly(divinylbenzene-gochloromethylstyrene)) 1500 g of water and polyvinyl alcohol (from Nippon Gosei Kagaku Kogyo Co., Ltd.) were placed at room temperature in a 31 Mitsuro flask equipped with a stirrer, a thermometer, and a cooling tube. 2.5 g of Gohsenol (commercially available as Gohsenol) and 80 g of sodium chloride were added and sufficiently stirred to dissolve. To this solution, 206 g of chloromethylstyrene (commercially available as CMS-AM from Seimi Chemical Co., Ltd.) and 19.5 g of divinylbenzene were added.
A solution of 4.0 g of benzoyl peroxide dissolved in 200 g of toluene was added at room temperature, and the mixture was stirred for 1 hour under a nitrogen stream at a speed of 1 l0 revolutions per minute.

After raising the temperature to 70°C and reacting for 7 hours, the resulting resin spheres were collected by filtration, and heated with 50°C of hot water for 5 hours. Soak in 3
Ultrasonic cleaning was performed for 0 minutes. Similarly, it was washed with 21 parts of methanol, 2 parts of acetone, and 2 parts of ethyl acetate, and dried at 100° C. under reduced pressure to obtain 221.2 g of spherical resin with a particle size of 1** or less.

The chlorine content of the resin was determined by elemental analysis, and the amount of chlorine was confirmed to be 5.89x IQ-2 moles per 1 g of resin.

(Synthesis of poly(divinylbenzene-coated butylammoniomethylstyrene chloride'l17I) (compound 3)) 20 g of the poly(divinylbenzene-cochloromethylstyrene) spherical particles synthesized above were added to a stirrer, a thermometer, and a cooling tube. 40 g of isopropyl alcohol, 40 g of dimethylacetamide, and 40 g of tributylamine were added, and the mixture was allowed to swell for 7 hours with stirring at room temperature. This was heated to 85°C and reacted for 8 hours while refluxing the solvent. after that,
The reaction system was cooled to room temperature, and the solid content (resin spheres) was collected by filtration. The resin sphere was immersed in warm water at 50°C and subjected to ultrasonic cleaning for 30 minutes, followed by 21 liters of methanol and 21 liters of acetone.
Ethyl acetate 2I! and acetone 21 for 20 minutes each, and dried at 120° C. under reduced pressure to obtain 38°6 g of spherical resin. The chloride ion content was 2.70xlO-3 (mol 7g resin).

Chloride ions swell the ground resin in IN sodium nitrate to 0. Calculated by titration using IN silver nitrate.

Synthesis Example 2 (Synthesis of N-vinylbenzyl-N,N,N-trihexylammonium chloride) 54.9 g of chloromethylstyrene in a 1-liter three-tube flask
(0.36 mol) tri-n-hexylamine 80.
7 g (0.30 mol), 0.5 g of nitrobenzene as a polymerization inhibitor, and acetonate (IJ) 400- were added, and the mixture was heated under reflux for 7 hours with stirring.

After cooling to room temperature, the solution was washed several times with 500 g of n-hexane to remove unreacted chloromethylstyrene.

The crystals precipitated by concentration were recrystallized with ethyl acetate (500%) to obtain the target product, N-vinylbenzyl-N,N,N-).
White crystals of lyhexylammonium chloride 103.8
9 g (yield 82.1%). The structure of the obtained compound was confirmed by IH-NMR1 elemental analysis.

(Poly(divinylhenzen-gotrihexylammoniomethylstyrene chloride) (synthesis of compound 4) 288 g of water, N-vinylbenzyl-
N,N,N-1 lyhexylammonium chloride 143
．． Add 5 g (0.34 mol) and thoroughly absorb water to form an oily substance. To this, 7.8 g of divinylbenzene (
0.06 mol) and 3.0 g of azobisisobutyronitrile (commercially available from Wako Pure Chemical Industries, Ltd. under the trade name V-60) were added and stirred to dissolve. Further, 1080 g of calcium chloride and 2.3 g of polyvinyl alcohol (same as above) dissolved in 1 liter of water (52 g) were added, and the mixture was stirred at room temperature under a nitrogen stream for 30 minutes at a speed of 135 revolutions per minute. This was heated to 70°C and continued stirring for 6 hours.

After cooling to room temperature, the solid content was filtered and added to distilled water at 50°C.
Ultrasonic cleaning was carried out for 30 minutes using e.g. Ultrasonic cleaning was performed using 21 l of acetone and 21 l of ethyl acetate, and the mixture was heated at 100°C under reduced pressure.
The mixture was dried to obtain 122.6 g of spherical particles. The chloride ion content is 1. 8XIO-' (mol 7g resin).

Synthesis Example 3 (Synthesis of poly(divinylbenzene-gotrihexylammoniomethylstyrene chloride-gochloromethylstyrene)) 360 g of water was added at room temperature to a 51 Mitsuro flask equipped with a stirrer, a thermometer, and a condenser. N-vinylbenzyl-N,N,N-)lyhexylammonium chloride 84
．． Add 4 g (0.2 mol) and thoroughly absorb water to form an oily substance. To this, 10.4 g of divinylbenzene (
0.08 mol), chloromethylstyrene (same as above), 18.3 g (0.12 mol), azobisisobutyronitrile (same as above), 2.9 g, and stir to dissolve. . Furthermore, add 864 g of calcium chloride, 2.0 g of polyvinyl alcohol (same as above), and 9 g of water.
A solution of 30 g was added thereto, and the mixture was stirred for 30 minutes at room temperature under a nitrogen stream at a speed of 120 revolutions per minute. The temperature of this was raised to 80°C, and stirring was continued for 7 hours.

After cooling to room temperature, the solid content was filtered and added to distilled water at 50°C.
1, ultrasonic cleaning was performed for 30 minutes. Next, ultrasonic cleaning was performed using methanol 2β, acetone 21, and ethyl acetate 21 as solvents, respectively, and drying was performed at 100° C. under reduced pressure to obtain 95.2 g of spherical particles. The total chlorine content of the resin was determined by elemental analysis, and the total chlorine content was 2.78X10-' (mol 7
g resin) was obtained. Further, when the chloride ion content was determined by titration, a value of 1.65xlO-' (mol 7g resin) was obtained.

(Poly(divinylbenzene-cotelyptylammoniomethylstyrene chloride-cotelyptylammoniomethylstyrene chloride) (synthesis of compound 51) The above obtained poly(divinylbenzene-cotelyptylammoniomethylstyrene chloride) 75 g of spherical particles (object - chloromethylstyrene) were placed in a 1 liter three flask equipped with a stirrer, a thermometer and a condenser, and 100 g of isopropyl alcohol and 100 g of acetonitrile were added.
150 g of l-liptylamine was added, and the mixture was allowed to swell for 7 hours while stirring at room temperature. This was heated to 80°C and reacted for 9 hours while refluxing the solvent. Thereafter, the reaction system was cooled to room temperature, and the solid content (resin spheres) was collected by filtration.

This resin ball was immersed in warm water at 50°C and subjected to ultrasonic cleaning for 30 minutes.
After running for 21 minutes, methanol 21, acetone 21, ethyl acetate 21. Ultrasonic cleaning using solvents in the order of acetone 21.

Synthesis Example 5 (Synthesis of poly(divinylbenzene-chloromethylstyrene)) 3000 g of water was placed at room temperature in a 51 Mitsuro flask equipped with a stirrer, a thermometer, and a condenser.

5.0 g of polyvinyl alcohol (commercially available as Gohsenol from Nippon Gosei Kagaku Kogyo Co., Ltd.) and 160 g of sodium chloride were added and sufficiently stirred to dissolve. To this solution, add 412 g of chloromethylstyrene (commercially available as CMS-AM from Seimi Chemical Co., Ltd.), 43.4 g of divinylbenzene, and 8.0 g of over-rlled benzoyl.
A solution of 500 g of toluene was added at room temperature,
Stirring was continued for 30 minutes under a nitrogen stream at a speed of 120 revolutions per minute, and then the temperature was raised to 70° C. and reacted for 7 hours.

