JP2888892B2 - Processing method of silver halide color photographic light-sensitive material - Google Patents

Description

The present invention relates to a method for processing a silver halide color photographic light-sensitive material.

<Prior Art> A silver halide color photographic light-sensitive material (hereinafter, referred to as a color photographic material) is subjected to processes such as color development, desilvering, washing with water, and stabilization after exposure.

A color developing solution is used for color development, a bleaching solution, a bleach-fixing solution and a fixing solution for desilvering, tap water or ion-exchanged water for washing, and a stabilizing solution for stabilizing treatment. The temperature of each processing solution is usually adjusted to 30 to 40 ° C., and the color photographic material is immersed in these processing solutions for processing.

Among such processing steps, the basics are a color development step and a desilvering step.

In the color developing step, the exposed silver halide is reduced by a color developing agent to generate silver, and the oxidized color developing agent reacts with a color forming agent (coupler) to give a dye image.

In the desilvering step subsequent to the color development step, silver produced in the color development step is oxidized by the action of a bleaching agent as an oxidizing agent, and then dissolved by a fixing agent as a complex ion forming agent of silver ions. Thus, only a dye image is formed.

The desilvering step includes a method in which the bleaching step and the fixing step are performed in the same bath, a method in which the bleaching step and the bleach-fixing step are performed in separate baths, and the like. In this case, each bath may be a multi-bath.

And, in addition to the above basic steps,
Various auxiliary steps are performed for the purpose of maintaining physical quality or improving storage stability. Such a process is performed using, for example, a hardening bath, a stop bath, a stabilizing bath, a washing bath, or the like.

The processes described above are usually performed using an automatic developing machine, and the continuous processing by the automatic developing machine generally requires the processing amount of the color photosensitive material in order to keep the performance of the processing solution constant. "Replenishment method" that replenishes replenisher according to
When the processing amount of the color photosensitive material reaches a predetermined amount,
There is a “batch method” in which part or all of the used processing solution is replaced with a new solution.

Of these systems, the replenishment system is often employed.

In recent years, with the spread of small in-store processing service systems called mini-labs, there has been a strong demand for faster processing.

In particular, the time required for the desilvering step has conventionally occupied most of the processing time required for all the steps, and it has been desired to reduce the time required for the desilvering step.

However, the ferric ethylenediaminetetraacetic acid complex salt, which is mainly used as a bleaching agent in a bleaching solution or a bleach-fixing solution, has a fundamental defect that the oxidizing power is weak, and various kinds of bleaching accelerators and the like are used. Despite improvements, these requirements have not been met.

On the other hand, red blood salts, dichromates, ferric chlorides, persulfates, bromates and the like are known as bleaching agents having a strong oxidizing power. Each of them has many disadvantages from the viewpoint of properties and the like, and cannot be widely used for storefront processing and the like.

Under such circumstances, for example, a bleaching solution containing a ferric complex of 1,3-diaminopropanetetraacetic acid having a high oxidizing power and having a pH of about 6 is disclosed in JP-A-62-222252. The publication discloses a bleaching solution (eg, pH 5.0) containing a ferric complex of 1,3-diaminopropanetetraacetic acid.

This method enables more rapid silver bleaching than a bleaching solution containing a ferric ethylenediaminetetraacetic acid complex salt, but particularly, when a bleaching treatment is carried out directly without using a color developing solution or an intermediate bath, bleaching fog is reduced. The drawback of generating color fogging, which is called "color fogging", is a major problem.

<Problems to be Solved by the Invention> In order to address the above-mentioned problems, the present inventors have previously developed an oxidizing agent having a high oxidizing power, such as 1,3-diaminopropanetetraacetic acid second complex, as a bleaching agent. It has been proposed to use a bleaching solution containing an agent (high potential oxidizing agent) at a pH of 2.5 to 4.2 (Japanese Patent Application No. 01-168348).

In this case, an organic acid such as acetic acid is usually used to obtain the above pH.

In fact, the present inventors have obtained an effect that by using such a bleaching solution, rapid processing can be performed without causing bleaching fog.

However, when processing a color photosensitive material by filling such a bleaching solution in a processing tank of an automatic developing machine, various rubber members are used as constituent members of a processing tank, a replenishing tank, or a replenishing pump, and other accessories. I have.

Conventionally, as such a rubber member, for example, fluorine rubber as a material used for a valve material of a replenishment pump, and chloroprene rubber as a material used as a seal material in a circulation system of a treatment tank are typically exemplified.

In addition, styrene-butadiene rubber is used for various insulating members and duct members, or a battery case, and acrylonitrile-butadiene rubber is used for a gasket.

However, it has been found that, in these conventional rubber members, when a bleaching solution containing a high potential oxidizing agent and an organic acid is used, the bleaching solution or the bleaching replenisher swells with time.

Then, for example, when the rubber member used for the valve of the refill pump swells, the discharge amount changes, and various problems occur, such that stable and good photographic performance cannot be obtained.

Such a problem also occurs in a bleach-fix solution containing an oxidizing agent having a high oxidizing power and an organic acid such as acetic acid.

The present invention is caused by the fact that a rubber member constituting a part of an automatic developing machine comes into contact with the above-mentioned processing solution and / or a replenisher thereof in rapid processing using a processing solution having a bleaching ability containing a high potential oxidizing agent. An object of the present invention is to provide a method for processing a silver halide color photographic light-sensitive material capable of solving various problems and stably obtaining good photographic performance.

<Means for Solving the Problems> In order to achieve the above object, the present invention has the following configuration (1).

(1) A compound having an oxidation-reduction potential of 150 mV or more containing 0.2 mol / or more and having an acid dissociation constant (pka) of 2 to 5.5 after color development of the silver halide color photographic light-sensitive material after imagewise exposure. In treating with a processing solution having a bleaching ability containing 0.5 mol / or more, an SP value selected from silicone rubber, ethylene-propylene rubber and butyl rubber is applied to a rubber member that comes into contact with a processing solution having a bleaching ability or a replenisher thereof. 7.0-8.0 (cal / cm
³ ) A method for processing a silver halide color photographic light-sensitive material, wherein a ^1/2 rubber material is used.

<Operation> According to the present invention, the silver halide color photographic light-sensitive material after imagewise exposure is processed using an automatic processor.

In this case, a bleaching treatment solution containing an oxidizing agent having a redox potential of 150 mV or more (high-potential oxidizing agent) at 0.2 mol / or more and containing a compound having an acid dissociation constant of 2 to 5.5 at 0.5 mol / or more, Since the specific rubber material is used for the replenisher or the rubber member constituting the part of the automatic developing machine that comes into contact with both, the processing solution having the bleaching ability and / or
Alternatively, it is possible to avoid a problem that the ink swells with the lapse of time upon contact with the replenisher and the discharge amount changes when the replenisher is used for a valve of a replenishment pump.

 Therefore, stable and good photographic performance can be obtained.

Incidentally, the above-mentioned trouble is not caused by a processing solution having a bleaching ability containing a ferric ethylenediaminetetraacetic acid complex which has been widely used as a conventional bleaching agent. This problem becomes apparent in rapid processing, and the present invention effectively solves this problem.

<Specific Configuration> Hereinafter, a specific configuration of the present invention will be described in detail.

In the present invention, a silver halide color photographic light-sensitive material after imagewise exposure (hereinafter also referred to as a color light-sensitive material or a light-sensitive material) is processed using an automatic developing machine.

In this case, at least one of silicone rubber, ethylene-propylene rubber and butyl rubber is used as a rubber member constituting a part of the automatic developing machine which comes into contact with a processing solution having a bleaching ability and / or a replenisher thereof.

The silicone rubber (Q) is represented by the following general formula (A), and has partially an inorganic and organic bond, and has no unsaturated bond in the main chain.

In the general formula (A), R is methyl, phenyl,
Represents vinyl, trifluoropropyl and the like.

Specifically, polydimethylsilicone rubber (MQ), methylvinylsilicone rubber (VMQ), methylphenylsilicone rubber (PMQ), fluorosilicone rubber (FVMQ) and the like are mentioned according to the type of R.

 The basic structure of each silicone rubber is shown below.

Of these, methyl vinyl silicone rubber (VMQ) and fluorosilicone rubber (FVMQ) are preferred, and among the vinyl vinyl silicone rubbers, those produced with a higher crosslinking density than usual are preferred. It is excellent in hydrolysis resistance and chemical resistance and can prevent rubber deterioration due to contact with a processing solution having bleaching ability and / or a replenisher thereof.

Such substances may optionally be vulcanizing agents, for example 2,5-
Dimethyl-2,5-di (tert-butylperoxy)
It is commercially available as a compound kit containing hexane or the like, and a rubber member can be molded using a commercially available product as it is.

