EP0465228B1 - A silver halide color photographic light-sensitive material processing method - Google Patents

Description

FIELD OF THE INVENTION

The present invention relates to a silver halide color photographic light-sensitive material processing method, more specifically to a silver halide color photographic light-sensitive material processing method which offers improvements in the prevention of residual dye stain and crystal deposition onto the processing tanks and rollers and which permits rapid processing and reduction in the amount of replenisher.

BACKGROUND OF THE INVENTION

For obtaining a color image by processing an imagewise-exposed silver halide color photographic light-sensitive material (hereinafter simply referred to as a light-sensitive material), it is a common practice to remove the metallic silver formed after the color developing process and subsequently process the light-sensitive material by washing, stabilization, stabilizing treatment without water washing and other processes.

Traditionally, the light-sensitive material is sent to a processing laboratory where it is processed in 24 to 48 hours from reception to finish. In recent years, however, as a trend toward increased service quality for users, there has been a need for rapid processing within several hours from reception to finish. More recently, with the popularization of the in-house processing equipment known as "mini-labo", there have been demands for rapid processing even within 1 hour from reception to finish in in-house processing, which requirement increasingly urges the development of techniques for more rapid processing.

In response to this trend, a rapid process for color paper known as the process RA-4 (development is carried out at 35°C for 3 minutes and the entire process comprises 45 seconds of color development, 45 seconds of bleach-fixation and 90 seconds of stabilization) has recently been proposed by Eastman Kodak Company.

The prior art techniques for rapid processing are roughly divided into three groups:

(1) those based on improvement in light-sensitive material,

(2) those based on the use of a physical means in the process, and

(3) those based on improvement in processing solution composition.

The methods classified under (1) above include:

1) the methods based on improvement in silver halide composition, such as the method of preparing fine grains of silver halide described in Japanese Patent O. P. I. Publication No. 77223/1976 and the method of reducing the silver bromide content of silver halide described in Japanese Patent O. P. I. Publication No.18142/1983 and Japanese Patent Examined Publication No. 18939/1981,

(2) the methods using an additive, such as the method described in Japanese Patent O. P. I. Publication No. 64339/1981, in which a 1-aryl-3-pyrazolidone having a particular structure is added to the light-sensitive material, and the method described in Japanese Patent O. P. I. Publication Nos. 144547/1982, 50534/1983, 50535/1983 and 50536/1983, in which 1-aryl-pyrazolidone is added to the light-sensitive material,

(3) the methods using a rapidly reactive coupler, such as the method using a rapid yellow coupler, described in Japanese Patent Examined Publication No. 10783/1976 and Japanese Patent O. P. I. Publication Nos. 123342/1975 and 102636/1976, and

(4) the methods based on the thinning of photographic structural layer, such as the method described in Japanese Patent O. P. I. Publication No. 65040/1987, in which the photographic structural layer is thinned.

The methods classified under (2) above include methods of stirring a processing solution, such as the method described in Japanese Patent O. P. I. Publication No. 180369/1987.

The methods classified under (3) above include:

(1) the method using a development accelerator,

(2) the method of thickening the color developing agent, and

(3) the method in which the concentration of halogen ion, particularly bromide ion, is reduced.

However, even when a rapid processing method described above is used, a short processing time can result in a problem of residual dye stain due to poor elution of the sensitizing dye or anti-irradiation dye (AI dye) contained in the light-sensitive material into the processing solution. Furthermore, the use of a stabilizing treatment without water washing poses another problem in keeping the white margin.

Traditionally, with the aim of solving these problems, attempts have been made to promote the elution of sensitizing dyes by adding a fluorescent brightening agent and other additives to the stabilizing solution such as the method described in Japanese Patent O. P. I. Publication No. 62359/1987 or to eliminate dye colors by using an AI dye of the bleach type (color elimination type) and allowing sulfite ions to be present in the processing solution.

However, even when these methods are used, the pigments and dyes eluted from the light-sensitive material accumulate in the processing solution during process running, which in turn dye back the light-sensitive material to cause severe residual dye stain and which in addition adhere to, and deposit on, the processing tanks and rollers. These problems of dyeing-back of the light-sensitive material by the eluted pigments and dyes and their deposition on the processing tank wall and rollers are liable to occur particularly in the final processing bath, i.e., the stabilizing bath. Moreover, with the recent trend toward rapid processing and reduction in the amount of replenisher, these problems have become more important.

SUMMARY OF THE INVENTION

It is an object of the present invention to provide a silver halide color photographic light-sensitive material processing method which prevents residual dye stain of color paper during processing and crystal deposition on processing tanks and rollers and which permits rapid processing and reduction in the amount of replenisher.

Other objects will become obvious through the description which follows.

BRIEF DESCRIPTION OF THE DRAWINGS

Figure 1 is a cross-sectional view of a mode of the automatic developing machine used for the present invention. Figure 2 is a plane view of the automatic developing machine. In these figures, the numerical symbols 1 through 16 respectively denote the following:
   1...main body of the developing machine, 2...negative light-sensitive material, 3...positive light-sensitive material, 4...supply portion, 5...take-out portion, 6...developer tank, 7...bleacher tank, 8...fixer tank, 9, 10 and 11...stabilizer tank, and 13,14, 15 and 16...cascade piping.