After the reaction, the resulting resin spheres were collected by filtration, immersed in warm water 51 at 50°C and subjected to ultrasonic cleaning for 30 minutes, then similarly washed with methanol 21, acetone 2e, and ethyl acetate 21, and heated at 100°C under reduced pressure. 440 g of dried spherical resin with a particle size of 11 or less
I got it. The chlorine content of the resin was determined by elemental analysis, and resin 1
A chlor content of 5.85 x to' moles per g was confirmed.

(Poly (divinylbenzene-go trimethylammoniomethylstyrene chloride-coated triptylammoniomethylstyrene chloride) (synthesis of compound 49) 20 g of poly (divinylbenzene-go chloromethylstyrene) spherical particles were added to a stirrer and a thermometer. , into a 500-Mitsuro flask equipped with a cooling tube, 70 g of isopropyl alcohol, 30 g of dimethylformamide, and 40 g of liptylamine were added, and the mixture was allowed to swell while stirring at room temperature for 30 minutes. This reaction system was heated to 80° C. and reacted for 6 hours while maintaining the reflux state of the solvent. After that, the reaction system was cooled to room temperature, the solid content was collected by filtration, 40 g of 30% trimethylamine aqueous solution was newly added, and the reaction was allowed to proceed at room temperature for 2 hours, and then the temperature was raised to 80 ° C. and heated for 1 hour. The granular resin in the system was filtered out. After thoroughly washing the resin sphere with hot water at 50°C, the solvent was changed in the order of methanol 21, acetone 21, ethyl acetate 21, and acetone 21, followed by ultrasonic cleaning for 30 minutes each, and dried at 120°C under reduced pressure. 30.0 g of spherical resin was obtained. The chloride ion content is 3.
1×10−” (mol 7 g resin).

Chloride ions were added by swelling the ground resin in IN sodium nitrate to 0. Calculated by titration using IN silver nitrate.

Synthesis Example 6 (Synthesis of poly(divinylbenzene-go-trihexylammoniomethylstyrene chloride-go-chloromethylstyrene)) 360 g of water was added at room temperature to a 51-sized three-turn flask equipped with a stirrer, a thermometer, and a condenser. N vinylbenzyl
N,N,N-4 lyhexylammonium chloride 168
．． Add 9g (0.40 mol) and let it absorb enough water,
It was made into an oily substance. Here, 5.2 g of divinylbenzene
(0.04 mol), chloromethylstyrene 9.2 g (
0°06 mol), 4.0 g of benzoyl peroxide was added, and while stirring, 1350 g of calcium chloride was added to 100 g of water.
2.9 g of polyvinyl alcohol (same as above) dissolved in 440 g of water was added. After stirring at a speed of 150 revolutions per minute at room temperature under a nitrogen stream for 30 minutes, the temperature was raised to 70° C. and stirring was continued for 6 hours.

After cooling to room temperature, the solid content was filtered and added to distilled water at 50°C.
1. Ultrasonic cleaning was performed for 30 minutes in step 1. Next, ultrasonic cleaning was performed using 21 methanol, 21 liters of acetone, and 21 liters of ethyl acetate as solvents, and dried at 100° C. under reduced pressure to obtain 176.8 g of spherical particles. Ta. (Contains chloride ions! 2.1 x 101 mol/g) (Poly(divinylbenzene-gotrimethylammoniomethylstyrene chloride-gotrihexylammoniomethylstyrene) (Synthesis of compound 1l348) Poly( 150 g of divinylbenzene-trihexyl ammoniomethyl chloride go chloromethyl styrene was placed in a 21-meter flask equipped with a stirrer, a thermometer, and a reflux device, and 300 m of dichloroethane was added at room temperature and allowed to swell for 30 minutes. Then, 30% trimethylamine aqueous solution 5001R1 was added, allowed to swell for 1 hour, and reacted at room temperature for 2 hours with stirring.Then, the temperature of the system was raised to 80°C, and dichloroethane was removed from the system by azeotropy. At this time, 500 ml of water was added in three parts to prevent the resin from drying out.After removing the solvent by azeotropy until no more dichloroethane came out, the solids were removed. It was collected by filtration and thoroughly washed with running water.After this, ultrasonic cleaning was performed for 30 minutes with warm water at 50°C, and then the medium was changed, using 2t of methanol, 2I of acetone, 21 of ethyl acetate, and 2J of acetone. , ultrasonic cleaning was performed for 30 minutes, and dried at 120°C under reduced pressure to obtain 147.2 g of spherical particle resin.The resin obtained here had a chloride ion content of 3.0XIQ-3 (mol/g). )Met.

In addition, the iodide ions in the above-maximum (■) are selectively removed,
It is particularly preferable that the functional group has a total number of carbon atoms of R+a, RIS and RI6 of 12 or more. Specifically, especially (3), (4), (5), (2), αbu, (to), (2
3), (24), (28), (29), (32), (4
4), (45), (46), (47), (48), (4
9) is preferred.

In the method of the present invention, when continuous treatment is performed while contacting an anion exchange resin, the column is filled and installed in the circulation pump piping of a tank with fixing ability, or in a subtank separate from the tank with fixing ability. Fill the tank and circulate the solution with fixing ability from the tank with fixing ability to the sub-tank,
Alternatively, it can be brought into contact with a processing liquid having a fixing ability by placing it in a bag made of fine mesh and immersing it in a tank having a fixing ability.

It is particularly preferable that the amount of the processing liquid having a fixing ability to be brought into contact with 1 liter of these anion exchange resins is from 20 fi to 20001, more preferably 20 ll-1ooo7! It is preferable that

The amount of processing liquid for 1 liter of anion exchange resin herein refers to the cumulative amount of replenisher that is replenished to 1 liter of the above 1 liter during continuous processing of photosensitive materials, and when the amount of replenisher of the present invention is replenished. This means that the anion exchange resin needs to be replaced.

Furthermore, the present invention can also be used in a so-called batch method in which a certain amount of photosensitive material is processed with a certain amount of processing solution without replenishment. In this case as well, the anion exchange resin and the treatment liquid can be brought into contact with each other in the same manner as described above.
The amount of processing liquid used per liter indicates the cumulative amount of liquid used until the resin is replaced.

Furthermore, the present invention can also be used when an overflow liquid in continuous processing of a liquid having fixing ability is regenerated with an anion exchange resin and used as a replenisher. In this case, the amount of treatment liquid used per resin 1e indicates the cumulative amount of treatment liquid that has been subjected to the regeneration treatment.

The light-sensitive material to be processed in the present invention is characterized by having an emulsion layer containing 1 mol % or more of silver waxide, but other structures will be described below.

The emulsion used in the present invention is usually one that has been subjected to physical ripening, chemical ripening and spectral sensitization. Additives used in such processes are described in Research Disclosure Vol. 176 @, 17643 (December 197B) and Vol. 187, -18716 (January 1979). They are summarized in the table below.

Known photographic additives that can be used in the present invention are also listed in the two Research Disclosures mentioned above, and their locations are shown in the table below.

Additive type 1 Chemical sensitization 2 Sensitivity increase 3 Spectral sensitization 4 Supersensitization 5 Increase White RD17643 RD1l1716 agent Page 23 Page 648 right column agent Same agent as above Page 23-24 Page 648 right column ~ agent Page 649 right column agent 24 Page 7 Kabra - Page 25 8 Organic solvent Page 25 1l Dye image stabilizer Page 25 12 Hardener Page 26 Page 651 left column 1
3 Binder Page 26 Same as above 14 Plasticizer, lubricant Page 27 Page 650 Right column A color coupler can be contained in the photosensitive material to be processed in the present invention. What is a color coupler here?
Typical examples of useful color couplers, which are compounds capable of forming dyes by coupling with oxidized aromatic primary amine developers, include naphthol or phenolic compounds, pyrazolone or pyrazoloazole compounds, and There are open-chain or heterocyclic ketomethylene compounds.

Specific examples of these cyan, magenta and yellow couplers that may be used in the present invention are found in the patents cited in Research Disclosure (RD) 17643 (December 1978) ■-D and RD 18717 (January 1979). Are listed.

The color coupler incorporated in the light-sensitive material is preferably diffusion-resistant by having a ballast group or being polymerized, and the coupling active position is substituted with a leaving group rather than a four-equivalent color coupler with a hydrogen atom. Two-equivalent color couplers can reduce the amount of coating iI. Couplers in which the coloring dye has adequate diffusivity, colorless couplers, or DIR couplers that release a development inhibitor or couplers that release a parent promoter upon coupling reaction can also be used.