Suitable examples include silicone rubber commercially available under the trade name KE850 (manufactured by Shin-Etsu Optical Co., Ltd.) and commercial products available under the trade names SRX495u, SH851u, SH745u (all manufactured by Toray Silicone Co., Ltd.). And a fluorosilicone rubber commercially available under the trade name PY37-016u (manufactured by Toray Silicone Co., Ltd.).

Among them, silicone rubber for steam resistance, such as the above-mentioned trade name SRX495u, has a higher crosslinking density than usual, and is particularly suitable.

The ethylene-propylene rubber in the present invention includes EPM, which is a copolymer of ethylene and propylene, or EPDM, which is a terpolymer obtained by copolymerizing a smaller amount of a third component.
The EPM is represented by the following general formula (B), and the EPDM is represented by the following general formula (C).

The third component in EPDM is a diene monomer for crosslinking such as ethylidene norbornene, dicyclopentadiene, 1,4-hexadiene and the like, which is bonded as a side chain as the X component in the following general formula (C). .

In the above, m / n is about 0.01 to 100 by weight ratio, p /
(M + n) is about 9 or less in weight ratio.

EPM and EPDM can be formed by a known method by adding a vulcanizing agent such as a peroxide or carbon black if necessary.

Among them, it is preferable to use EPDM, for example, EPDM
MITSUI EPT1045 (Mitsui Petrochemical Industry Co., Ltd.)
And the like are preferred.

The vulcanizing agent used in the present invention is preferably a peroxide-based one rather than a sulfur-based one. This is because peroxides do not chemically react with the silver halide light-sensitive material, thereby preventing fogging.

As the rubber used in the present invention, butyl rubber (II
R) can also be used.

Butyl rubber (IIR) is obtained by copolymerizing isobutylene with a small amount of isoprene, also called isobutylene-isoprene rubber, and includes those represented by the following general formula (D).

In this case, r / s is about 0.01 to 100 in weight ratio.

Of these rubber materials, the SP value of silicone rubber is
About 7.3 to about 7.6 (cal / cm ³ ) ^1/2 , and the SP value of ethylene-propylene rubber is about 7.9 to about 8.0 (cal / cm ³ ) ^1/2 , and the SP value of butyl rubber is about 7.85 ( cal / cm ³ ) About ^1/2 .

The SP value in this case is for the raw rubber (raw rubber) before adding an additive such as a vulcanizing agent.

As is well known, the SP value (solubility index, solubility parameter, δ) is an index of the intermolecular cohesion of molecules and is given by the square root of the cohesive energy density.

For the method of measuring the SP value of rubber and the numerical values, see Shinzo Yamashita, "Basics of Rubber Technology", edited by The Rubber Association of Japan, §1, Basic properties p1 ~
50 (1983).

The processing solution or the replenisher having the bleaching ability used in the present invention contains a compound having an acid dissociation constant (pKa) of 2 to 5.5 typified by acetic acid or the like, mainly an organic acid or the like at 0.5 mol / or more, as described later. It is contained.

 And, for example, the SP value of acetic acid is 10.1.

Therefore, the swelling due to the use of the rubber member over time and the accompanying troubles occur because the rubber member, in particular,
The reason that these problems are solved according to the present invention is that the difference between the SP value of the rubber material and the SP value between the organic acid and the like is increased by being attacked by an organic acid such as acetic acid. It is presumed to be.

The lower limit of the SP value of the rubber material is about 7.0 (cal / cm ³ ) ^1/2 or more in order to exhibit good rubber properties.

Rubbers commonly used as rubber materials for members of automatic developing machines, such as fluorine rubber (FKM) used for valve materials of refill pumps and chloroprene rubber used for sealing materials in the circulation system of processing tanks In (CR), troubles such as swelling increase.

Similar troubles occur with styrene-butadiene rubber (SBR) and acrylonitrile-butadiene rubber (NBR).

 The rubber member may be formed by a known method.

In the present invention, the member of the automatic developing machine that comes into contact with the processing solution having the bleaching ability and / or the replenisher thereof is a rubber member constituting a processing tank, a replenishing tank, a replenishing pump, and other accessories. Specific examples thereof include a valve of a replenishing pump, a seal in a circulation system of a treatment tank, packing of a flow system, a flexible hose, a joint part thereof, a rubber material used for a squeeze blade, and the like.

In the present invention, specific examples of rubber members in which it is preferable to use silicone rubber and ethylene-propylene rubber are shown below.

(1) Silicone rubber Valve material for refill pumps, sealing material for the circulation system of the processing tank, sealing material such as O-rings used for the replenishment filter, rubber tubes for preventing scratches such as films used for racks in the processing tank And rubber materials used for sheets and rollers.

(2) Ethylene-propylene rubber Valve material, diaphragm, etc. for refill pumps.

In the present invention, the color photographic material after the color development processing is processed with a processing solution having a bleaching ability.

The processing solution having the bleaching ability used at this time is, specifically, a bleaching solution or a bleach-fixing solution. Typical desilvering steps including the processing with such a processing solution are as follows. .

Bleaching → fixing bleaching → bleaching fixing bleaching → washing → fixing rinsing → bleaching → fixing bleaching → bleaching fixing → fixing washing → bleaching fixing bleaching fixing → bleaching fixing In particular, in the present invention, like a color negative film or a color reversal film, Since the purpose of the present invention is to rapidly desilver a color light-sensitive material composed of silver halide containing silver iodide, the above steps are particularly preferable. It is disclosed in JP-A-61-75352.

Further, the processing bath such as the bleaching bath and the fixing bath applied to the above-mentioned process may have a single bath configuration of two or more layers (for example, 2 to 4 layers).
(In this case, a counter-current system is preferable).

The treatment with the processing solution having the bleaching ability in the present invention,
After the color development,
The effect is great.

Therefore, the bleaching liquid applied to the bleaching step immediately after the color development processing will be described as a representative.

Such a bleaching process preferably employs a replenishment method in which replenishment is performed using a bleaching replenisher, and the bleaching replenisher is used in order to maintain the processing performance of the bleaching solution at a constant level. It is a liquid used for replenishment, and is usually used in continuous processing by an automatic developing machine.

The bleaching solution and / or the bleaching replenisher used in the present invention (hereinafter, both solutions may be collectively referred to as a bleaching solution) have a redox potential of 150 mV or more, preferably 180 mV or more.
As described above, an oxidizing agent of more than 200 mV, that is, a bleaching agent is contained.

The redox potential of the bleach above is determined by the Transactions of the Faraday Society (Tran
sactions of the Faraday Society), 55 (1959)
Year), defined by the oxidation-reduction potential obtained by the method described on pages 1312 to 1313.

The oxidation-reduction potential in this case was obtained by the above-described method under the condition of pH 6.0.

Thus, the potential determined at pH 6.0 is adopted as p
This is because the vicinity of H6.0 is used as a guide for the occurrence of bleaching fog.

That is, the present inventors, in fact, when the color developing process is completed and the photosensitive material enters the bleaching solution,
It has been confirmed that when the pH decreases rapidly, the bleaching fog is small when the pH decreases rapidly, and the bleaching fog increases when the pH decreases slowly or when the pH of the bleaching solution is high. Based on pH 6.0.

In the present invention, a bleaching agent having a redox potential of 150 mV or more is used because a sufficient oxidizing power can be obtained by such a bleaching agent, and a rapid bleaching treatment can be performed.

Examples of such a bleaching agent include inorganic compounds such as red blood salt, ferric chloride, dichromate, persulfate, and bromate, and some organic compounds of iron (III) complex aminopolycarboxylate. Can be mentioned.

In the present invention, it is preferable to use an aminopolycarboxylate iron (III) complex salt in view of environmental protection, handling safety, metal corrosiveness and the like.

Hereinafter, iron aminopolycarboxylate (II
I) Specific examples of the complex salt will be given below, but it should not be construed that the invention is limited thereto. In addition, the oxidation-reduction potential in the above definition is described.

Among these, particularly preferred is compound No. 7
1,3-propylenediaminetetraacetate iron (III) complex salt (hereinafter, referred to as
1,3-PDTA.Fe (III)).
62-222252 and JP-A-64-24253, which are the same compounds as the iron (III) complex salt of 1,3-diaminopropanetetraacetate).

The aminopolycarboxylate iron (III) complex salt is used as a salt of sodium, potassium, ammonium or the like, and an ammonium salt is preferred in terms of the fastest bleaching.

The iron (III) complex salt of ethylenediaminetetraacetate (EDTA · Fe (III), which is widely used in the industry, is 110 mV, and the iron (III) complex salt of diethylenetriaminepentaacetate or trans-1,2-cyclohexanediaminetetraacetate is used. (III) Complex salts and the like are 80 mV and are excluded from those in the present invention.