DETAILED DESCRIPTION OF THE INVENTION

The object described above is accomplished by a silver halide color photographic light-sensitive material processing method wherein a silver halide color photographic light-sensitive material comprising a support and a silver halide emulsion having an average silver chloride content of not less than 80 mol% coated thereon is subjected to imagewise exposure, after which it is subjected to color development and subsequent bleaching, fixation and stabilization and wherein a water-soluble surfactant is added to the stabilizer so that the surface tension of the stabilizer is 15 to 60 dyne/cm and ion exchange resin or adsorbent is brought into contact with the light-sensitive material in the stabilizing bath.

In the processing method of the invention, the water-soluble surfactant is represented by the following formula I or II. Preferably a silver halide color photographic light-sensitive material comprising a support and a silver halide emulsion having an average silver iodide content of not less than 2 mol% coated thereon and another silver halide color photographic light-sensitive material comprising a support and a silver halide emulsion having an average silver chloride content of not less than 80 mol% coated thereon are subjected to mixed processing using at least one same replenisher in a processing bath other than the color developing bath and wherein a part or all of the overflow is allowed to enter in the stabilizing bath to process the former silver halide color photographic light-sensitive material therein.

wherein R represents a hydrogen atom or a linear or branched alkyl group having a carbon number of 4 to 25 which may have a substituent or

(R₁ and R₂ independently represent a hydrogen atom or an alkyl group having a carbon number of 1 to 20 which may have a substituent; ℓ represents an integer of 0 to 4) or a hydrogen atom; n and m independently represent an integer of 0 to 200, but they are not 0 concurrently; A and B, whether identical or not, independently represent

wherein n₁, m₁ and ℓ₁ independently represent 0, 1, 2 or 3, but n₁, m₁ and ℓ₁ are not 0 concurrently; D represents a hydrogen atom or -SO₃M or -PO₃M group, wherein M represents a hydrogen atom, alkali metal or ammonium.

wherein R₃ represents a hydrogen atom, hydroxyl group, lower alkyl group, alkoxy group or

or

R₄, R₅ and R₆, whether identical or not, independently represent a lower alkyl group, with preference given to an alkyl group having a carbon number of 1 to 3, such as a methyl, ethyl or propyl group; ℓ₁ through ℓ₃ independently represent an integer of 0 to 4; p, q₁ and q₂ independently represent an integer of 1 to 15.

The present invention is described in more detail below.

As stated above, the pigments and dyes accumulated during running processing dye back the light-sensitive material in the conventional countermeasure against residual dye stain. The present invention thus aims at promoting the elution of weakly hydrophilic sensitizing dyes by adding a water-soluble surfactant to the stabilizing bath, in which dying is likely to occur, and at preventing the dying-back of the pigments and dyes accumulated in the stabilizer to the light-sensitive material and their crystal deposition onto the processing tank wall and rollers by removing the pigments and dyes by adding ion exchange resin or adsorbent to the stabilizing bath.

As a result, it has become feasible to significantly suppress residual dye stain even in rapid processing with a reduced amount of replenisher and to prevent the deposition of the pigments and dyes accumulated in the stabilizing bath onto the rollers and tank wall.

In an automatic developing machine for processing both color negative films and paper wherein the same replenisher tanks, pumps and other devices are used for both color negative films and paper to reduce the equipment size and cost, applying the processing method of the present invention has been found to prevent residual dye stain of paper and the deposition of the accumulated pigments and dyes on the rollers and tank wall.

Examples of the compound represented by the formula I or II are given below, but the present invention is not to be interpreted as limited thereby.

Exemplified Compounds

I -1    C₁₂H₂₅O(C₂H₄O)₁₀H I - 2    C₈H₁₇O(C₃H₆O)₁₅H I - 3    C₉H₁₉O(C₂H₄O)₄SO₃Na I - 4    C₁₀H₂₁O(C₂H₄O)₁₅PO₃Na₂

Exemplified Compounds

The ion exchange resin or adsorbent used for the present invention is commercially available under various trade names such as Diaion (produced by Mitsubishi Chemical Industries Ltd.), Amberlite (produced by Japan Organo Co., Ltd.), Duolite, Sumikaion and Sumichelate (all produced by Sumitomo Chemical Co., Ltd.) and ^*Uniselek^* (produced by Unitika Ltd.).

Anion exchange resin is particularly preferred for the enhancement of the effect of the invention, and its chemical structure is exemplified as follows:

Commercial products: Mitsubishi Diaion SA-10A, SA-11A, PA-308

Commercial products: Mitsubishi Diaion SA-20A, SA-21A, PA-408

wherein R represents a hydrogen atom, N(R')₂ or lower alkyl group (R' represents a hydrogen atom or lower alkyl group, but the two R' members do not represent a hydrogen atom concurrently); n represents an integer of 0 to 3. Commercial products: Mitsubishi Diaion WA-10, WA-11

wherein n represents an integer of 0 or 1.
Commercial products: Mitsubishi Diaion WA-20, WA-21

wherein n represents an integer of 1 to 3.
Commercial product: Mitsubishi Diaion WA-30

These basic ion exchange resins are not subject to limitation with respect to the anion substituent, but preference is given to OH^-, Cℓ^-, SO 2- / 4 , Br^-, COOH^-, CO 2- / 3 and SO 2- / 3.