Magenta couplers that can be used in the present invention include oil-protected indacylon or cyanoacetyl couplers, preferably pyrazoloazole couplers such as 5-pyrazolone and pyrazolotriazoles. The 5-pyrazolone coupler is preferably a coupler in which the 3-position is substituted with an arylamino group or an acylamino group from the viewpoint of the hue and color density of the coloring dye, and typical examples thereof include U.S. Pat. 2nd °34
3.103, 2,600,788, 2.9
No. 08.573, No. 3,062,653, No. 3,
No. 152.896 and No. 3936.015, etc. As a leaving group for a two-equivalent 5-pyrazolone coupler, the nitrogen atom leaving group described in U.S. Pat. No. 4,310,619 or the leaving group of U.S. Pat.
The arylthio group described in European Patent No. 97 is preferred, and the 5
- Pyrazolone couplers provide high color density.

As a pyrazoloazole coupler, U.S. Patent No. 3,
369.879, preferably pyrazolo(5,1-c)(1,2,4) triazoles described in U.S. Pat. No. 3,725.067, Research Disclosure 24220 (
Pyrazolotetrazoles and Research Disclosure 24230 (June 1984) and Research Disclosure 24230 (June 1984)
The imidazo (1) described in European Patent No. 119,741 in terms of low yellow side absorption and light fastness of color-forming dyes include the pyrazolopyrazoles described in
, 2-b) pyrazoles are preferred, as described in European Patent No. 1l9
Hirazoro [1°5-b) (1,2,
4) Triazoles are particularly preferred.

Cyan couplers that can be used in the present invention include oil-protected naphthol-based and phenol-based couplers, preferably the naphthol-based couplers described in U.S. Pat.
, No. 212, No. 4゜146.396, No. 4,22
Typical examples include the oxygen atom elimination type two-equivalent naphthol couplers described in No. 8,233 and No. 4,296.200. Specific examples of phenolic couplers include U.S. Patent No. 2,369.929 and U.S. Pat.
No. 01,171, same No. 2. 772. No. 162, No. 2', No. 895,826, etc. Cyan couplers that are robust to humidity and temperature are preferably used in the present invention, exemplified by U.S. Pat.
Phenolic cyan coupler having an alkyl group equal to or higher than ethyl group at the meta-position of the phenol nucleus described in U.S. Pat. No. 772,002, U.S. Pat.
．． No. 758,308, No. 4.126,396, No. 4,334,01l, No. 4.327173, West German Patent Publication No. 3.329,729, and Patent Application No. 1983-4
2,5-diacylamino-substituted phenolic couplers described in US Pat. No. 3,446, etc.
No. 622, No. 4.333,999, No. 4. 45
1. These include phenolic couplers having a phenylureido group at the 2-position and an acylamino group at the 5-position, which are described in No. 559 and No. 4,427.767.

Granularity can be improved by using a coupler in which the coloring dye has an appropriate diffusibility. Examples of such dye-diffusive couplers include magenta couplers in U.S. Pat. No. 4,366.237 and British Pat. No. 3,234°533 describes specific examples of yellow, magenta or cyan couplers.

The dye-forming couplers and special couplers described above may form polymers of dimers or more. Typical examples of polymerized dye-forming couplers are described in U.S. Pat. No. 3,451,82.
No. 0 and No. 4,080°21l. Specific examples of polymerized magenta couplers are described in British Patent No. 2,102,173 and U.S. Patent No. 4,367.2.
It is described in No. 82.

The various couplers used in the present invention can be used in combination in two or more layers in the same photosensitive layer, or in two or more different layers using the same compound, in order to satisfy the characteristics required for the photosensitive material. It can also be introduced into

Typical amounts used for color couplers are: - in the range of 0.001 to 1 mole per mole of photosensitive silver halide, preferably 0.001 to 1 mole for yellow couplers; Ol or 0
．． 5 mo J, magenta coupler 0.003 to 0
．． 3 moles, and 0.002 to 0 for cyan couplers.
．． It is 3 moles.

The coupler used in the present invention can be introduced into the light-sensitive material by various known dispersion methods. An example of a high boiling point organic solvent used in the oil-in-water dispersion method is disclosed in U.S. Patent No. 2,322,02.
It is stated in issue 7 etc.

Further, the process of latex dispersion method, effects, and specific examples of latex for impregnation are described in U.S. Patent No. 4.199゜363, OLS Patent Application No. 2,541゜274 and OLS No. 2.541,230. It is written in the number etc.

The photographic light-sensitive material to be processed in the present invention is coated on a commonly used flexible support such as a plastic film (cellulose nitrate, cellulose acetate, polyethylene terephthalate, etc.), paper, or the like. For details on supports and coating methods, please refer to Rl5EARCHDISCLO3U
RE 1 7 6 @, summer tes17643 standing term C
p, 27) Section X4 (p, 28) (December 1978 issue)
It is described in.

The photosensitive materials of the present invention include color negative films for general use or movies, color reversal films for slides or television, color paper color positive films, color reversal paper direct positive color photosensitive materials, black and white films, black and white papers, X-ray films, Typical examples include photosensitive materials for printing.

Hair treatment method The treatment method of the present invention includes various combinations of treatment steps, specifically: (i) development - bleaching - constant washing - drying - (ii) s - # - # - Stabilization-Drying (iii) # --~ -Stabilization-Drying (
iv) # - Bleach-fixing, washing, drying (v) 〃
--- Stabilization-Drying (yi) s -# -Washing-Stabilization-Drying (
vi) Development - bleaching - bleach-fixing - washing - drying (yi)
# - / F - # - ~ - Stabilization-Drying (IX) ~ -〃-〃 - Stabilization-Drying and other processing methods can be mentioned. Here, washing with water may be provided between development and bleaching or bleach-fixing, or between bleaching and fixing. The treatment bath may be of any type, such as a single tank, a multi-stage countercurrent system, or a multi-stage parallel current system. The above development process consists of black and white development, water washing, reversal, and color development.
A reversal color development step may be included.

The color developing solution used in the development of light-sensitive materials is preferably an alkaline aqueous solution containing an aromatic primary amine color developing agent as a main component. Aminophenol compounds are also useful as color developing agents, but p-phenylenediamine compounds are preferably used, representative examples of which are 3-methyl-4-amino-N, N-diethylaniline, 3-methyl- 4-amino-N-ethyl-N-β-hydroxylethylaniline, 3-methyl-4-amino-N-
Ethyl-N-β-methanesulfonamide ethylaniline, 3-methyl-4-amino-N-ethyl-N-β-methoxyethylaniline and their sulfates, hydrochlorides or I)-)luenesulfonates, etc. Can be mentioned. These diamines are generally more stable in their salt form than in their free state, and are therefore preferably used.

The color developer may contain pH-reducing agents such as alkali metal carbonates, borates or phosphates, development inhibitors or capri-inhibitors such as bromides, iodides, benzimidazoles, benzothiazoles or mercapto compounds. Generally, it includes the sides, etc. If necessary, hydroxylamine, diethylhydroxylamine, sulfite, various preservatives such as those described in Japanese Patent Application No. 61-280792, organic solvents such as triethanolamine and diethylene glycol, benzyl alcohol, polyethylene glycol, and development accelerators such as grade ammonium salts, amines, dye-forming couplers, competitive couplers, fogging agents such as sodium boron hydride, auxiliary developers such as 1'-phenyl-3-pyrazolidone, tackifiers, aminopolymer Various chelating agents such as carboxylic acid, aminopolyphosphonic acid, alkylphosphonic acid, and phosphonocarboxylic acid, West German Patent Application (OLS) No. 2 and 6
Antioxidants such as those described in No. 22.950 may be added to the color developer.

Further, when performing reversal processing, black and white development is usually performed and then color development is performed. This black and white developer contains dihydroxybenzenes such as hydroquinone, ■-phenyl-3-
Known black and white developers such as 3-pyrazolidones such as pyrazolidone or aminophenols such as N-methyl-p-thiaminophenol can be used alone or in combination.