The bleaching solution in the present invention contains a bleaching agent in an amount of 0.2 mol / or more, preferably 0.3 to 0.7 mol /, more preferably 0.4 to 0.7 mol /.
~ 0.6 mol / content.

By setting the content of the bleaching agent within the above range, the processing can be speeded up and bleaching fog and stain can be reduced. However, the use of an excessively high concentration liquid adversely affects the bleaching reaction, so the upper limit concentration is 0.
It is good to be about 7 mol.

The concentration of the iron (III) aminopolycarboxylate complex preferably used in the present invention is preferably in the above range.

In the present invention, the bleaching agent may be used alone even if it is used alone.
More than one species may be used in combination.

When two or more kinds are used in combination, the total concentration may be within the above range.

Further, in the present invention, a bleaching agent having an oxidation-reduction potential of less than 150 mV may be used in addition to a bleaching agent having an oxidation-reduction potential of 150 mV or more. However, the amount of oxidation
It is preferable that the amount be about 0.5 mol or less per mol of the bleaching agent of 150 mV or more.

Examples of such a compound include a ferric complex of ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, and cyclohexanediaminetetraacetic acid having a redox potential of 150 mV or more, particularly when used in combination with an aminopolycarboxylic acid iron (III) complex salt. be able to.

When the aminopolycarboxylic acid iron (III) complex salt is used in the bleaching solution, it can be added in the form of a complex salt as described above. However, the aminopolycarboxylic acid which is a complex-forming compound and a ferric salt (for example, , Ferric sulfate, ferric chloride, ferric nitrate, ferric ammonium sulfate, ferric phosphate) to form a complex salt in the bleaching solution.

In the case of this complex formation, the aminopolycarboxylic acid is
It may be added slightly in excess of the amount required for complex formation with ferric ion, and when added in excess, usually 0.01 to
The excess is preferably in the range of 10%.

In the bleaching solution and / or the bleaching replenisher of the present invention, a compound having an acid dissociation constant (pka) of 2 to 5.5 contains 0.5 mol /
Or more, preferably 0.7 to 3 mol /, more preferably 1.5
~ 2.5 mol / content.

The acid dissociation constant (pka) in the present invention is generally called an acid dissociation constant and represents a logarithm of a reciprocal of that represented by Ka, and indicates a value obtained at an ionic strength of 0.1 mol / at 25 ° C.

In the present invention, the bleaching solution is generally used at pH 2-8.

In particular, in order to speed up the treatment, the pH is preferably set to 2.5 to 4.2, preferably 2.5 to 4.0, particularly preferably 2.5 to 3.5, and the replenisher is usually used at 1.0 to 4.0.

For this reason, by including the above compound in the bleaching solution and / or the bleaching replenisher within the above range,
It is possible to adjust the pH to the above-mentioned range, in particular, a preferable range.

When the above compounds are used in combination, the total amount may be within the above range.

By containing a compound having a pKa of 2 to 5.5 in this manner, bleaching fog can be further eliminated, and an increase in stain in an uncolored portion after processing can be improved.

Examples of the compound having a pKa of 2 to 5.5 include inorganic acids such as phosphoric acid, acetic acid, malonic acid, and organic acids such as citric acid.
Although any of these may be used, the acid having a pKa of 2 to 5.5 which is effective by the above-mentioned improvement is an organic acid. Further, among the organic acids, an organic acid having a carboxyl group is particularly preferable.

The organic acid having a pKa of 2 to 5.5 may be a monobasic acid or a polybasic acid. In the case of a polybasic acid, it can be used as a metal salt (for example, a sodium or potassium salt) or an ammonium salt if its pKa is within the above range of 2 to 5.5. Further, two or more organic acids having a pKa of 2 to 5.5 can be used in combination. However, aminopolycarboxylic acid and its Fe complex salt are excluded.

Preferred specific examples of the organic acid having a pKa of 2 to 5.5 used in the present invention include formic acid, acetic acid, monochloroacetic acid, monobromoacetic acid, glycolic acid, propionic acid, monochloropropionic acid, lactic acid, pyruvic acid, acrylic acid, butyric acid, and isomeric acid. Aliphatic monobasic acids such as butyric acid, pivalic acid, aminobutyric acid, valeric acid and isovaleric acid; amino acid compounds such as asparagine, alanine, arginine, ethionine, glycine, glutamine, cysteine, serine, methionine, leucine; Acids and monosubstituted benzoic acids such as chloro and hydroxy; aromatic monobasic acids such as nicotinic acid; oxalic acid, malonic acid, succinic acid, tartaric acid, malic acid, maleic acid, fumaric acid, oxaloacetic acid, glutaric acid, Aliphatic dibasic acids such as adipic acid; aspartic acid, glutamic acid, glutaric acid, cystine And various organic acids such as amino acid-based dibasic acids such as acetic acid and ascorbic acid; aromatic dibasic acids such as phthalic acid and terephthalic acid; and polybasic acids such as citric acid.

In the present invention, among these, a monobasic acid having a carboxyl group is preferred, and acetic acid and glycolic acid (hydroxyacetic acid) are most preferred. Also, a combination of acetic acid and glycolic acid is preferable.

When adjusting the pH of the bleaching solution and / or the bleaching replenisher to the above range, the acid and the alkali agent (for example, aqueous ammonia, KOH, and NaOH) may be used in combination. Among them, aqueous ammonia is preferable.

In the present invention, a bleaching solution and / or a bleaching replenisher,
Alternatively, various bleaching accelerators can be added to the prebath.

For such bleaching accelerators, for example, U.S. Patent No. 3,893,858, German Patent No. 1,290,812, British Patent No. 1,138,842, JP-A-53-95630, Research Disclosure No. 17129 (1978
A compound having a mercapto group or a disulfide group, a thiazolidine derivative described in JP-A-50-140129, a thiourea derivative described in U.S. Pat. No. 3,706,561; The iodides described in JP-A 16235, the polyethylene oxides described in German Patent No. 2,748,430, the polyamine compounds described in JP-B No. 45-8836, and the like can be used. Particularly preferred are mercapto compounds as described in GB 1,138,842.

In the bleaching solution of the present invention, in addition to the bleaching agent and the above compounds, a rehalogenating agent such as a bromide such as potassium bromide, sodium bromide, ammonium bromide or chloride such as potassium chloride, sodium chloride or ammonium chloride Can be included. The concentration of the rehalogenating agent is 0.1 to 5 mol per 1 as a bleaching solution, preferably
0.5 to 3 mol.

Further, it is preferable to use ammonium nitrate as the metal corrosion inhibitor.

In the present invention, it is preferable to employ a replenishing method, and the replenishing amount of the bleaching solution is 200 ml or less, preferably 140 to 10 ml per 1 m ² of the light-sensitive material.

The bleaching treatment time is 120 seconds or less, preferably 50 seconds or less, and more preferably 40 seconds or less. The present invention is effective in such a shortened processing time.

In the treatment, iron (III) aminopolycarboxylate
It is preferable that the bleaching solution using the complex salt is subjected to aeration to oxidize the resulting iron (III) aminopolycarboxylate complex salt.

In a preferred desilvering step of the present invention, the photosensitive material that has been bleached with the above-described bleaching solution is processed with a processing solution having a fixing ability.

Processing solutions having fixing ability in this case are specifically a fixing solution and a bleach-fixing solution, and these processing solutions contain a fixing agent.

As fixing agents, sodium thiosulfate, ammonium thiosulfate, sodium ammonium thiosulfate, thiosulfates such as potassium thiosulfate, sodium thiocyanate,
Thiocyanates such as ammonium thiocyanate and potassium thiocyanate, (rodane salts), thiourea, thioether and the like can be used.

Among them, it is preferable to use ammonium thiosulfate. The amount of the fixing agent is 0.1% per fixing solution or bleach-fixing solution.
It is 3 to 3 mol, preferably 0.5 to 2 mol.

From the viewpoint of promoting fixing, it is also preferable to use the above ammonium thiocyanate (rhodanammonium), thiourea, and thioether (for example, 3,6-dithia-1,8-octanediol) in combination. Is generally about 0.01 to 0.1 mol per fixing solution or bleach-fixing solution. However, in some cases, the use of 1 to 3 mol can greatly enhance the fixing promoting effect.

As a fixing agent in a fixing solution or a bleach-fixing solution, in order to speed up processing, it is particularly preferable to use a thiosulfate and a thiocyanate in combination, and particularly to use a combination of ammonium thiosulfate and ammonium thiocyanate. Is preferred.

In this case, the thiosulfate may be used at 0.3 to 3 mol / and the thiocyanate may be used at 1 to 3 mol /, preferably 1 to 2.5 mol /.