In the present invention, the following adsorbents can also be used.
Adsorbents

(a) Activated charcoal

(b) Clay substance

(c) Polyamide polymer compounds

(d) Polyurethane polymer compounds

(e) Phenol resin

(f) Epoxy resin

(g) Polymer compounds having a hydrazide group

(h) Polymer compounds having polytetrafluoroethylene

(i) Copolymer of methacrylic acid monoester of monohydric or polyhydric alcohol and methacrylic acid polyester of polyhydric alcohol

The activated charcoal (a) may be any activated charcoal, as long as it is adsorptive. The activated charcoal may be made from any of wood, sawdust, coconut shell, lignin, bovine bone, blood, lignite, brown coal, peat and coal. Morphologically two types are available, namely powdery and granular, both of which can be used for the present invention. To produce powdered activated charcoal, the raw material is pulverized and then carbonated at high temperature for activation. In some cases, activation is carried out by steam sparging at high temperature or by burning carbonization after immersion in a solution such as of zinc chloride, phosphoric acid, sulfuric acid or alkali. Another carbonization method is available in which charcoal is partially oxidized by ignition under reduced pressure or by heating in air, carbon dioxide or gaseous chlorine. Activation is normally followed by washing to remove the ash and chemicals, pulverization and drying to yield powdered activated charcoal. Granular activated charcoal is obtained by forming pulverized charcoal powder to a given granularity in the presence of a caking agent such as tar or pitch, drying and burning. When coconut shell or coal is used, it is pulverized and sieved, after which it is carbonized at high temperature for activation to yield granular activated charcoal. In the present invention, irrespective of the raw material and the method of activation, any form of activated charcoal can be used, whether it is powdery or granular, but preference is given to granular activated charcoal. More preference is given to coconut shell activated charcoal and activated charcoal capable of molecular sieving. The activated charcoal capable of molecular sieving is defined to have slit-like pores, whose size is desirably not less than 6 Angstrom in diameter and not more than 15 Angstrom in width. Such activated charcoal capable of molecular sieving can be prepared in accordance with Japanese Patent O. P. I. Publication No. 14831/1983 of the present applicant.

The clay substance (b) is an inorganic substance containing silica and alumina as the essential components and, as necessary, other components, including silica gel, bentonite, activated clay, acid clay, kaolin and substances in the zeolite group such as zeolite. Bentonite is a clay acid based on hydrated aluminum silicate, derived mainly from montmorillonite ore. Activated clay is a clay substance derived mainly from montmorillonite or halloysite ore. Acid clay is a similar clay substance. Kaolin is a clay substance comprising naturally-occurring hydrated aluminum silicate. Substances in the zeolite group such as zeolite are clay substances which comprise naturally-occurring or synthetic zeolite, which have uniform pore size and which act as a molecular sieve. Examples of non-zeolite substances in the zeolite group include natrolite and chabazite.

The polyamide polymer compound (c) is a polymer having an acid amide bond, such as 6-nylon, 6,6-nylon or 6,10-nylon.

The polyurethane polymer compound (d) is a polymer compound having the urethane linkage -NHCOO- in the repeat unit of the principal chain.

The phenol resin (e) includes resins prepared from a phenolic substance such as phenol, cresol, xylenol or resorcinol and an aldehyde such as formaldehyde, acetaldehyde or furfural, and modified resins thereof, with preference given to phenol-formaldehyde resin. Examples of commercial products include Duolite S-761 resin, produced by Sumitomo Chemical Co., Ltd.

The polymer compound (g) having a hydrazide group include adducts of sulfohydrazide group, carbonylhydrazide group or hydrazide group with methyl acrylate-divinylbenzene copolymer, styrene-divinylbenzene copolymer or the like.

The polytetrafluoroethylene-containing polymer compound (h) is a mixture of polytetrafluoroethylene and polyethylene, polypropylene or polyvinyl chloride, or pure polytetrafluoroethylene. The polytetrafluoroethylene content is preferably not less than 50%.

Any methacrylate copolymer serves as the methacrylic acid monoester of monohydric or polyhydric alcohol as a component of the copolymer (i) of methacrylic acid monoester of monohydric or polyhydric alcohol and methacrylic acid polyester of polyhydric alcohol, with preference given to methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, 2-hydroxy-ethyl methacrylate and 2-hydroxy-propyl methacrylate. As the methacrylic acid polyester of polyhydric alcohol for crosslinking monomer, ethylene glycol dimethacrylate is most preferable. Also preferred are polyethylene glycol (n = 1 to 10) dimethacrylates such as diethylene glycol dimethacrylate and triethylene glycol dimethacrylate. Also usable are trimethylolpropane trimethacrylate and pentaerythritol tetramethacrylate. This methacrylate copolymer is preferably porous. The porous methacrylate copolymer should contain 10 to 90% by weight of methacrylic acid monoester of monohydric or polyhydric alcohol. The content of methacrylic acid polyester of polyhydric alcohol is preferably not more than 50%. Examples of preferred commercial products include Amberlite XDA-7, 8 and 9, produced by Rohm & Haas Company.

These substances are preferably porous, having a large surface area. The specific surface area is preferably about 1 to 3000 m²/g, more preferably 100 to 1000 m²/g. The pore radius is preferably 4 to 2000 Angstrom.