The amount of replenishment of these color developing solutions and black-and-white developing solutions depends on the color photographic light-sensitive material being processed, but is generally 3°C or less per square menitol of the light-sensitive material, but the concentration of bromide ions in the replenisher should be kept low. It can also be reduced to 500- or less. When reducing the amount of replenishment, it is preferable to reduce the opening area of the processing tank to prevent evaporation and air oxidation of the solution.Also, by using means to suppress the accumulation of bromide ions in the developer, It is also possible to reduce the amount of replenishment.

I Wataru 1 Ashi Yutaka After color development, the photographic emulsion layer is usually bleached.

The bleaching process may be performed simultaneously with the fixing process, or may be performed separately. Furthermore, in order to speed up the processing, it is also possible to use a processing method in which continuous fixing processing is performed after bleaching processing. Further, a fixing treatment can be carried out before the bleach-fixing treatment, or a bleaching treatment can be carried out after the bleach-fixing treatment depending on the purpose. Examples of bleaching agents include iron (■) and cobalt (■).
, compounds of polyvalent metals such as chromium (■), steel (II),
iIA acids, quinones, nitrone compounds, etc. are used.

Typical bleaching agents include ferricyanide; dichromate; organic complex salts of iron (I[I) or cobalt (III), such as ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, methyliminodiacetic acid, 1.3 - Using complex salts of aminopolycarboxylic acids such as diaminopropanetetraacetic acid and glycol ether diaminetetraacetic acid, or organic acids such as citric acid, tartaric acid, and malic acid; persulfates: bromates; manganates; nitrosophenols, etc. Can be done. Among these, aminopolycarboxylic acid iron(III) salts and persulfates, including ethylenediaminetetraacetic acid iron(III) salts, are preferable from the viewpoint of rapid processing and environmental pollution.Furthermore, aminopolycarboxylic acid iron(III) complex salts are preferred. Even in independent bleaching solutions,
- Also particularly useful in bath bleach-fix solutions.

Examples of fixatives include thiosulfates, thiocyanates, thioureas, 1,000-onythyl compounds, and large amounts of iodides, but thiosulfates are commonly used, and ammonium 1,000-sulfate is the most widely used. Can be used for As the preservative for the bleach-fix solution and the fix solution, sulfites, bisulfites, or carbonyl bisulfite adducts are preferred.

Among the processing solutions for the above-mentioned desilvering step, the replenishment amount of the processing solution having fixing ability is preferably 300- or more per 1rd photosensitive material, particularly preferably 300-100 or less. . In addition, when processing with a bleach solution, the replenishment amount is preferably 50 - or more, particularly 100 -
d or more and 50 (preferably ld or less).

After desilvering, the silver halide color photographic material of the present invention is generally subjected to a washing and/or stabilization process.

The washing life in the washing process depends on the characteristics of the photosensitive material (for example, depending on the materials used such as couplers), the application, the washing water temperature, the number of washing tanks (number of stages), the replenishment method such as countercurrent or forward flow, and various other conditions. Can be set over a wide range. Among these, the relationship between the number of washing tanks and the amount of water in the multistage countercurrent method is
urnal of the Society of Mot
ion Picture and Television
nEngineers Vol. 64, P, 248-253
(May 1955 issue).

According to the multi-stage countercurrent method described in the above-mentioned literature, the amount of water used for washing can be greatly reduced, but the increased residence time of water in the tank causes bacteria to propagate and the generated suspended matter to adhere to the photosensitive material. Problems such as this arise. In the processing of the color light-sensitive material of the present invention, as a solution to such problems, the method for reducing calcium and magnesium described in Japanese Patent Application No. 131632/1988 can be used very effectively. In addition, chlorine-based disinfectants such as isothiazolone compounds, cyabendazole, chlorinated sodium isocyanurate, and other benzotriazoles described in JP-A No. 57-8542, "Chemistry of Antibacterial and Antifungal Agents" by Hiroshi Horiguchi , "Sterilization, sterilization, and anti-mildew technology of microorganisms" edited by Sanitation Technology Society, and "Encyclopedia of antibacterial and anti-fungal agents" edited by Japanese Society of Antibacterial and Mildew Prevention can also be used.

The pH of the washing water in the processing of the photosensitive material of the present invention is 4-
9, preferably 5-8. The washing water temperature and washing time can also be set variously depending on the characteristics of the photosensitive material, its use, etc., but generally it is 20 seconds to 10 minutes at 15-45°C, preferably 25
A range of 30 seconds to 5 minutes at -40°C is selected.

Furthermore, the photosensitive material of the present invention can also be directly processed with a stabilizing solution instead of washing with water. In such stabilization treatment, Japanese Patent Application Laid-Open Nos. 57-8543 and 58-1483
All known methods described in No. 4, No. 60-220345, etc. can be used.

Further, following the water washing treatment, a further stabilization treatment may be carried out, such as a stabilizing bath containing formalin and a surfactant, which is used as a final bath for color photosensitive materials for photography. .

Various kinds of bovine chloride agents and anti-fungal agents can also be added to this stabilizing bath.

The overflow liquid resulting from the water washing and/or replenishment of the stabilizing liquid can be reused in other processes such as the desilvering process.

The silver halide color light-sensitive material of the present invention may contain a color developing agent for the purpose of simplifying and speeding up processing.
In order to incorporate various types of developer, it is preferable to use a developer. For example, U.S. Pat. No. 3,342,
Indoaniline compounds described in No. 597, No. 3,34
No. 2,599, Research Disclosure 14.8
Schiff base type compounds described in No. 50 and No. 15,159, aldol compounds described in No. 13,924, metal salt complexes described in U.S. Pat.
Examples include urethane compounds described in No. 3-135628.

The silver halide color photosensitive material of the present invention may contain various 1-phenyl-
Typical compounds that may incorporate 3-pyrazolidones are described in JP-A-56-64339, JP-A-57-144547, and JP-A-58-115438.

Various treatment liquids in the present invention are used at 10°C to 50°C. The standard temperature is 33°C to 38°C, but it is possible to accelerate the processing and shorten the processing time by increasing the temperature higher than S.
Conversely, it is possible to improve the image quality and the stability of the processing solution by lowering the temperature. In addition, in order to save silver on photosensitive materials, West German Patent No. 2226.770 or U.S. Patent No. 3,
A treatment using cobalt intensification or hydrogen peroxide intensification as described in No. 674.499 may also be carried out.

A heater, a temperature sensor, a liquid level sensor, a circulation pump, a filter, a floating pig, a squeegee, etc. may be provided in the various processing baths as necessary.

Further, during continuous processing, a constant finish can be obtained by using a replenisher for each processing solution to prevent fluctuations in the solution composition. The replenishment amount can be reduced to half or less than the standard replenishment amount to reduce costs.

(Example) Next, the present invention will be explained with reference to Examples, but the present invention is not limited thereto.

Example 1 On a subbed cellulose triacetate film support,
Sample 101, which is a multilayer color light-sensitive material consisting of each layer having the composition shown below, was prepared.

(Composition of photosensitive layer) The coating amount is expressed in g/rd unit of silver for silver halide and colloidal silver, and the amount expressed in g/rtr unit for coupler additive and gelatin. The number of moles of the dye is expressed per mole of silver halide in the same layer.