Other compounds other than thiocyanate which can be used in combination with thiosulfate (particularly ammonium thiosulfate) include thiourea and thioether (eg, 3,6-dithia-
1,8-octanediol) and the like.

The amount of these compounds to be used in combination is generally about 0.01 to 0.1 mol per 1 fixer or bleach-fixer, but may be 1 to 3 mol depending on the case.

The fixing solution or the bleach-fixing solution contains a sulfite (eg, sodium sulfite, potassium sulfite, ammonium sulfite) and a bisulfite adduct of hydroxylamine, hydrazine, aldehyde compound (eg, sodium acetaldehyde bisulfite) as a preservative. It can be contained. Further, various fluorescent whitening agents, defoaming agents or surfactants, polyvinylpyrrolidone, organic solvents such as methanol can be contained. It is preferable to use a sulfinic acid compound of

The bleach-fixing solution may contain the above-mentioned known bleaching agent. Preferably, it is a ferric aminopolycarboxylic acid complex salt.

In the bleach-fix solution, the amount of the bleaching agent per bleach-fix solution is from 0.01 to 0.5 mol, preferably from 0.015 to 0.3 mol, particularly preferably from 0.02 to 0.2 mol.

In the present invention, the bleach-fix solution at the start of processing (mother liquor)
Is prepared by dissolving the compound used in the above-mentioned bleach-fixing solution in water, but may be prepared by mixing separately prepared bleaching solution and fixing solution in appropriate amounts. The fixing solution has a pH of 5 to 5.
9 is preferable, and 7-8 are more preferable. Further, the pH of the bleach-fixing solution is preferably from 6 to 8.5, more preferably from 6.5 to 8.5.
~ 8.0 is preferred.

In addition, as such a bleach-fix solution, an oxidation-reduction potential of 15
0.2 mol / or more of oxidizing agent of 0 mV or more, and pKa2-5.5
A compound containing 0.5 mol / or more of the compound may be used. Use of such a compound is preferable in terms of speeding up the treatment.

In such a case, any of silicone rubber, ethylene-propylene rubber and butyl rubber is used as the rubber material as described above, which comes into contact with the bleach-fixing solution and / or its replenisher.

When the replenishment method is employed, the replenisher of the fixing solution or the bleach-fixing solution is preferably from 300 to 3000 ml, more preferably from 300 to 1000 ml, per m ² of the light-sensitive material.

Further, it is preferable to add various aminopolycarboxylic acids or organic phosphonic acids to the fixing solution or the bleach-fixing solution for the purpose of stabilizing the solution.

In the present invention, the total processing time of the fixing process or the bleach-fixing process performed after the bleaching process is preferably 0.5 to 2 minutes, particularly preferably 1 to 1.5 minutes.

The shorter the total processing time of the desilvering step of the present invention is, the more the effect of the present invention can be obtained. The preferred time is 1-4 minutes,
More preferably, it is 1 minute 30 seconds to 3 minutes. Further, the processing temperature is 25 to 50 ° C, preferably 35 to 45 ° C. In a preferable temperature range, the desilvering speed is improved, and generation of stain after processing is effectively prevented.

In the above description, the bleaching step immediately after the color development processing, which is the preferred desilvering step in the present invention, has been described. Also, the present invention can be applied.

The bleach-fixing solution and / or its replenisher used in this treatment contains an oxidizing agent having an oxidation-reduction potential of 150 mV or more at 0.2 mol / or more and a compound having a pKa of 2 to 5.5 at 0.5 mol / or more. The same compound as the bleach-fix solution thus prepared can be contained.

Even in such a treatment, troubles due to swelling of the rubber and the like can be prevented because silicone rubber, ethylene-propylene rubber, and butyl rubber are used for the rubber material as described above.

As described above, the present invention can be applied not only to bleaching or bleach-fixing immediately after color development, or bleach-fixing subsequent to bleaching, but also to redox potential such as bleaching via a stop bath or the like. The invention can be applied to any treatment solution containing an oxidizing agent (high potential oxidizing agent) of 150 mV or more and a compound having a pKa of 2 to 5.5 within the scope of the present invention.

In the desilvering process such as bleaching, bleach-fixing and fixing of the present invention, the stirring can be enhanced as much as possible. As a specific method of strengthening stirring,
JP-A-62-183460 and JP-A-62-183461.
A method of increasing the stirring effect by using the rotating means of No. 61, and further improving the stirring effect by moving the photosensitive material while bringing the wiper blade provided in the liquid into contact with the emulsion surface and causing the emulsion surface to be turbulent. And a method for increasing the circulating flow rate of the entire processing liquid. Such a stirring improving means is effective for any of the bleaching solution, the bleach-fixing solution and the fixing solution. It is considered that the improvement of the stirring speeds up the supply of the bleaching agent and the fixing agent into the emulsion film, and consequently increases the desilvering speed. The means for improving the stirring is more effective when a bleaching accelerator is used, and can significantly increase the bleaching accelerating effect or eliminate the fixing inhibiting effect of the bleaching accelerator.

The present invention is generally carried out by applying an automatic developing machine and performing continuous processing. The automatic developing machines used in the present invention are described in JP-A-60-191257, JP-A-60-191258 and JP-A-60-191259. It is preferable to have the photosensitive material conveying means described in (1).
As described in Japanese Patent Application Laid-Open No. 60-191257, such a transport means can significantly reduce the carry-in of the processing solution from the pre-bath to the post-bath, and is highly effective in preventing the performance of the processing solution from deteriorating. Such an effect is particularly effective for reducing the processing time in each step and reducing the replenishing amount of the processing solution.

The present invention is preferably applied to processing in which the total processing time (however, excluding the drying time) is short. Specifically, the present invention is effective in processing in which the total processing time is 8 minutes or less, and more preferably 7 minutes or less. .

In the present invention, a known color developing agent for a primary aromatic amine is contained in a color developing solution used in a color developing process performed prior to a process using a processing solution having a bleaching ability. Preferred examples are p-phenylenediamine derivatives, and known ones can be used.

As a preservative, a sulfite such as sodium sulfite, potassium sulfite, sodium bisulfite, potassium bisulfite, sodium metasulfite, potassium metasulfite, or a carbonyl sulfite adduct may be added to the color developing solution as necessary. it can.

The preferred amount of the preservative is 0.5 to 0.5 per color developing solution.
1010 g, more preferably 1-5 g.

Further, as the compound for directly preserving the aromatic primary amine color developing agent, various hydroxylamines, hydroxamic acids described in Japanese Patent Application No.
Hydrazines and hydrazides described in No. 170756, ibid.
Phenols described in 188742 and 61-203253;
It is preferable to add α-hydroxyketones and α-aminoketones described in 61-188741 and / or various sugars described in 61-180616. Further, in combination with the above compounds, Japanese Patent Application Nos. 61-147823, 61-166664 and 61-1656.
No. 21, 61-164515, 61-170789 and 61-16
Monoamines described in No. 8159, etc., Nos. 61-173595, 61
-164515, diamines described in 61-186560 and the like,
Polyamines described in 61-165621, 61-169789 and 61-1888619, nitroxy radicals described in 61-197760, alcohols described in 61-186561 and 61-197419, It is preferable to use the oximes described in 61-198987 and the tertiary amines described in 61-265149.

Other preservatives include JP-A-57-44148 and JP-A-57-44148.
No. 53749, salicylic acids described in JP-A-59-180588, alkanolamines described in JP-A-54-3582, polyethyleneimines described in JP-A-56-94349, U.S. Pat. An aromatic polyhydroxy compound described in No. 3,746,544 may be contained as necessary. Particularly, addition of an aromatic polyhydroxy compound is preferred.

The color developing solution used in the present invention is preferably pH 9-1.
2, more preferably 9 to 11.0, and the color developing solution may further contain a compound of a known developing component.

In order to maintain the above pH, it is preferable to use various buffers.

Specific examples of the buffer include sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, trisodium phosphate, tripotassium phosphate, disodium phosphate, dipotassium phosphate, sodium borate, potassium borate, Sodium tetrafonate (borax), potassium tetrafonate, sodium o-hydroxybenzoate (sodium salicylate), potassium o-hydroxybenzoate, sodium 5-sulfo-2-hydroxybenzoate (sodium 5-sulfosalicylate), Potassium 5-sulfo-2-hydroxybenzoate (potassium 5-sulfosalicylate) and the like can be mentioned. However, the invention is not limited to these compounds.

The amount of the buffer added to the color developing solution is preferably 0.1 mol / or more, and particularly preferably 0.1 to 0.4 mol /.

In addition, various chelating agents can be used in the color developing solution as an inhibitor of precipitation of calcium or magnesium, or for improving the stability of the color developing solution.