In the present invention, the color developer used for the color developing process preferably incorporates an organic preservative selected from the group comprising the hydroxylamine derivatives described in Japanese Patent O. P. I. Publication Nos. 146043/1988, 146042/1988, 146041/1988, 146040/1988, 135938/1988 and 118748/1988, the hydroxamic acids, hydrazines, hydrazides, phenols, α-hydroxyketones, α-aminoketones, sugars, monoamines, diamines, quaternary ammonium salts, nitroxyl radicals, alcohols, oximes, diazide compounds and condensed cyclic amines described in Japanese Patent O. P. I. Publication No. 62639/1989, in place of hydroxylamine, a conventionally used preservative. It is particularly preferable from the viewpoint of the enhancement of the effect of the invention to use the compound represented by the following formula IV.

wherein R₁ and R₂ independently represent an alkyl group or hydrogen atom. R₁ and R₂ do not represent a hydrogen atom concurrently. R₁ and R₂ may bind together to form a ring.

With respect to the formula IV, R₁ and R₂ independently represent an alkyl group or hydrogen atom, but they do not represent a hydrogen atom concurrently. The alkyl groups represented by R₁ and R₂ may be identical or not, each of which preferably has a carbon number of 1 to 3. The alkyl groups for R₁ and R₂ include those having a substituent. R₁ and R₂ may bind together to form a ring, such as a heterocyclic ring like a piperidine or morpholine ring.

Examples of the hydroxylamine compound represented by the formula IV are given in US Patent Nos. 3,287,125, 3,293,034 and 3,287,124 and other publications. Particularly preferable compounds are exemplified as follows:

These compounds are used normally in the forms of free amine, hydrochloride, sulfate, p-toluenesulfonate, oxalate, phosphate, acetate and others.

The concentration of the compound represented by the formula IV in the color developer is normally 0.2 g/ℓ to 50 g/ℓ, preferably 0.5 g/ℓ to 30 g/ℓ, and still more preferably 1 g/ℓ to 15 g/ℓ.

Although the compound represented by the formula IV may be used in combination with conventionally used hydroxylamine and an organic preservative, it is preferable from the viewpoint of developability to avoid the use of hydroxylamine.

The compound represented by the following formula V is preferably used in the color developer since it serves to prevent the air oxidation of the color developer without having an adverse effect on the bleach-fixer even in the event of contamination.

wherein R₂₁ represents a hydroxylalkyl group having a carbon number of 2 to 6; R₂₂ and R₂₃ independently represent a hydrogen atom, alkyl group having a carbon number of 1 to 6, hydroxylalkyl group having a carbon number of 2 to 6, benzyl group or -Cn₁H₂n₁-N (n₁ is an integer of 1 to 6; X' and Y' independently represent a hydrogen atom, an alkyl group having a carbon number of 1 to 6 or hydroxylalkyl group having a carbon number of 2 to 6).

The compound represented by the above formula V is preferably exemplified as follows:

V-1:

Ethanolamine

V-2:

Diethanolamine

V-3:

Triethanolamine

V-4:

Diisopropanolamine

V-5:

2-methylaminoethanol

V-6:

2-ethylaminoethane;

V-7:

2-dimethylaminoethanol

V-8:

2-diethylaminoethanol

V-9:

1-diethylamino-1-propanol

V-10:

1-diethylamino-1-propanol

V-11:

3-dimethylamino-1-propanol

V-12:

Isopropylaminoethanol

V-13:

3-amino-1-propanol

V-14:

2-amino-2-methyl-1,3-propanediol

V-15:

Ethylenediaminetetraisopropanol

V-16:

Benzyldiethanolamine

V-17:

2-amino-2-(hydroxymethyl)-1,3-propanediol

From the viewpoint of prevention of air oxidation, the compound represented by the formula V is used preferably at 1 to 100 g, more preferably 2 to 30 g per liter of color developer.

The color developing agent for the color developer is preferably a p-phenylenediamine compound having a water-soluble group. At least one water-soluble group is present on the amino group or benzene nucleus of the p-phenylenediamine compound. Examples of preferred water-soluble groups include - (CH₂)_n-CH₂OH, - (CH₂)_m-NHSO₂-(CH₂)_n-CH₃, - (CH₂)_m-O-(CH₂)_n-CH₃, - (CH₂CH₂O)_nC_mH_2m+1 (m and n independently represent any integer,
-COOH group and -SO₃H group.

Examples of preferably used color developing agents are given below.

Exemplified Color Developing Agents

Of the color developing agents exemplified above, Exemplified Compound Nos. CD-1, CD-2, CD-3, CD-4, CD-6, CD-7 and CD-15 are preferred, with more preference given to Exemplified Compound No. CD-1.

The color developing agent is used normally in the form of a salt such as hydrochloride, sulfate or p-toluenesulfonate.

The amount of addition of the preferably used p-phenylenediamine compound is preferably not less than 0.5 x 10^-2 mol, more preferably 1.0 x 10^-2 to 1.0 x 10^-1 mol, ideally 1.5 x 10^-2 to 7.0 x 10^-2 mol per liter of color developer.

Even when the sulfite concentration in the color developer is low, specifically below 1.0 x 10^-2 mol, and even below 5.0 x 10^-4 mol, staining and deposition in the stabilizer are well prevented.

The color developer may contain the following developer components in addition to the components described above.

Alkalis such as sodium hydroxide, potassium hydroxide, silicate, sodium metaborate, potassium metaborate, trisodium phosphate, tripotassium phosphate and borax, whether singly or in combination, can be added, as long as their addition has a pH stabilizing effect without causing precipitation. Also, for purposes such as the facilitation of preparation and increase in ion strength, various salts such as disodium hydrogen phosphate, dipotassium hydrogen phosphate, sodium bicarbonate, potassium bicarbonate and borate can be used.