1st layer (antihalation layer) Black colloidal silver 0. 2 gelatin 1.3 coupler (, -10,
06 Ultraviolet absorber UV-10,1 Ultraviolet absorber UV-20,2 Dispersion oil 0i1-10.01 Same as above Oil -20,01 2nd layer (intermediate layer) Fine grain silver bromide (average particle size 0.07μ) 0 , 15 gelatin 1゜0 coupler C-
20,02 Dispersion oil 0il-10,1 Third layer (first red-sensitive emulsion layer) Silver iodobromide emulsion (silver iodide 2 mol%, ratio 2.5, average grain size 0.3μ, type) Silver gelatin Sensitizing dye ■ 1° Sensitizing dye II 3° Sensitizing dye ■ Coupler C-3 Coupler C-4 Coupler C-8 Coupler C-2 Dispersion oil 041-1 Same as above 0i1-3 4th NC 2nd red-sensitive emulsion layer) Silver bromide emulsion (silver iodide 5 mol%, ratio 4.0, average grain size 0.7μ, type) tl Sensitizing color dye Sensitizing dye■ Internal height of diameter/thickness Ag1 O14 0,6 oxto-' 0XIO -' I -3 Coupler c-4 Coupler C-8 Coupler c-2 Dispersion oil Oi l-1 Same as above 0i1-3 5th layer (3rd emulsion layer) Silver iodobromide emulsion (silver iodide 10 mol%, Ratio 1.3, average particle size 0.8μ, i type) Gelatin sensitizing dye ■ Aggravating dye ■ Sensitizing dye ■ Coupler C-6 Coupler C-7 Dispersion oil 01l Same as above Oil No. 61 (intermediate layer) Diameter/j7 Internal height Ag 1.0 1, 0 IXIO"3X10-'lXl0-' 0.05 0.1 Olol 0.05 lXl0-' 0, 24 0, 24 0, 04 0, 04 0, 15 0, 02 Gelatin 1.0 Compound Cpd
-A 0.03 dispersion oil oil-1
0.05 7th layer (first green-sensitive emulsion layer) Silver iodobromide emulsifier (silver iodide 2 mol%, diameter/thickness ratio 2.05)
5. Average particle size 0.3μ, internal cylinder AgI type)
Resentment 0. 3 Exacerbation dye IV
5X10-' sensitizing dye Vl O,
3XlO"4 sensitizing dye v 2xl
O-' Gelatin 1.0 Coupler C-90,2 Coupler C-50,03 Coupler C-10,03 Compound Cpd-C0,012 Dispersion oil 0il-10,5 8th layer (second green-sensitive emulsion layer) Silver bromide emulsion (silver iodide 4 mol%, diameter/thickness ratio 4.0)
, average particle size 0.6μ, internal high Agl type)
Silver O14 Sensitizing Dye ■ Sensitizing Dye V Sensitizing Dye VI O.

Coupler C-9 Coupler C-1 Coupler C-10 Coupler C-5 Compound cpa-c Dispersion oil Oil-1 9th layer (third green-sensitive emulsion layer) Silver iodobromide emulsion (silver iodide 6 mol%, Ratio 1.2, average particle size 1.Oμ, type) Silver gelatin sensitizing dye■ 3゜sensitizing dye■ 1゜Coupler C-13 Coupler C-12 Coupler C-9 Coupler C-t 5X10-'2XlO-'3X10-' 0,25 0,03 0.015 0, Ol O,012 0,2 Diameter/thickness internal height Ag1 O385 1,0 5X10-'4X10-' 0.01 0.03 0.20 0.02 Coupler C-150° Dispersion oil 0il-10° Same as above 0il-20° 1st O layer (yellow filter layer) Gelatin 1° Yellow colloidal silver 0° Compound Cpd-B
O.

Dispersed oil 0il-10° 1st layer (first blue-sensitive emulsion layer) Monodisperse silver iodobromide emulsion (silver iodide 4 mol%, thickness ratio 1.5
, average particle size 0.5μ, Agl type)
tri O.

Gelatin L/Sensitizing dye ■ 2×1 coupler C-1
40° Coupler C-50° Dispersion oil 0il-10° 12th layer (second blue-sensitive emulsion layer) Silver iodobromide emulsion (silver iodide 10 mol%, ratio 4.5, average grain size 1.3μ, Diameter/Thickness Internal height Ag Diameter/Internal high summer type) Gelatin sensitizing dye■ Coupler C-14 Dispersion oil Oi+-1 13th layer (1st protective layer) Gelatin ultraviolet absorber UV- as above UV-2 Dispersion oil Oi I-1 Dispersion oil 0il-2 No. 141 (second protective layer) Particulate bromide I! (Average particle size 00 07μ) 0.5 Gelatin 0.45 Polymethylmethacrylate particles (diameter 1.5μ) 0, 2 Hardener H-10,4 Silver 0.4 0.6 IXIO-' 0, 25 0, 07 0.8 0.1 0.2 0, 01 0, Ol p-Hydroxybenzoic acid n-butyl formaldehyde scavenger 5-10.5 Formaldehyde scavenger 5-20, 5 In addition to the above components, each layer contains , a surfactant was added as a coating aid.

Next, the chemical structural formula or chemical name of the compound used in this example is shown below (-cut-c +V-+CIl□-○±).

N UV-2 0,012 Tricresyl nonate dibutyl phthalate i1 Bis(2-ethylhexyl) phthalate l 1(, C-C-CH3 CH2 C(CH))3 OCHgCllzSCHzCOOH H H (n)CtH* H ( n) CJ+s CH3 COOC4)+9 C-1l C pd-A pd-B H3 H H pd-C l (CHg)ssOiH-N(CtHs)s(CIl□)
zsOs.

(C1l□)ssO+H-N(Czlls)z sensitizing dye■ (CHz) 4 SO,.

(C1l□)4 S031lN (CzHs) :+ CHI = CHS(h CIIZ C0NHCH
! ■ CHz =CHSOz CHz C0NHCtl□
■ On a subbed cellulose triacetate film support,
Sample 102, which is a multilayer color photosensitive material, was prepared by coating layers having the compositions shown below.

(Photosensitive layer composition) The numbers corresponding to each component indicate the coating amount expressed in g/rd units, and for silver halide, the coating amount is expressed in terms of silver. However, for sensitizing dyes, the coating amount is expressed in moles per mole of silver halide in the same layer.

(Sample 101) 1st layer; antihalation layer black colloid 0.18 gelatin 0.40 2nd layer; intermediate layer 2.5-di-t-pentadecylhydroquinone 0.18EX-10
,07 EX-30,02 EX-120,002 U-10,06 U-20,08 U-30,10 HBS-10,10 HBS-20,02 Gelatin 1.04 Third layer (first red-sensitive emulsion layer) Monodispersed silver iodobromide emulsion (silver iodide 6 mol%, average grain size 0)
．． 6μ, coefficient of variation regarding particle size 0°15)
Silver 0.55 Sensitizing dye 1 6.
9X10-' Sensitizing Dye II 1.8x
lO-5 sensitizing dye III 3.1X1
0-' Sensitizing dye N 4.0X10-S
EX-20,350 HBS-10,005 EX-100,020 Gelatin 1.20 Fourth layer (second red-sensitive emulsion layer) Tabular silver iodobromide emulsion (silver iodide 10 mol%, average grain size 0. 7μ, average aspect ratio 5.5, average thickness 0.2μ
) Silver 1.0 Sensitizing dye 1 5.
1X10-' Sensitizing Dye II 1.4X
10-' Sensitizing dye [[[2,3X10-' Sensitizing dye IV 3.0X10-'EX
-20,400 EX-30,050 EX-100,015 Gelatin 1.30 Fifth layer (third red-sensitive emulsion layer) Silver iodobromide emulsion (silver iodide 16 mol%, average grain size 1.
1 μ) S 1, 60 sensitizing dye IX 5
．． 4X10-' Sensitizing Dye II 1.4
X10-' Sensitizing Dye 1 [12,4XIO-' Sensitizing Dye IV 3. lX1O-SEX
-30,240 2X-40,120 8BS-10,22 HBS-20,10 Gelatin 1.63 6th layer (middle layer) EX-50,040 HBS-10,020 EX-120,004 Gelatin 0.80 layer 7 layers (first green-sensitive emulsion layer) Tabular silver iodobromide emulsion (iodide!!! 6 mol%, average grain size 0.6μ, average aspect ratio 6.0, average thickness 0.1
5) Silver 0.40 sensitizing dye V
3.0X10-S sensitizing dye Vl
1.0X10-'sensitizing dye ■ 3.8X
10-'EX-60,260 EX-10,021 EX-70,030 8X-80,025 HBS-10,100 HBS-40,010 Gelatin 0.75 8th layer (second green-sensitive emulsion layer) Monodisperse Silver iodobromide emulsion (silver iodide 9 mol%, average grain size 0
．． 7μ, coefficient of variation regarding particle size 0°18)
SIo, 80
Sensitizing dye V2. lX10-5 sensitizing dye Vl 7.0X10-' sensitizing dye ■
2.6X10-'EX-60,180 EX-80,010 EX-10,008 EX-70,012 HBS-10,160 HBS-40,008 Gelatin 1.10 9th N (3rd green-sensitive emulsion layer) Silver bromide emulsion (silver iodide 12 mol%, average grain size 1
, 0μ) i艮
1. 2 sensitizing dye V 3.5X
10-' Sensitizing dye Vl 8.0XlO
-'Sensitizing dye ■ a, oxto-'EX
-60,065 EX-1l0,030 8X-10,025 HBS-10,25 8BS-20,10 Gelatin 1.74 1st O layer (
Yellow filter layer) Yellow colloidal silver Silver 0.05EX-5
0,08 HBS-30,03 Gelatin 0.95 1st l layer (
1st blue-sensitive emulsion layer) Average silver iodobromide emulsion (iodide!!6 mol%, average grain size 0.6μ, average aspect ratio 5.7, average thickness 0.15
) Silver 0.24 sensitizing dye■
3.5xlO-'BX-90,85 EX-80,12 HBS-10,28 Gelatin 1.28 12th layer (
Second blue emulsion layer) Monodisperse silver iodobromide emulsion (silver iodide 10 mol%, average grain size 0.8 μ, coefficient of variation regarding grain size 0.16)
Silver 0.45 sensitizing dye ■ 2
．． lX10-'EX-90,20 EX-100,015 8BS-10,03 Gelatin 0.46 13th layer (
Third blue-sensitive emulsion layer) Silver iodobromide emulsion (silver iodide 14 mol%, average grain size 1.3
μ) Silver 0.77 increasing dye■
2.2X10-'EX-90,20 HBS-10,07 Gelatin 0.69 No. 14M (
1st protective layer) Silver iodobromide emulsion (silver iodide 1 mol%, average grain size 0,
07 μ)!议
0.5B5-1 Gelatin 15th layer (second protective layer) Polymethyl acrylate particles (diameter approximately 1.5 μm) In addition to the above components, 1 and a surfactant were added to each gelatin layer.