As the chelating agent, an organic acid compound is preferable, and examples thereof include aminopolycarboxylic acids, organic phosphonic acids, and phosphonocarboxylic acids. Specifically, nitrilotriacetic acid, diethylenetriaminepentaacetic acid, ethylenediaminetetraacetic acid, N, N, N-trimethylenephosphonic acid, ethylenediamine-N, N, N ', N'-tetramethylenephosphonic acid, transcyclohexanediaminetetraacetic acid 1,2-diaminopropanetetraacetic acid, hydroxyethyliminodiacetic acid, glycol ether diaminetetraacetic acid, ethylenediamine orthohydroxyphenylacetic acid, 2-phosphonobutane-1,2,4-tricarboxylic acid, 1-hydroxyethylidene-1,1- Examples thereof include diphosphonic acid and N, N'-bis (2-hydroxybenzyl) ethylenediamine-N, N'-diacetic acid. These chelating agents may be used in combination of two or more as necessary. These chelating agents may be added in an amount sufficient to block metal ions in the color developing solution, for example, 0.1 to 10 g per one.

In the present invention, an optional antifoggant can be further added, if necessary. As antifoggants, alkali metal halides such as sodium chloride, potassium bromide and potassium iodide and organic antifoggants can be used. Examples of the organic antifoggant include benzotriazole, 6-nitrobenzimidazole, 5-hydroxyloisoindazole, 5-methylbenzotriazole, 5-hydroxylobenzotriazole, 5-chloro-benzotriazole, 2-thiazolyl-benzimidazole, Representative examples include nitrogen-containing heterocyclic compounds such as -thiazolylmethyl-benzimidazole, indazole, hydroxyazaindolizine, and adenine.

The color developer used in the present invention may contain a fluorescent whitening agent. As the fluorescent whitening agent, a 4,4'-diamino-2,2'-disulfostilbene compound is preferable. The amount added is 0.5 g / preferably 0.1 g to 4 g /.

Further, various surfactants such as alkylsulfonic acid, arylsulfonic acid, aliphatic carboxylic acid, and aromatic carboxylic acid may be added as necessary.

The processing temperature in the color developing solution in the present invention is 20 to 50 ° C,
Preferably it is 30-45 degreeC. The processing time is 20 seconds to 5 minutes, preferably 30 seconds to 3 minutes 20 seconds. When the replenishment method is adopted, the replenishment amount is preferably smaller, but is preferably 100 to 1500 ml, preferably 100 to 800 ml per 1 m ^{2 of} the light-sensitive material. More preferably, the volume is 100 to 400 ml.

In addition, the color developing bath is divided into two or more baths as necessary,
The color developing replenisher may be replenished from the first bath or the last bath to shorten the developing time and reduce the replenishing amount.

The processing method of the present invention can also be used for color reversal processing. The black-and-white developing solution used at this time is a so-called black-and-white first developing solution which is generally used for reversal processing of a color photosensitive material. Various well-known additives used in a black-and-white developing solution used in a processing solution for a black-and-white silver halide light-sensitive material are added to a black-and-white first color reversal material.
It can be contained in a developer.

Representative additives include developing agents such as 1-phenyl-3-pyrazolidone, methol and hydroquinone, preservatives such as sulfites, and accelerators composed of alkalis such as sodium hydroxide, sodium carbonate and potassium carbonate. And inorganic or organic inhibitors such as potassium bromide, 2-methylbenzimidazole and methylbenzthiazole, water softeners such as polyphosphates, and development inhibitors consisting of trace amounts of iodides and mercapto compounds. Can be.

The processing method of the present invention comprises the above-described processing steps such as color development, bleaching, bleach-fixing, and fixing. Here, after the bleach-fixing or fixing step, processing steps such as water washing and stabilization are generally performed, but after processing with a processing solution having a fixing ability, substantially no water washing is performed. A simple treatment method for performing a stabilization treatment can also be used.

Known additives can be added to the washing water used in the washing step, if necessary.

For example, water softeners such as inorganic phosphoric acid, aminopolycarboxylic acid, and organic phosphoric acid, fungicides that prevent the growth of various bacteria and algae, and deterrents (eg, isothiazolone, organochlorine fungicides, benzotriazole, etc.) , A drying load, and a surfactant for preventing unevenness. Or LEWest. “Water Quality Criteria”, Ph
ot. Sci. and Eng., vol. 9, No. 6, p. 344-359 (1965) and the like can also be used.

As a stabilizing solution used in the stabilizing step, a processing solution for stabilizing a dye image is used. For example, a liquid having a buffer capacity of pH 3 to 6, a liquid containing an aldehyde (for example, formalin), or the like can be used. The stabilizing solution may contain, if necessary, an ammonium compound, a metal compound such as Bi or Al, a fluorescent brightener, a chelating agent (eg, 1-hydroxyethylidene-1,1-diphosphonic acid), a bactericide, a deterrent agent, Hardening agents, surfactants, alkanolamines and the like can be used.

In the washing step and the stabilizing step, a multi-stage countercurrent method is preferable, and the number of stages is preferably two to four. The replenishment amount is 1 to 50 times, preferably 2 to 30 times, more preferably 2 to 15 times the amount brought in from the previous bath per unit area.

Water used in these washing or stabilizing steps is not limited to tap water, and may be C
a, It is preferable to use water deionized to an Mg concentration of 5 mg / or less, or water sterilized by halogen, an ultraviolet germicidal lamp, or the like.

In each processing step of the above color photosensitive material, when continuous processing is performed by an automatic developing machine, concentration of the processing liquid may occur due to evaporation, particularly when the processing amount is small or when the opening area of the processing liquid is large. Will be noticeable. In order to correct such concentration of the processing solution, it is preferable to replenish an appropriate amount of water or a correction solution.

Further, by using a method in which the overflow solution in the washing step or the stabilization step is caused to flow into a bath having a fixing ability, which is a pre-bath, the amount of waste liquid can be reduced.

The light-sensitive material of the present invention may be provided with at least one of a blue-sensitive layer, a green-sensitive layer, and a red-sensitive layer of a silver halide emulsion layer on a support. There is no particular limitation on the number and order of the emulsion layers and the non-light-sensitive layers. A typical example is a silver halide color photographic light-sensitive material having a light-sensitive layer comprising a plurality of silver halide emulsion layers having substantially the same color sensitivity but different sensitivities on a support. The photosensitive layer is a unit photosensitive layer having color sensitivity to any of blue light, green light and red light, and in a multilayer silver halide color photographic light-sensitive material,
In general, the arrangement of the unit photosensitive layers is provided in the order of red-sensitive layer, green-sensitive layer, and blue-sensitive layer in order from the support side. However, depending on the purpose, the above-mentioned order of installation may be reversed, or another installation order in which different color-sensitive layers are sandwiched between the same color-sensitive layers.

Any of these layer arrangements can be used in the color light-sensitive material of the present invention, but in the present invention, the dried film thickness of all the constituent layers except the support and the undercoat layer and the back layer of the color light-sensitive material is 20.0 μm or less. It is preferable to achieve the object of the present invention. More preferably 18.0μ
It is as follows. The definition of these film thicknesses is based on the color developing agent incorporated in these layers of the color photographic material during and after processing, and greatly affects bleaching fog and stain generated during image storage after processing depending on the amount of remaining color developing agent. By influencing. In particular, the occurrence of bleaching fog and stain is considered to be caused by the green-sensitive color-sensitive layer, and the increase in magenta color is larger than that in other cyan and yellow colors. It is desirable that the lower limit in the film thickness regulation is reduced within the range not significantly deteriorating the performance of the photosensitive material from the above regulation. The lower limit of the total dry film thickness of the constituent layers of the photosensitive material excluding the support and the undercoat layer of the support is 12.0μ, and the structure provided between the photosensitive layer closest to the support and the undercoat layer of the support The lower limit of the total dry thickness of the layer is 1.0 μm.

Further, the reduction of the film thickness may be applied to any of the photosensitive layer and the non-photosensitive layer.

The film thickness of the multilayer color light-sensitive material in the present invention is measured by the following method.

The photosensitive material to be measured is stored at 25 ° C. and 50% RH for 7 days after the preparation of the photosensitive material. First, the total thickness of the photosensitive material was measured, and then the thickness of the coating layer on the support was removed and the thickness was measured again. Thickness. This thickness is measured, for example, by a film thickness measuring device (An
ritus Electric Co. Ltd., K-402B Stand.). The removal of the coating layer on the support can be performed using an aqueous solution of sodium hypochlorite.

Subsequently, using a scanning electron microscope, a cross-sectional photograph of the photosensitive material is taken (preferably at a magnification of 3,000 or more),
The total thickness on the support and the thickness of each layer are measured, and the thickness of each layer can be calculated by comparing the measured value of the total thickness (absolute value of the actually measured thickness) with the above-mentioned film thickness measuring device.