An inorganic or organic anti-fogging agent may be added as necessary.

A development accelerator may also be used as necessary. Examples of developing accelerators include the various pyridinium compounds described in US Patent Nos. 2,648,604 and 3,671,247 and Japanese Patent Examined Publication No. 9503/1969 and other cationic compounds, cationic pigments such as phenosafranine, neutral salts such as thallium nitrate, the polyethylene glycol and its derivatives described in US Patent Nos. 2,533,990, 2,531,832, 2,950,970 and 2,577,127 and Japanese Patent Examined Publication No. 9504/1969, nonionic compounds such as polythioethers, the phenethyl alcohol described in US Patent No. 2,304,925, and acetylene glycol, methyl ethyl ketone, cyclohexanone, thioethers, pyridine, ammonia, hydrazine and amines.

In the present invention, it is undesirable to use benzyl alcohol, and it is preferable to avoid the use of a poor organic solvent such as phenetyl alcohol. Its use is liable to cause tar formation during long term use of color developer, particularly during a running process using a reduced amount of replenisher, which tar formation can even cause a significant failure, namely considerable damage of the commercial value of the paper light-sensitive material to be processed by adhering thereto. In addition, since a poor organic solvent is weakly soluble in water, its use is troublesome, for example, a stirrer is required to prepare the color developer but also the obtained development accelerating effect is limited by the low solubility even when such a stirrer is used. Moreover, poor organic solvents must not be disposed of as such to sewage or rivers, thus requiring waste treatment because the biochemical oxygen demand (BOD) is high. Such waste treatment is extremely laborious and expensive. It is therefore preferable to minimize or totally avoid the use of benzyl alcohol and other poor organic solvents.

The color developer may contain the fluorescent brightening agent represented by the above formula Z-1.

The color developer may also appropriately incorporate organic solvents such as ethylene glycol, methyl cellosolve, methanol, acetone, dimethylformamide, β-cyclodextrin and the compounds described in Japanese Patent Examined Publication Nos. 33378/1972 and 9509/1969 for increasing the solubility of the developing agent.

An auxiliary developing agent may be used in combination with the principal developing agent. Examples of such auxiliary developing agents include N-methyl-p-aminophenol sulfate (Metol), phenidone, N,N-diethyl-p-aminophenol hydrochloride and N,N,N',N'-tetramethyl-p-phenylenediamine hydrochloride. The amount of their addition is preferably 0.01 to 1.0 g/ℓ.

It is also possible to use various additives such as an anti-staining agent, anti-sludge agent and lamination effect enhancer.

The color developer may appropriately contain chelating agents represented by the above formulas K-I through K-XV.

The color developer components can be prepared by sequential addition to a given amount of water with stirring. In this case, the components which are less soluble in water can be added in mixture with triethanolamine or another organic solvent described above. More commonly, a color developer can be obtained by adding to, and stirring in, water a dense aqueous solution or solid of a plurality of components which are capable of stable presence, previously prepared in a small vessel.

The color developer can be used in any pH range, but the pH is preferably 9.5 to 13.0, more preferably 9.8 to 12.0 from the viewpoint of rapid processing.

The color developer processing temperature is normally over 30°C, preferably over 33°C, and ideally over 35 to 65°C. The processing time is preferably within 90 seconds, more preferably between 3 seconds and 60 seconds, and ideally between 3 seconds and 45 seconds.

The amount of replenishment for the color developer is preferably 20 to 150 mℓ/m², more preferably 30 to 120 mℓ/m² for the desired anti-staining effect, since the effect of the present invention is enhanced when the amount of replenishment is small.

Color development can be achieved by various methods such as the spray method using the processing solution in the form of a spray, the web method based on the contact of the light-sensitive material with a carrier impregnated with the processing solution and the developing method using a viscous processing solution, as well as the one-bath processing method.

Examples of the bleaching agent for the bleacher of the present invention include ferric complex salts of the organic acid represented by the following formula A-I or B-I and ferric complex salts of Exemplified Compounds A'-1 through A'-16 shown below, with preference given to ferric complex salts of the organic acid represented by the following formula A-I or B-I.

wherein A₁ through A₄, whether identical or not, independently represent -CH₂OH, -COOM or -PO₃M₁M₂; M, M₁ and M₂ independently represent a hydrogen atom, atom of alkali metal such as sodium or potassium, or an ammonium group.

X represents a substituted or unsubstituted alkylene group having a carbon number of 3 to 6, such propylene, butylene or pentamethylene. Examples of the substituent include a hydrogen group and an alkyl group having a carbon number of 1 to 3.

Examples of preferred compounds represented by the above formula A-I are given below.

The ferric complex salt of these compounds A₁-1 through A₁-12 may be the sodium salt, potassium salt or ammonium salt thereof.

Of the compounds exemplified above, A₁-1, A₁-3, A₁-4, A₁-5 and A₁-9 are preferred, with more preference given to A₁-1.

wherein A₁ through A₄ have the same definitions as above; n represents an integer of 1 to 8. B₁ and B₂, whether identical or not, independently represent a substituted or unsubstituted alkylene group having a carbon number of 2 to 5, such as an ethylene, propylene, butylene or pentamethylene group. Examples of the substituent include a hydroxyl group and a lower alkyl group having a carbon number of 1 to 3, such as a methyl group, ethyl group and propyl group.

Examples of preferred compounds represented by the above formula B-I are given below.