0,54 0, 15 0,05 0, 72 Gelatin hardener H X-1 EX-2 0H (i)Call*0CONll EX-3 0 ■ place EX 0 ■ (i) CaHqOCONH OCHzCHzSCFIzCOO1l X-7 I EX-8 Hs EX-9 EX-5 H EX EX-10 il L EX-1l X B5-1 HBS-2 B5-3 B5-4 tricresyl phosphate dibutyl phthalate Bis(2-ethylexyl) lid rate (t) L;sH+ C,)IS C,H.

CH,=CI+ CIl□=CH Exacerbating dye SO□-CHzCONII Ctl□5o2Ctlz
-CONH-C1l□ (C1lz) 3sOJa ■ (CH2) l5Oj.

(CI+2) 5sOJa ■ (C1l□) 4503° (C1l□) asOJ On a cellulose triacetate film support with an undercoat,
Sample 103, which is a multilayer color photosensitive material consisting of each layer having the composition shown below, was prepared.

(Composition of the photosensitive layer) The coating amount is expressed in g/rd of silver for silver halide and colloidal silver, and in g/% for coupler additives and gelatin. The number of moles of the dye is expressed per mole of silver halide in the same layer.

1st layer (antihalation layer) Black colloidal silver 0.2 gelatin
1. 3ExM-90,06 UV-10,03 UV-20,06 UV-30,06 Solv-10,15 Solv-20,15 Soly-30,05 2nd layer (middle layer) Gelatin 1. 0TJV-1
0,03 ExC-40,02 ExF-10,004 Solv-10,l 5olv-20,1 3rd layer (low-sensitivity red-sensitive emulsion layer) Silver iodobromide emulsion (Ag14 mol%, uniform-Agl type, spherical Equivalent diameter 0.5μ, coefficient of variation of equivalent sphere diameter 20%, plate-shaped particles, diameter/thickness ratio 3.α) Coated silver 1l. 2 Silver iodobromide emulsion (Ag 13 mol%, uniform Agl type, equivalent sphere diameter 0.3 μ, coefficient of variation of equivalent sphere diameter 15%, spherical grains, diameter/thickness ratio 1.0) Coated silver amount 0.6 Gelatin 1.0ExS-14
xto-' ExS-25 Ag 16 mol%, internal high Agl type with core shell ratio 1:1, equivalent sphere diameter 0.7 μ, coefficient of variation of equivalent sphere diameter 15%, plate-shaped particles, diameter/thickness ratio 5.0) Coated silver amount 0.7 gelatin 1.0E
xS-13X10-'ExS-22,3xto-' ExC-60.1l ExC-70,05 ExC-40,05 Solv-10,05 Solv-30,05 5th layer (middle layer) Gelatin 0.5Cpd-IQ
・l 5olv-10,05 6th layer (low-sensitivity green-sensitive emulsion N) Silver iodobromide emulsion (Ag14 mol%, surface height Agl type with core-shell ratio 1:1, equivalent sphere diameter 0.5μ, equivalent sphere diameter Coefficient of variation 15%, plate-like grains, diameter/thickness ratio 4.0) Coated silver amount 0.35 Silver iodobromide emulsion <Ag 13 mol%, uniform Ag
L type, equivalent sphere diameter 0.3 μ, coefficient of variation of equivalent sphere diameter 25%,
Spherical particles, diameter/thickness ratio 1.0) Coated silver amount 0620 Gelatin! ,0ExS-35
X10-'ExS-43xto-'ExS-5txto-' ExM-80,4 ExM-90,07 ExM-100,02 ExY-1l0,03 Solv-10,3 Solv-40,05 7th layer (high sensitivity green Sensitive emulsion layer) Silver iodobromide emulsion (Ag 14 mol%, internal high Agl type with core-shell ratio 1:3, equivalent sphere diameter 0.7 μ, coefficient of variation of equivalent sphere diameter 20%, plate-like grains, diameter/thickness ratio 5) .0) Coated silver 1
0.8 Gelatin 0.5ExS-35
x1o-'ExS-43xto-'ExS-5txto-' ExM-80,1 ExM-90,02 ExY-1l0,03 ExC-20,03 ExM-140,01 Solv-10,2 Solv-40,01 8th Layer (middle layer) Gelatin 0. 5Cpd-I
Q. 05 Solv-10,02 9th layer (donor layer for interlayer effect on the red-sensitive layer) Silver iodobromide emulsion G 12 mol%, core shell ratio 2:1 internal height A
gI type, equivalent sphere diameter 1.0μ, coefficient of variation of equivalent sphere diameter 15%
, plate-like particles, diameter/thickness ratio 6.0) Coated silver amount 0.
35 silver iodobromide emulsion (Ag+2 mol%, core shell ratio 1:
1 internal high Agl type, equivalent sphere diameter 0.4 μ, coefficient of variation of equivalent sphere diameter 20%, plate-shaped particles, diameter/W-view ratio 6.0) Coated silver amount 0.20 gelatin
0. 5ExS-38xlO-' ExY-130,1l ExM-120,03 ExM-140,10 Solv-10,20 1st O layer (yellow filter layer) Yellow colloidal silver 0.05 Gelatin 0. 5Cpd-20,13 Solv-10,13 cpd-1o,t.

First layer (low-sensitivity blue-sensitive emulsion layer) Silver iodobromide emulsion (Ag+4.5 mol%, uniform-Agl type, equivalent sphere diameter 0.7μ, coefficient of variation of equivalent sphere diameter 15%, plate-like grains, diameter /thickness ratio 7.0) Coating amount 5M 0.3 Silver iodobromide emulsion (Ag + 3 mol %, uniform -Agl type, equivalent sphere diameter 0.3 μ, coefficient of variation of equivalent sphere diameter V 1.25%, plate-like grains, Diameter/thickness ratio 7.0) Coated silver amount 0.15 Gelatin 1.6ExS-62
X10-' ExC-160,05 ExC-20,10 ExC-30,02 ExY-130,07 ExY-151,0 Solv-10,20 12th layer (high grade blue-sensitive emulsion N) Silver iodobromide emulsion (Ag1l0mol%, internal height gI type, equivalent sphere diameter 1.0μ, coefficient of variation of equivalent sphere diameter 25%, multiple twinned plate-like particles, diameter/thickness ratio 2.0) Coated silver l
0.5 gelatin 0.5Ex
S-61XIO-' ExY-150,20 E-xY-130,01 Solv-10,10 13th layer (first protective layer) Gelatin 0.8UV-40,
l UV-50,15 Solv-10,01 Solv-20,01 14th layer (second protective layer) Fine grain silver bromide emulsion (Ag+2 mol%, uniform Agl type, equivalent sphere diameter 0.07μ) 0.5 Gelatin 0.45 polymethyl methacrylate particle diameter 1.5μ 0.2H-10,4 Cpd-50,5 cpci-6o,5 In addition to the above ingredients, each layer contains emulsion stabilizer Cpd-3 (0
,04g/rr? ) Surfactant Cpd-4 (0,02g
/+d) was added as a coating aid.