Swelling ratio of photosensitive material in the present invention [(25 ° C., equilibrium swelling thickness in H ₂ O−25 ° C., dry film thickness at 55% RH / 25 ° C., 55 ° C.
% Dry thickness at 100% RH) x 100] is preferably 50 to 200%,
70-150% is more preferred. If the swelling ratio deviates from the above value, the residual amount of the color developing agent increases, and adversely affects photographic performance, image quality such as desilvering properties, and film properties such as film strength.

Further, the swelling speed of the light-sensitive material in the present invention is defined as 90% of the maximum swelling film thickness reached when processing in a color developing solution (38 ° C., 3 minutes 15 seconds), and the saturated swelling speed, When the time required to reach the film thickness is defined as the swelling rate 1/2, T1 / 2 is preferably 15 seconds or less. More preferably, T1 / 2 is 9 seconds or less.

The color light-sensitive material used in the present invention is, as described above, a color composed of silver halide containing silver iodide, such as a color negative film for general use or a movie or a color reversal film for slides or a television. It is preferably a photosensitive material. In such a color light-sensitive material, a preferred silver halide contained in the photographic emulsion layer is silver iodobromide, silver iodochloride, or silver iodochlorobromide containing about 30 mol% or less of silver iodide. . Particularly preferred is silver iodobromide or silver iodochlorobromide containing from about 2 mol% to about 25 mol% silver iodide.

In the present invention, the desilvering step can be sped up by using such a color photosensitive material, and the effect of the present invention is exhibited.

In the present invention, color photographic paper may be used as the color photographic material. In the case of color photographic paper, the silver halide contained in the photographic emulsion layer substantially contains silver iodide. Those which do not contain silver chlorobromide or silver chloride can be preferably used. Here, “contains substantially no silver iodide” means that the silver iodide content is 1 mol% or less, preferably 0.2 mol% or less. Regarding the halogen composition of these silver chlorobromide emulsions, any silver bromide /
Silver chloride can be used. This ratio can take a wide range depending on the purpose, but means that the silver chloride ratio is 2 mol% or less. Regarding the halogen composition of these silver chlorobromide emulsions, any silver bromide / silver chloride emulsion can be used. Although this ratio can take a wide range depending on the purpose, a silver chloride ratio of 2 mol% or less can be preferably used. A so-called high silver chloride emulsion having a high silver chloride content is preferably used for a color light-sensitive material suitable for rapid processing. The silver chloride content of these high silver chloride emulsions is 90%
It is preferably at least 95 mol%, more preferably at least 95 mol%. For the purpose of reducing the replenishment amount of the developing solution, an emulsion of substantially pure silver chloride having a silver chloride content of 98 to 100 mol% is also preferably used.

The silver halide grains of a photographic emulsion include those having regular crystals such as cubic, octahedral, and tetrahedral, those having irregular crystal forms such as spheres and plates, and those having twin planes. It may have a crystal defect or a composite form thereof.

The silver halide may be fine grains having a grain size of about 0.2 μm or less or large grains having a projected area diameter of about 10 μm, and may be a polydisperse emulsion or a monodisperse emulsion.

As the silver halide emulsion, usually, those subjected to physical ripening, chemical ripening and spectral sensitization are used. The additive used in such a process is Research Disclosure No. 1
7643 and No. 18716, and the relevant portions are summarized in the table below.

Known photographic additives that can be used in the present invention are also described in the above two Research Disclosures, and the relevant portions are shown in the following table.

Various color couplers can be used in the present invention, and specific examples thereof are described in the patents described in the aforementioned Research Disclosure (RD) No. 17643, VII-CG. As the dye-forming coupler, a coupler which provides the three primary colors of the subtractive color method (that is, yellow, magenta and cyan) by color development is important. Specific examples of the 4-equivalent or 2-equivalent coupler having diffusion resistance are described in the above-mentioned DR17643, VII-
In addition to the couplers described in the patents described in C and D,
The following can be preferably used in the present invention.

Typical examples of the yellow coupler that can be used include known oxygen atom-eliminable yellow couplers and nitrogen atom-eliminable yellow couplers. α-
Pivaloyl acetanilide couplers are excellent in the fastness of coloring dyes, especially in light fastness, while α-benzoylacetanilide couplers provide high color density.

Magenta couplers that can be used in the present invention include hydrophobic 5-pyrazolone-based and pyrazoloazole-based couplers having a ballast group. As the 5-pyrazolone coupler, a coupler in which the 3-position is substituted with an arylamino group or an acylamino group is preferable from the viewpoint of the hue and color density of the coloring dye.

Cyan couplers usable in the present invention include hydrophobic and nondiffusible naphthol-based couplers and phenol-based couplers, and a preferred example is an oxygen atom-eliminating double-equivalent naphthol-based coupler. Further, couplers capable of forming a cyan dye which is robust against humidity and temperature are preferably used, and typical examples thereof include U.S. Pat.
No. 3,772,002, a phenolic cyan coupler having an alkyl group at the meta-position of the phenol nucleus or an alkyl group having an ethyl group or more, a 2,5-diacylamino-substituted phenolic coupler, a phenylureido group at the 2-position and 5- Phenolic couplers having an acylamino group at the 1-position, and 5-amidonaphthol-based cyan couplers described in European Patent No. 161626A.

Granularity can be improved by using a coupler in which the coloring dye has an appropriate diffusibility. Such couplers are specific examples of magenta couplers in U.S. Pat.No. 4,366,237 and the like, and yellow in European Patent No. 96,570 and the like.
Specific examples of magenta or cyan couplers are described.

Dye-forming couplers and the above-mentioned special couplers may form polymers of dimers or more. Typical examples of polymerized dye-forming couplers are described in U.S. Pat. No. 3,451,820. Specific examples of the polymerized magenta coupler are described in U.S. Pat. No. 4,367,282.

Couplers that release a photographically useful residue upon coupling can also be preferably used in the present invention. As the DIR coupler releasing the development inhibitor, the couplers of the patents described in the aforementioned RD17643, VII-F are useful.

In the light-sensitive material of the present invention, a coupler that releases an image-like nucleating agent or a development accelerator or a precursor thereof during development can be used. Specific examples of such compounds are described in British Patent Nos. 2,097,140 and 2,131,188. In addition, DIR redox compound releasing couplers described in JP-A-60-185950 and the like, European Patent No. 17
Couplers that release a dye that recolors after elimination described in 3,302A can be used.

The coupler used in the present invention can be introduced into the light-sensitive material by various known dispersion methods. Examples of high boiling organic solvents used in the oil-in-water dispersion method are described in US Pat. No. 2,322,027 and the like. Further, the steps and effects of the latex dispersion method as one of the polymer dispersion methods and specific examples of the latex for impregnation are described in US Pat. No. 4,199,363 and West German patent application (O.
LS) Nos. 2,541,274 and 2,541,230 disclose a dispersion method using an organic solvent-soluble polymer in PCT Application No. JP87 / 00492.

Examples of the organic solvent used in the above-described oil-in-water dispersion method include alkyl phthalates (eg, dibutyl phthalate, dioctyl phthalate), phosphates (eg, diphenyl phosphate, triphenyl phosphate, tricresyl phosphate, diacryl). Butyl phosphate), citrate (eg, tributyl acetyl citrate), benzoate (eg, octyl benzoate), alkyl amide (eg, diethyl lauryl amide), fatty acid esters (eg, dibutoxyethyl succinate, diethyl azelate) , Trimesic esters (eg, tributyl trimesate),
Or an organic solvent having a boiling point of about 30 to 150 ° C., for example, ethyl acetate, lower alkyl acetate such as butyl acetate, ethyl propionate, secondary butyl alcohol, methyl isobutyl ketone, β-ethoxyethyl acetate, methylcellosolve acetate, etc. May be.

Suitable supports that can be used in the present invention include, for example, those described above.
RD No. 17643, page 28 and No. 18716, page 647, right column, 64
It is described in the left column on page 8.

<Experimental Examples and Examples> Hereinafter, the present invention will be specifically described with experimental examples and examples.

EXPERIMENTAL EXAMPLE 1 Rubber samples molded from various compound kits shown in Table 1 were used as bleach replenishers A and B having the following compositions, respectively.
Each was immersed for one month (30 days), and the dimensional change and weight change were examined.

The temperature of the bleaching replenisher was 50 ° C, and 6.5 during immersion.
The liquid was circulated at a rate of / min.

The sample had a size of 116 mm × 20 mm × 2 mm, and the weight was as shown in Table 1.