The ferric complex salt of these compounds B₁-1 through B₁-7 may be the sodium salt, potassium salt or ammonium salt thereof.

It is preferable for the embodiment of the present invention that the ferric complex salt of the organic acid represented by the above formula A-I or B-I be sufficiently oxidative and the ammonium salt content be not more than 50 mol%, more preferably not more than 20 mol%, and ideally not more than 10 mol% from the viewpoint of prevention of environmental pollution.

Of the compounds exemplified above, B₁-1, B₁-2 and B₁-7 are preferred, with more preference given to B₁-1.

The amount of addition of the ferric complex salt of organic acid is preferably 0.1 to 2.0 mol, more preferably 0.15 to 1.5 mol per liter of bleacher.

Examples of preferred bleachers other than the compound represented by the above formula A-I or B-I include the ferric complex salts such as ammonium, sodium, potassium and triethanolamine salts of the following compounds, but these are not to be construed as limitative.

A'-1:

Ethylenediaminetetraacetic acid

A'-2:

trans-1,2-cyclohexanediaminetetraacetic acid

A'-3:

Dihydroxyethylglycinic acid

A'-4:

Ethylenediaminetetrakismethylenephosphonic acid

A'-5:

Nitrilotrismethylenephosphonic acid

A'-6:

Diethylenetriaminepentakismethylenephosphonic acid

A'-7:

Diethylenetriaminepentaacetic acid

A'-8:

Ethylenediaminediorthohydroxyphenylacetic acid

A'-9:

Hydroxyethylethylenediaminetriacetic acid

A'-10:

Ethylenediaminedipropionic acid

A'-11:

Ethylenediaminediacetic acid

A'-12:

Hydroxyethyliminodiacetic acid

A'-13:

Nitrilotriacetic acid

A'-14:

Nitrilotripropionic acid

A'-15:

Triethylenetetraminehexaacetic acid

A'-16:

Ethylenediaminetetrapropionic acid

The bleacher may incorporate one or more ferric complex salts of the compounds A'-1 through A'-16 in combination with the ferric complex salt of the compound represented by the above formula A-I or B-I.

When using two or more ferric complex salts of organic acid in combination, it is preferable for the enhancement of the effect of the present invention that the ferric complex salt of the compound represented by the above formula A-I or B-I account for not less than 70 mol%, more preferably not less than 90 mol%, and ideally not less than 95 mol%.

From the viewpoint of rapid processing, ammonium is desirable as the cation in the bleacher, but it is possible to use non-ammonium salt such as potassium, sodium or alkanolamine salt, since the ferric complex salt of the organic acid represented by the above formula A-I or B-I is highly oxidative as stated above, which forms a preferred mode of the embodiment of the invention. In this case, the ammonium salt content is preferably not more than 50 mol%, more preferably not more than 20 mol%, and ideally not more than 10 mol% of the total cation content for the enhancement of the desired effect.

The iron (III) complex salt of organic acid may be used in the form of a complex salt as such or may be converted to an iron (III) ion complex salt by reaction in a solution between an iron (III) salt such as ferrous sulfate, ferrous chloride, ferrous acetate, ferrous ammonium sulfate or ferrous phosphate and aminopolycarboxylic acid or its salt. When using in the form of a complex salt as such, one or more complex salts may be used. When using a ferrous salt and aminopolycarboxylic acid to form a complex salt in a solution, one or more ferrous salts may be used. Similarly, one or more aminopolycarboxylic acids may be used. In either case, aminopolycarboxylic acid may be used in excess for the formation of iron (III) ion complex salt.

The bleach-fixer or bleacher containing the iron (III) ion complex may incorporate an ion complex salt of a metal other than iron, such as cobalt, copper, nickel or zinc.

The rapid processing effect can be enhanced by incorporating in the bleacher at least one of the imidazole described in Japanese Patent Application No. 48931/1988 and its derivatives and the compounds represented by the formulas I through IX described in the same patent application.

In addition to the bleaching accelerators described above, it is possible to use the compounds exemplified in Japanese Patent Application No. 263568/1985, pp. 51-115, the compounds exemplified in Japanese Patent O. P. I. Publication No. 17445/1988, pp. 22-25, and the compounds described in Japanese Patent O. P. I. Publication Nos. 95630/1978 and 28426/1978.

These bleaching accelerators may be used alone or in combination. The amount of their addition is preferably about 0.01 to 100 g, more preferably 0.05 to 50 g, and ideally 0.05 to 15 g per liter of bleacher.

The bleaching accelerator may be added and dissolved as such, but it is common practice to add it in solution in water, alkali or organic acid, and an organic solvent such as methanol, ethanol or acetone may be appropriately used to dissolve it before its addition.

The temperature of the bleacher is normally 20 to 50°C, and desirably 25 to 45°C.

The pH of the bleacher is preferably not more than 6.0, more preferably not less than 1.0 and not more than 5.5.

It should be noted that the pH of the bleacher means the pH in the silver halide light-sensitive material processing tank solution and is clearly differentiated from the pH of the replenisher.

The bleacher normally incorporates a halide such as ammonium bromide, potassium bromide or sodium bromide. Various fluorescent brightening agents, defoaming agents and surfactants may be added.

The amount of bleacher replenisher is normally not more than 500 mℓ, preferably 20 to 400 mℓ, and ideally 40 to 350 mℓ per m² of silver halide color photographic light-sensitive material. As the amount of replenisher decreases, the effect of the present invention is more enhanced.