UV-2 ■0 v N UV-5 olv-1 tricresyl phosphate olv dibutyl phthalate pd-4 pd pd-6 xC H xC-2 H (i) C4H90CNH 0IV-3 pa-t H pd-2 pd-3 xC-3 H xC-4 0 ■ xC H C1l□ xC R H, C-C-CH.

CH.

C(CHI)3 xM-9 Cβ xM xC H xM-8 CH3 COOC4Hq xY xM-12 ExY-13 C1l゜ xS xS ans CH3 ExY-15 xC-16 H 5L;HzL;tlzUυzLH* xS-5 ExS=6 CHz = CHS (h CHz C0NIIth CH,=C1-8O3 lh 0NH CH.

xF-1 gHs C2H% Samples 101, 102 and 10 prepared as above
Samples 104, 105 and 106 were prepared in the same manner except that all the silver halide emulsions in Sample No. 3 were replaced with silver bromide.

After exposing the color photographic materials 101 to 106 as described above, each of them was processed using an automatic processor in the following manner (the cumulative replenishment amount of bleach-fix solution was 3 times the capacity of the mother liquor tank).
(until doubled).

Processing method (A) Process Processing time Processing temperature Replenishment amount 1 capacity Color development 3 minutes 15 seconds 38℃ 45ml ION bleaching 1 minute 00 seconds 38℃ 7-4
ββ Bleaching 3 minutes 15 seconds 38℃ lQ+*18N
Water washing (2) 1 minute 00 seconds 35℃ 3Qml
4β Stable 40 seconds 38℃ '10m
1 41 Drying 1 minute 15 seconds 55°C Replenishment amount is 35 cranes per meter length Next, write down the composition of the treatment solution.

(Color developer) Diethylenetriaminepentaacetic acid -Hydroxyethythene-1,1-diphosphonic acid Sodium sulfite Potassium carbonate Potassium bromide Potassium iodide Hydroxylamine sulfate 4-[N-ethyl-N (β-hydroxyethyl)amino] - Add 2-methylaniline sulfate aqueous solution H Mother liquor (g) 1.0 3.0 4.0 30.0 1.4 1.5■ 2.4 Replenisher (g) 1.1 2.8 4. 5 5.5 1.0e 1.0ri 10.05 10.10 (Bleach solution) Common to mother liquor and replenisher (unit: g) Ethylenediaminetetraacetic acid ferric ammonium trihydrate 120.0 Ethylenediaminetetraacetic acid disodium salt 10 .0 Ammonium Bromide 100.0 Ammonium Nitrate
IO30 bleach accelerator
0005 mol Aqueous ammonia (27%) Add water and p (Unit: g) 50゜Thorium salt Sodium sulfite 5゜12゜Ammonium thiosulfate water/8v & (70%) 28L
d Ammonia water (27% > 6.0ml
Add water to 1.0RpH7,
2 (Water washing solution) Mother solution and replenisher Common tap water was filled with 1L type strongly acidic cation exchange resin (Amberlite IR-120B manufactured by Rohm and Haas) and OH type anion exchange resin (Amberlite IR-400 manufactured by Rohm and Haas). Water was passed through a mixed bed column to reduce the concentration of calcium and magnesium ions to 3/A or less, and then 20 mg/l of sodium isocyanurate dichloride and 1.5 g/l of sodium sulfate were added.

The pH of this solution was in the range of 6.5-7.5.

(Stable m,) Common to mother liquor and replenisher (unit: g) Formalin (
37%') 2.0d Polyoxyethylene-p-monononylphenyl ether (average degree of polymerization 10) 0.3 Ethylenediaminetetraacetic acid distrium salt 0.05 Add water 1.01 pH 5,0-8,0 Each sample was subjected to continuous processing after imagewise exposure by incorporating a column filled with 120 sf of strong basic anion exchange resin, DIAION PA418 manufactured by Mitsubishi Kasei Co., Ltd., into the circulation pump system piping of the bleach-fixing bath (processing method B). ). Next, continuous treatment was performed while changing the amount of ion exchange resin in the column as shown in Table 1. 4 at the end of each successive process
Samples exposed to 800' and 100 CMS (n-light samples) were processed and the residual silver 1it (μg/ru) was examined by fluorescent X-ray analysis. (Unexposed sample) was also treated in the same way at the end of the continuous treatment and the amount of residual silver was examined.The obtained results are shown in Table 1.The circulation rate by the circulation pump in this experiment was 5e/min. The column was sized according to the resin, but in the case of 120-cm, a cylindrical column with a diameter of 4.6 cm and a length of 12 cm was used, and both ends were covered with fine plastic nets to form particles. This made it possible to press the resin.

As is clear from Table 1, in the method of treating the bleach-fixing solution with an ion exchange resin, when the continuously processed irradiated material contains silver iodide, the amount of residual silver decreases (
n-light sample). Since there is almost no difference from the remaining ill of the unexposed sample, this is considered to be due to an improvement in the fixing processing ability.

Example 2 Preparation of 8゛ grains 1 30g of gelatin and 6g of potassium bromide were added to water B, and in a container kept at 60°C, an aqueous solution of silver nitrate (5g as silver nitrate) and 0.15g of potassium iodide were added while stirring. An aqueous solution of potassium bromide was added over 1 minute using a double jet method. More soluble silver nitrate? & (145g as silver nitrate) and potassium iodide4.
An aqueous solution of potassium bromide containing 2 g was added by double jet method. At this time, the addition flow rate was accelerated so that the flow rate at the end of addition was five times that at the start of addition. After the addition was completed, soluble salts were removed at 35°C by the sedimentation method, the temperature was raised to 40°C, 75 g of gelatin was removed, and the pH was adjusted to 6.
．． Adjusted to 7. The resulting emulsion has a projected area diameter of 0.9
The grains were tabular grains of 8 μm and average thickness of 0.138 μm, and the silver iodide content was 3 mol %. This emulsion was chemically sensitized using gold and sulfur sensitization.

As a surface protective layer, in addition to gelatin, an average molecular weight of 8000
polyacrylamide, polysodium polyethylene sulfonate,
Polymethyl methacrylate fine particles (average particle size 3.
An aqueous gelatin solution containing 0 μm), polyethylene oxide, and a hardening agent was used. A sensitizing dye and potassium iodide were added to the emulsion in the following proportions. Furthermore, as stabilizers, 4-hydroxy-6-methyl-1,3,3a,7-titrazaindene and 2,6bis(hydroxyamino)-4-
diethylamino-1,3,5-triazine and nitrone, trimethylolpropane as drying antifoggant,
Photographic material 201 was prepared by adding a coating aid and a hardening agent to form a coating solution, which was coated on both sides of a polyethylene terephthalate support at the same time as the surface protective layer and dried. The amount of coated silver for each photographic material is summarized below.

Process I is the following method.

<Developer formulation) Part A Potassium hydroxide Potassium sulfite Sodium bicarbonate Borate diethylene glycol ethylene diamine tetraacetic acid 5-Methylhensitriazole For 38f 107g 680g 85g 8g 56g 63.5g 2.28g Hydroquinone - Add soil and water 9 .50lPart B Glacial acetic acid 416.5g Diethylene glycol 644.5g 5-nitroindazole 9.5g 1-phenyl-3-pyrazolidone -L-Part
C Geltar aldehyde 187.3g Sodium metabisulfite ↓Add water
950- Starter acetic acid 270 Potassium bromide 300 Add water
1.51 (Developer preparation method) Add water 201 to the replenisher stock tank of about 501, and then add the above PartAsPartB, Part
C was sequentially added and dissolved with stirring, and finally the solution was adjusted to 381 with water to obtain a developer replenisher (pH 10.30).