Bleaching replenisher A Ferric ammonium 1,3-propylenediaminetetraacetate
Monohydrate 210 (0.53 mol) Ammonium bromide 120 g Ammonium nitrate 25 g Hydroxyacetic acid 90 g (1.2 mol) Acetic acid (98%) 50 g (0.82 mol) Add water to 1 pH [adjust with aqueous ammonia (28%)] 2.8 Replenish bleaching Liquid B 100 sodium ferric ethylenediaminetetraacetate trihydrate
0g Ethylenediaminetetraacetic acid disodium salt 10.0g Ammonium bromide 140.0g Ammonium nitrate 30.0g Ammonia water (27%) 6.5ml The brand name of the rubber sample used at 1 pH 6.0 or below with water added.

(1) Silicone rubber (Q) SRX495u, SH851u, SH745u (from Toray Silicone Rubber Co., Ltd.) KE850 (Shin-Etsu Chemical Co., Ltd.) (2) EPDM rubber (EPDM) MITSUI EPT1045 (Mitsui Petrochemical Industries, Ltd.) (3) Fluoro rubber (FKM) Viton rubber (manufactured by Showa Denko / Dupont) (4) Chloroprene rubber (CR) V-ring (manufactured by Nippon Seikaring Co., Ltd.) and NEOPRENE O-ring (showa neoprene (5) Styrene-butadiene rubber (SBR) JSR # 1500 (Nippon Synthetic Rubber Co., Ltd.) (6) Acrylonitrile-butadiene rubber (NBR) JSR N220S (Nippon Synthetic Rubber Co., Ltd.) It is shown in FIG. Table 1 also shows data for butyl rubber (IIR) and silicone rubbers with different SP values.

The bleaching replenishers A and B are shown as A and B in Table 1.

As shown in Table 1, the weight change and the dimensional change of the silicone rubber, EPDM rubber and butyl rubber having SP values of 7.0 to 8.0 were higher than those of the bleach replenisher A containing the high potential oxidizing agent and the organic acid (the present invention). Both are hardly observed, indicating that the rubber material is suitable for use in such a chemical solution.

On the other hand, it can be seen that in the conventional bleaching replenisher B containing the ferric complex of EDTA, the change hardly depends on the rubber type as compared with the bleaching replenisher A. In addition, it is also found that such a chemical solution does not cause significant problems such as swelling.

Therefore, silicone rubber, EPDM rubber, and butyl rubber having an SP value of 7.0 to 8.0 exhibit the effect on their properties only when applied to the bleaching replenisher of the present invention.

Further, the silicone rubber, EPDM rubber and butyl rubber having an SP value of 7.0 to 8.0 were examined for changes in hardness, tensile elongation and tensile strength with respect to the bleaching replenisher A under the above-mentioned conditions.

In addition, the change after 73 days was confirmed to be relatively small.

 Next, an example based on the above experimental example will be described.

Example 1 On an undercoated cellulose triacetate film support, a sample as a multi-layer color light-sensitive material composed of each layer having the following composition was prepared.

(Composition of Photosensitive Layer) The number for each component indicates the coating amount in g / m ² . However, for silver halide, colloidal silver and couplers, the amount was expressed in g / m ^{2 of} silver, and for sensitizing dyes, it was expressed in mol per mol of silver halide in the same layer. The numerical value in parentheses at the end of each layer indicates the film thickness [unit: μ].

First layer: Antihalation layer Black colloidal silver Silver coating amount 0.20 Gelatin 1.90 UV-1 0.10 UV-2 0.20 Cpd-1 0.05 Solv-1 0.01 Solv-2 0.01 Solv-3 0.08 (2.0) Second layer: Intermediate layer Fine particles Silver bromide (sphere equivalent diameter 0.07μ) Silver coating amount 0.15 Gelatin 0.90 Cpd-2 0.20 (0.9) Third layer: First red-sensitive emulsion layer Silver iodobromide emulsion (AgI 10.0 mol%, internal high AgI type, spherical) 0.7μ equivalent diameter, coefficient of variation of equivalent sphere diameter 14%, tetrahedral particle) Silver coating amount 0.50 Silver iodobromide emulsion (AgI 4.0mol%, internal high AgI type, equivalent equivalent diameter of sphere 0.4μ, variation coefficient of equivalent sphere diameter) Silver coating amount 0.40 Gelatin 1.90 ExS-1 9.0 × 10 ^-4 mol ExS-2 3.0 × 10 ^-4 mol ExS-3 0.8 × 10 ^-4 mol ExS-4 0.6 × 10 ^-4 mol ExC -1 0.33 ExC-2 0.009 ExC-3 0.028 ExC-6 0.14 (2.2) Fourth layer: Second red-sensitive emulsion layer Silver iodobromide emulsion (AgI 16 mol%, internal high AgI type, equivalent sphere diameter 1.0 μm) Coefficient of variation of equivalent ball diameter 25% Plate-like particles, diameter /
Thickness ratio 4.0) Silver coating amount 0.80 Gelatin 1.20 ExS-1 4.0 × 10 ^-4 mol ExS-2 1.5 × 10 ^-4 mol ExS-3 0.4 × 10 ^-4 mol ExS-4 0.4 × 10 ^-4 mol ExC-3 0.05 ExC-4 0.10 ExC-6 0.08 (1.4) Fifth layer: Third red-sensitive emulsion layer Silver iodobromide emulsion (AgI 10.6 mol%, internal high AgI type, equivalent spherical diameter 1.2 μm, coefficient of variation of equivalent spherical diameter 28) %, Plate-like particles, diameter / thickness ratio 6.0) Silver coating amount 1.10 Gelatin 1.00 ExS-1 2.5 × 10 ^-4 mol ExS-2 0.7 × 10 ^-4 mol ExS-3 0.2 × 10 ^-4 mol ExC-4 0.07 ExC -5 0.06 Solv-1 0.12 Solv-2 0.12 (1.4) Sixth layer: Intermediate layer Gelatin 1.30 Cpd-4 0.10 (1.0) Seventh layer: First green-sensitive emulsion layer Silver iodobromide emulsion (AgI 10.0 mol%, Internal high AgI type, sphere equivalent diameter 0.7μ, coefficient of variation of sphere equivalent diameter 14%, tetrahedral grains) Silver coating amount 0.20 Silver iodobromide emulsion (AgI 4.0 mol%, internal high AgI type, sphere equivalent diameter 0.4μ, Coefficient of variation of sphere equivalent diameter 22%, tetrahedral particles) Silver coating amount 0.10 1.30 ExS-5 5 × 10 ^-4 mol ExS-6 2 × 10 ^-4 mol ExS-7 1 × 10 ^-4 mol ExM-1 0.21 ExM-6 0.31 ExM-2 0.10 ExM-5 0.03 Solv-1 0.20 Solv- 5 0.03 (1.8) Eighth layer: Second green-sensitive emulsion layer Silver iodobromide emulsion (AgI 10 mol%, internal high iodine type, equivalent spherical diameter 1.0 μ, coefficient of variation of equivalent spherical diameter 25%, plate-like grains, Diameter / thickness ratio 3.0) Silver coating amount 0.50 Gelatin 0.45 ExS-5 4.5 × 10 ^-4 mol ExS-6 1.8 × 10 ^-4 mol ExS-7 0.9 × 10 ^-4 mol ExM-1 0.09 ExM-3 0.01 Solv-1 0.15 Solv-5 0.03 (0.8) Ninth layer: Intermediate layer Gelatin 0.50 (0.4) Tenth layer: Third green-sensitive emulsion layer Silver iodobromide emulsion (AgI 10.0 mol%, internal high AgI type, equivalent sphere diameter 1.2 μm) , Coefficient of variation of sphere equivalent diameter 28%, plate-like particles, diameter / thickness ratio 6.0) Silver coating amount 1.20 Gelatin 1.20 ExS-5 2.4 × 10 ^-4 mol ExS-6 1.0 × 10 ^-4 mol ExS-7 1.0 × 10 ^-4 mol ExM-3 0.01 ExM-4 0.14 ExM-1 0.04 ExC-4 0.005 Solv-1 0. 2 (1.6) 11th layer: yellow filter layer Cpd-3 0.05 gelatin 0.50 Solv-1 0.10 (0.5) 12th layer: intermediate layer gelatin 0.05 Cpd-2 0.05 (0.5) 13th layer: first blue-sensitive emulsion layer Silver bromide emulsion (AgI 10.0 mol%, internal high AgI type, equivalent sphere diameter 0.7 μ, coefficient of variation of equivalent sphere diameter 14%, tetrahedral grains) Silver coating amount 0.15 Silver iodobromide emulsion (AgI 4.0 mol%, internal High AgI type, equivalent spherical diameter 0.4μ, coefficient of variation of equivalent spherical diameter 22%, tetrahedral particles) Silver coating amount 0.08 Gelatin 1.00 ExS-8 4.5 × 10 ^-4 mol ExY-1 0.62 ExY-2 0.02 Solv-1 0.20 (1.7) 14th layer: 2nd blue-sensitive emulsion layer Silver iodobromide emulsion (AgI 19.0 mol%, internal high AgI type, equivalent sphere diameter 1.0μ, equivalent coefficient of sphere variation coefficient 16%, tetradecahedral grains) Silver coating Amount 0.80 Gelatin 0.30 ExS-8 3.0 × 10 ^-4 mol ExY-1 0.22 Solv-1 0.07 (0.7) 15th layer: Intermediate layer Fine grain silver iodobromide (AgI 2 mol%, uniform type, equivalent sphere diameter 0.1)
3μ) Silver coating amount 0.20 Gelatin 0.26 (0.3) 16th layer: 3rd blue-sensitive emulsion layer Silver iodobromide emulsion (AgI 14.0 mol%, internal high AgI type, equivalent spherical diameter 1.5μ, coefficient of variation of equivalent spherical diameter 28) %, Plate-like particles, diameter / thickness ratio 5.0) Silver coating amount 1.20 Gelatin 0.80 ExS-8 1.8 × 10 ^-4 mol ExY-1 0.20 Solv-1 0.07 (1.5) 17th layer: 1st protective layer Gelatin 1.80 UX- 1 0.10 UX-2 0.20 Solv-1 0.01 Solv-2 0.01 (1.5) 18th layer: 2nd protective layer Fine grain silver iodobromide (sphere equivalent diameter 0.07μ) Silver coating amount 0.18 Gelatin 0.90 Polymethyl methacrylate particles (diameter 1.5) μ) 0.20 W-1 0.20 H-1 0.40 Cpd-5 1.00 (2.0) This sample was cut and processed into a width of 35 mm, subjected to imagewise exposure, and then processed according to the following processing steps using a modification of an automatic developing machine FP203B manufactured by Fuji Photo Film Co., Ltd.
Incidentally, the photosensitive material processing amount per day was set to 0.8 m ^2, 6 months,
I ran the automatic machine every day.