In the present invention, to increase the activity of the bleacher, air or oxygen sparging may be carried out in the processing bath and in the replenisher storage tank if necessary, and an appropriate oxidant such as hydrogen peroxide, hydrobromate or persulfate may be appropriately added.

The fixing agent used in the fixer in the fixation process following the bleaching process is at least 0.2 mol/ℓ thiosulfate as stated above, but its use in combination with thiocyanate offers improvement in the prevention of sagging, a problem to be solved by the invention.

The amount of addition of thiocyanate is preferably 0.1 to 3.0 mol/ℓ, more preferably 0.2 to 2.5 mol/ℓ.

In addition to these fixing agents, the fixer may contain one or more pH buffers selected from the group comprising various acids and salts such as boric acid, borax, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, acetic acid, sodium acetate and ammonium hydroxide.

It is also desirable to add a large amount of a re-halogenating agent such as an alkali halide or ammonium halide, such as potassium bromide, sodium bromide, sodium chloride or ammonium bromide. It is also possible to appropriately add pH buffers such as borate, oxalate, acetate, carbonate and phosphate and compounds which are known as additives to the fixer such as alkylamines and polyethylene oxides.

With respect to the fixer of the present invention, it is a preferred mode of the embodiment of the invention that the ammonium ion concentration is not more than 50 mol%, more preferably not more than 20 mol%, and ideally 0 to 10 mol% of the total cation content from the viewpoint of prevention of staining upon processing with fixer immediately after bleaching and suppression of environmental pollution by reducing the ammonium ion concentration. However, reduction in the ammonium ion concentration can affect the fixability; therefore, it is preferable to concomitantly use thiocyanate at about 0.1 to 3.0 mol/ℓ, or to keep the thiosulfate concentration at not less than 0.5 mol/ℓ, more preferably not less than 1.0 mol/ℓ, and ideally 1.2 to 2.5 mol/ℓ.

Silver may be recovered from the fixer by a known method. Examples of method which serve well for this purpose include the electrolytic method described in French Patent No. 2,299,667, the precipitation method described in Japanese Patent O. P. I. Publication No. 73037/1977 and German Patent No. 2,331,220, the ion exchange method described in Japanese Patent O. P. I. Publication No. 17114/1976 and German Patent No. 2,548,237 and the metal replacement method described in British Patent No. 1,353,805.

For silver recovery, it is particularly preferable to recover silver from the tank solution on an in-line basis using the electrolytic method or ion exchange resin method, since the rapid processing suitability improves, but silver may be recovered from the overflow waste liquid for recycled use.

The amount of replenishment for the fixer is preferably not more than 1200 mℓ, more preferably 20 to 1000 mℓ, and ideally 50 to 800 mℓ per m² of light-sensitive material.

The pH of the fixer is preferably 4 to 8.

A compound represented by the formula FA described in Japanese Patent Application No. 48931/1988, pp. 56 may be added to the fixer, which offers an additional effect in that sludge formation is significantly suppressed during prolonged processing of a small amount of light-sensitive material with a bleach-fixer or fixer.

A compound represented by the formula FA can be synthesized by the ordinary method described in US Patent Nos. 3,335,161 and 3,260,718. These compounds represented by the formula FA may be used alone or in combination.

Use of these compounds represented by the formula FA yields good results when they are added in amounts of 0.1 to 200 g per liter of processing solution.

The fixer may incorporate a sulfite and sulfite-releasing compound. Examples of such compounds include potassium sulfite, sodium sulfite, ammonium sulfite, ammonium hydrogen sulfite, potassium hydrogen sulfite, sodium hydrogen sulfite, potassium metabisulfite, sodium metabisulfite and ammonium metabisulfite, as well as the compound represented by the formula B-1 or B-2 described in Japanese Patent Application No. 48931/1988, p. 60.

These sulfites and sulfite-releasing compounds should necessarily be present in an amount of at least 0.1 mol as sulfite ion per liter of fixer, but their concentration is preferably 0.12 to 0.65 mol/ℓ, more preferably 0.15 to 0.50 mol/ℓ, and ideally 0.20 to 0.40 mol/ℓ.

The processing times respectively for the bleacher and fixer of the present invention may be set at any level, but each processing time is preferably shorter than 4 minutes and 30 seconds, more preferably 20 seconds to 3 minutes and 20 seconds, more preferably 40 seconds to 3 minutes, and ideally 60 seconds to 2 minutes and 40 seconds.

In the processing method of the present invention, it is a preferred mode of embodiment to conduct forced stirring of the bleacher and fixer. This is because it not only enhances the desired effect of the invention but also improves the rapid processing suitability. Here, forced stirring does not imply ordinary diffusive migration of solution but implies stirring by means of a stirrer. This forced stirring can be achieved by the methods described in Japanese Patent Application No. 48930/1988 and Japanese Patent O. P. I. Publication No. 206343/1989.

In the present invention, bleach fogging, an additional effect of the invention, is effected when the crossover time between processing solution tanks such as between the color developer tank and the bleach tank is within 10 seconds, preferably within 7 seconds. It is another preferred mode of the embodiment of the invention to reduce the amount of processing solution carried by the light-sensitive material by means of, for example, a duckbill valve, which enhances the effect of the invention.