After first filling the development processing tank of an automatic processor with a developer added at a ratio of 20 - of the starter to this developer replenisher i (pH 10, Is), the developer is replenished every time a photosensitive material is processed. Cut the liquid into 45-/1 piece (101 nc)
hX 121nch) supplemented.

<Fixer prescription) (Formulation for 381) Pa
rtA Fixer Preparation Method) Add 2 liters of water to an approximately 501 liter replenisher stock tank,
Next, Part A and Part B are sequentially added and dissolved while stirring, and finally, 387% is added with water. It was used as a fixer replenisher.

The fixing tank of an automatic processor was first filled with the same fixer replenisher (pH 4, 25).

After that, every time the sensitive material is processed, apply the above fixer replenisher at 30#1.
l/four cuts! (IO1nch x 121nch) was replenished.

Part Furthermore, the processing time of Dry to Dry is 9 for processing i.
6 seconds Then, in the same manner as in Example 1, various anion exchange resins were used in the circulation pump system piping of the fixing bath, and continuous treatment was performed until the cumulative replenishment amount of the fixing solution became three times the tank capacity.
After processing, 2.1 unexposed photosensitive materials were processed and the amount of remaining silver was measured. The results are shown in Table 2.

Table 2 When the exchange resin was used, favorable results were obtained in which the amount of residual silver was clearly lower than that using the weakly basic anion exchange resin.

Example 3 Example 1 After imagewise exposure of sample 101, continuous processing was performed in the following processing steps.

6.5 μgird Comparative Example Resin
1) 20 seconds 38°C Water washing 121 20 seconds 38°C 20m” Stable 20 seconds 38°C 20d drying 60 seconds 60°C *Water washing (2) → (2 tank countercurrent method to 1 liter).

The processing solutions used are as follows.

(Color developer) Tank liquid Replenisher diethylenetriamine As shown in Table 2, strongly basic anion exchange pentaacetic acid
2.0g 2.0g 1-Hydroxyethythene-1,1-diphosphonic acid (60%) Sodium sulfite 3.0g 4.0g 3.0g 7.0g Potassium carbonate Potassium bromide Potassium iodide Hydroxylamine sulfate 4-[ N-ethyl-N β-hydroxyethylamino]-2 Add methylaniline sulfate solution H (bleach-fix solution) 30.0 g 30.0 g 1.4 g 1.5 2.4 g 4.0 g 4. 5g 8.0g 1.01 1.01 10.05 10.25 Tank liquid Replenisher Ethylenediaminetetranodic acid ferric ammonium dihydrate 90.0 120 g Ethylenediamine tetranodic acid disodium salt 5.0 5.0g Sulfurous acid Sodium 12.0 30 g Ammonium thiosulfate aqueous solution (70%) 260.0 m 300a
d Acetic acid (98%) 3. Oaf 8.
0m bleach accelerator (I[1-(51) 0.01
Add 0.015 mol water 1. (
H! 1.01 pH 6,56,0 (Water wash/&) (tank liquid and replenisher are the same) Tap water is mixed with H-type strongly acidic cation exchange resin (Amberlite IR-120B manufactured by Rohm and Haas) and OH-type anion exchange resin. Water was passed through a mixed bed column packed with Amberlite IR-400 to reduce the concentration of calcium and magnesium ions to 3/l or less, followed by sodium dichloride isocyanurate 20/1 and sodium sulfate. 0.15g
/l was added.

The pH of this solution is in the range of 6.5-7.5.

(Stabilizing liquid) (Tank liquid and refilling liquid are the same) Formalin (3
7%) 2. Od polyoxyethylene-
p-monononylphenyl ether (average degree of polymerization 10) 0.3 Ethylenediaminetetraacetic acid disodium salt 0.05 Add water
1.0RpH 5,0-8,0 Next, in the same manner as in Example 1, a column filled with 120 m of various resins was installed in the circulation system of the bleach-fix solution, and the treatment steps BSC, D, E, F were carried out. .

G1 and [■].

In each processing step, 6000 ml of sample 101 was further processed (1000 ml of bleach-fix solution per 1 liter of resin), and then sample 101 was exposed to light using H:I OOCMS and processed in each processing step to determine the amount of remaining silver. The results obtained using X-rays are shown in Table 3 (exposed sample).

Next, the above-mentioned exposure was not carried out, but the same treatment was carried out to determine the amount of remaining silver, which is shown in Table 3.

In the present invention, the fact that there is almost no difference in the amount of residual silver between the exposed sample and the unexposed sample shows that the desilvering performance is improved due to the improvement in the fixing ability. Especially process DSE, F, G and H
The effect is remarkable.

(Example 4) After imagewise exposure in Example 1 processing 102, continuous processing was performed in the following processing step (2).

Process Processing time Processing temperature replenishment amount (351 x 1) Color development 3 minutes 15 seconds 38℃ 40M1 bleaching
White 45 seconds 38℃ 51l
1 fixation 1 minute 38℃ 15
m Stable + 1l 20 seconds 38℃ Stable +21 20 seconds 38℃ Stable (3) 20 seconds 38℃ 20-Drying 1 second 60℃ .

The processing solutions used are as follows.

(Color developer) Mother liquid axis) Replenisher (g) Diethylenetriaminepentaacetic acid Sodium sulfite Potassium carbonate Potassium bromide Potassium iodide 5.0 6.0 4.0 4.4 30.0 37.0 1.3 0.9 12*Hydroxylamine sulfate 4-[N-ethyl-N-β-hydroxyethylamino]-2 Add methylaniline sulfate water and pi( (bleach solution) 2.0 2.8 4.7 5.3 1. 01l.O&' 10.00 10.05 Mother liquor (g) Replenishment solution) Ethylenediaminetetranodic acid ferric ammonium dihydrate 1.3-diaminopropane tetraacetic acid ferric salt Ethylenediamine tetranodic acid ammonium bromide Ammonium nitrate 0g 20 g 0g 0g 4.0 5.0 100.0 160.0 30.0 5G, 0 Ammonia water (27%) Acetic acid (98%) Add water and pH (fixer) 20, Od 9, 〇- 1 ,01 5,5 Mother liquor axis) Ethylenediamine tetranodic acid disodium salt Sodium sulfite Sodium bisulfite Ammonium periosulfate aqueous solution (70%) Add water to pH (Stable solution) Mother liquor, replenisher Common formalin (37%) 5-chloro -2-Methyl-4-Isothiazoline-3-230.0ad 0.5 7.0 5.0 1.01 6.7 N23.0+d 15, Od 1.01 4.5 Replenisher (g) 0. 7 260.0sd 1.01 6.6 1.2- 6,0 ■ Phosphorus-3-one 3.0 Paar surfactant
0.4(C+.H□-0+CHz
CII*O+ +. Old ethylene glycol
Add 1.0 water 1.01p
H5,0-7,0 Processes using an ion exchange resin were designated as Processes J, L, and M in the same manner as in Example (3). Sample 1 with IOcMS
02 was subjected to wedge-shaped exposure, and the sample was processed at the start and end of continuous processing, and the residual silver amount at the maximum gradation part and the minimum magenta density (Dcmin) were measured (exposed sample).

Next, the same treatment was carried out without carrying out the above-mentioned exposure, and the amount of remaining silver was measured. The results are shown in Table 4.

2-Methyl-4-isothiazo In the present invention, even at the end of running, there is no defective desilvering due to poor fixing, and magenta tin (D
No increase in Gwin> was observed, and good photographic properties were maintained.

Claims (1)

[Claims] In a processing method in which a silver halide photographic light-sensitive material having at least one silver iodobromide emulsion layer on a support is processed with a processing liquid having fixing ability after development, the processing liquid having fixing ability is applied to an anion exchange resin. A method for processing a silver halide photographic light-sensitive material, characterized in that the processing is carried out while contacting the material, and the amount of the processing liquid having the fixing ability used is 20 liters or more and up to 2,000 liters per liter of the anion exchange resin.