Processing step Processing time Processing temperature Replenishment amount ^* Tank capacity Color development 2 minutes 30 seconds 38 ° C 20ml 10 Bleaching 25 seconds 38 ° C 5ml 4 Bleaching and fixing 40 seconds 38 ° C -4 Fixing 40 seconds 38 ° C 30ml 4 Washing with water (1) 30 Second 38 ° C -2 Washing (2) 20 seconds 38 ° C 30ml 2 Stability 20 seconds 38 ° C 20ml 2 Drying 1 minute 55 ° C * The replenishment amount is 35mm width per 1m length. This was a countercurrent method to 1), and the bleaching solution and the overflow solution of the fixing solution were all introduced into the bleach-fixing.

The amount of the bleach-fix solution brought into the washing step in the above process was 2 ml per 1 m of the 35 mm-wide photosensitive material.

 The composition of the treatment liquid is shown below.

(Bleaching / fixing mother liquor) Bleaching solution and fixing solution mixed at a volume ratio of 1: 2 (Fixing solution) Common to mother liquor and replenisher (g) Ethylenediaminetetraacetic acid disodium salt 25.0 Ammonium sulfite 20.0 Aqueous ammonium thiosulfate (700 g /) 280 ml Imidazole 35.0 g Ammonia water (27%) 15.0 ml Add water 1.0 pH 7.4 (Washing water) Common for mother liquor and replenisher Tap water is H-type strongly acidic cation exchange resin (Amberlite IR-120B manufactured by Rohm and Haas) And a OH-type strongly basic anion exchange resin (Amberlite IRA-400) filled with mixed-bed columns to treat the calcium and magnesium ion concentrations to 3 mg / or less, followed by isocyanuric dichloride Sodium 20mg / and sodium sulfate 150
mg / was added. The pH of this solution was in the range of 6.5 to 7.5.

(Stabilizing solution) Common for mother liquor and replenisher (unit: g) Formalin (37%) 2.0 ml Polyoxyethylene-p-monononylphenyl ether (average degree of polymerization: 10) 0.3 Disodium ethylenediaminetetraacetate 0.05 Add water 1.0 pH 5.8-8.0 In the bleaching tank of the automatic processing machine described above, a diaphragm pump was used as a replenishment pump for replenishing the bleach replenisher. In this case, the valve material was fluoro rubber (Viton rubber: manufactured by Showa Denko DuPont).

The sealing material in the circulation part of the bleaching tank was chloroprene rubber (V-ring: manufactured by Nippon Securing Co., Ltd.).

In addition, chloroprene rubber (neoprene rubber O-ring: manufactured by Showa Neoprene Co., Ltd.) or the like was used as the rubber member that comes into contact with the bleaching solution and / or the bleaching replenisher in the bleaching step.

 This is referred to as processing 1A.

The processing was carried out in the same manner as in processing 1A, except that silicone rubber (as shown in the experimental example) was applied to all the rubber members that come into contact with the bleaching solution and / or the bleaching replenisher in the bleaching step.

For example, SRX495u (trade name, manufactured by Toray Silicone Rubber Co., Ltd.) was used as the valve material.

Further, instead of the V-ring made of chloroprene rubber, an O-ring was made of silicone rubber of SRX495u (trade name, manufactured by Toray Silicone Rubber Co., Ltd.) and used.

 This is referred to as processing 1B.

Regarding the above treatments 1A and 1B, changes in the discharge amount of the replenishing pump and changes in the sealability in the bleaching step of the used automatic developing machine were examined.

Further, with respect to the sample after the processing, the photographic performance at the start of the processing and after 6 months and the rate of change thereof were examined.

The photographic performance was evaluated for poor bleaching and bleaching fog, and evaluated as follows.

(1) Poor bleaching (defective desilvering) Evaluation was made by measuring the amount of residual silver (μg / cm ² ) in the maximum image density portion (Dmax) by a fluorescent X-ray method.

(2) Bleaching fog The bleaching fog was defined as the difference between the magenta density of the unexposed area of the sample processed with the above photosensitive material and the magenta density of the unexposed sample processed by replacing the bleaching solution with the following reference solution in the above processing.

These results are summarized in Table 2.

As shown in Table 2, in the treatment 1B using the silicone rubber, there was no change in the pump discharge amount, the sealability, and the like, and a stable treatment could be performed over a long period of time. As a result, an image with good photographic performance was obtained. It turned out to be obtained.

Example 2 The same process as in process 1B of Example 1 was carried out except that a bellows pump was used as a replenishing pump for the bleaching replenisher. However, the valve material of this bellows pump was the same fluororubber as in the treatment 1A of Example 1.

This is referred to as treatment 2A. In treatment 2A, the same treatment was carried out except that the valve material of the bellows pump was EPDM rubber (MITSUI EPT1045: manufactured by Mitsui Petrochemical Industries, Ltd.).

 This is referred to as processing 2B.

Table 3 summarizes the pump discharge amount and photographic performance in the processes 2A and 2B, as in the first embodiment.

As shown in Table 3, in the process 2A, it was difficult to obtain stable photographic performance due to a change in the discharge amount of the replenishing pump, but in the process 2B, good photographic performance was obtained over a long period of time.

As can be seen from the experimental examples described above, when the conventional ferric complex of EDTA is used as an oxidizing agent (bleaching agent) as the bleaching solution, the problem that the processing performance of the bleaching solution changes depending on the rubber material to be applied is as follows. It was not noticeable, and it was confirmed that almost the same photographic performance can be obtained by any of the above-described automatic processing machines.

<Effect of the Invention> According to the present invention, when performing rapid processing using a processing solution having a bleaching ability containing a high-potential oxidizing agent, parts of an automatic processing machine that come into contact with the processing solution and / or a replenisher thereof are used. Various troubles caused by swelling of the rubber material can be solved, and adverse effects on photographic characteristics (such as fog) can be reduced.

As a result of resolving mechanical problems, stable processing performance can be maintained, and stable photographic performance can be always obtained even after long-term development processing.

 ──────────────────────────────────────────────────続 き Continuation of the front page (56) References JP-A-62-249145 (JP, A) JP-A-63-151944 (JP, A) JP-A-58-83852 (JP, A) JP-A 61-249 250647 (JP, A)

Claims (1)

(57) [Claims] 1. A silver halide color photographic light-sensitive material after imagewise exposure is subjected to color development processing, and then contains an oxidizing agent having an oxidation-reduction potential of 150 mV or more at 0.2 mol / or more, and has an acid dissociation constant (p
ka) In treating with a processing solution having a bleaching ability containing a compound of 2 to 5.5 at 0.5 mol / or more, a silicone rubber, ethylene-propylene rubber and SP value selected from butyl rubber 7.0-8.0 (cal / c
m ³⁾ The method for processing a silver halide color photographic material, which comprises using the ^half of the rubber material.