It is preferable to add sulfite to the stabilizer. Any sulfite, whether organic or inorganic, can be used, as long as it releases sulfite ions, but preference is given to an inorganic salt. Examples of preferred compounds include sodium sulfite, potassium sulfite, ammonium sulfite, ammonium bisulfite, potassium bisulfite, sodium bisulfite, sodium metabisulfite, potassium metabisulfite, ammonium metabisulfite and hydrosulfite. The sulfite is added preferably in amounts such that its concentration in the stabilizer is at least 1 x 10^-3 mol/ℓ, more preferably 5 x 10^-3 mol/ℓ to 10^-1 mol/ℓ. Its addition is preferred, since it has an anti-staining effect. Although it may be added directly to the stabilizer, it is preferable to add it to the stabilizer replenisher.

Ammonium compounds are particularly desirable for addition to the stabilizer. They are supplied via ammonium salts of various inorganic compounds. Examples thereof include ammonium hydroxide, ammonium bromide, ammonium carbonate, ammonium chloride, ammonium hypophosphite, ammonium phosphate, ammonium fluoride, acidic ammonium fluoride, ammonium fluoroborate, ammonium arsenate, ammonium hydrogen carbonate, ammonium hydrofluoride, ammonium hydrogen sulfite, ammonium sulfate, ammonium iodide, ammonium nitrate, ammonium pentaborate, ammonium acetate, ammonium adipate, ammonium laurin tricarboxylate, ammonium benzoate, ammonium carbamate, ammonium citrate, ammonium diethyldithiocarbamate, ammonium formate, ammonium hydrogen malate, ammonium hydrogen oxalate, ammonium phthalate, ammonium hydrogen tartrate, ammonium thiosulfate, ammonium sulfite, ammonium ethylenediaminetetraacetate, ferric ammonium ethylenediaminetetraacetate, ammonium lactate, ammonium malate, ammonium maleate, ammonium oxalate, ammonium phthalate, ammonium picrate, ammonium pyrrolidine dithiocarbamate, ammonium salicylate, ammonium succinate, ammonium sulfanilate, ammonium tartrate, ammonium thioglycollate and 2,4,6-trinitrophenol ammonium. These compounds may be used singly or in combination.

The amount of addition of ammonium compounds is preferably 0.001 to 1.0 mol, more preferably 0.002 to 2.0 mol per liter of stabilizer.

It is particularly preferable to add a chelating agent having an iron ion chelate stability constant of over 8 to the stabilizer from the viewpoint of the enhancement of the desired effect of the invention. Here, the chelate stability constant is the constant which is well known in L. G. Sillen and A. E. Martell, "Stability Constants of Metal Ion Complexes", the Chemical Society, London (1964), S. Chaberek and A. E. Martell in "Organic Sequestering Agents", Wiley (1959), and other publications.

Examples of chelating agents having an iron ion chelate stability constant of over 8 include organic carboxylic acid chelating agents, organic phosphoric acid chelating agents, inorganic phosphoric acid chelating agents and polyhydroxy compounds. The iron ion means the ferric ion (Fe³⁺).

Examples of chelating agents having a ferric ion chelate stability constant of over 8 include ethylenediaminediorthohydroxyphenylacetic acid, diaminopropanetetraacetic acid, nitrilotriacetic acid, hydroxyethylenediaminetriacetic acid, dihydroxyethyl glycine, ethylenediaminediacetic acid, ethylenediaminedipropionic acid, iminodiacetic acid, diethylenetriaminepentaacetic acid, hydroxyethyliminodiacetic acid, diaminopropanoltetraacetic acid, trans-cyclohexanediaminetetraacetic acid, glycol ether diaminetetraacetic acid, ethylenediaminetetrakismethylenephosphonic acid, nitrilotrimethylenephosphonic acid, 1-hydroxyethylidene-1,1-diphosphonic acid, 1,1-diphosphonoethane-2-carboxylic acid, 2-phosphonobutane-1,2,4-tricarboxylic acid, 1-hydroxy-1-phosphonopropane-1,2,3-tricarboxylic acid, catechol-3,5-diphosphonic acid, sodium pyrophosphate, sodium tetrapolyphosphate and sodium hexametaphosphate, but these are not to be construed as limitative. Of these compounds, diethylenetriaminepentaacetic acid, nitrilotriacetic acid, nitrilotrimethylenephosphonic acid and 1-hydroxyethylidene-1,1-diphosphonic acid are more preferable, with most preference given to 1-hydroxyethylidene-1,1-diphosphonic acid.

The amount of the chelating agent is preferably 0.01 to 50 g, more preferably 0.05 to 20 g per liter of stabilizer.

Examples of other commonly known compounds which can be added to the stabilizer include polyvinylpyrrolidone (PVPK-15, K-30, K-90), salts of organic acid such as citric acid, acetic acid, succinic acid, oxalic acid and benzoic acid, pH regulators such as phosphate, borate, hydrochloric acid and sulfuric acid, antifungal agents such as phenol derivatives, catechol derivatives, imidazole derivatives, triazole derivatives, cyabendazole derivatives, organic halides and others known as slime controlling agents in the paper-pulp industry, fluorescent brightening agents, surfactants, preservatives, and salts of metals such as Bi, Mg, Zn, Ni, Aℓ, Sn, Ti and Zr. These compounds may be used in any combination, as long as they are necessary to maintain a desired pH level in the stabilizing bath and it does not affect the storage stability of color photographic images or cause precipitation.

The stabilization processing temperature is normally 15 to 70°C, preferably 20 to 55°C. The processing time is preferably within 120 seconds, more preferably 3 to 90 seconds, and ideally 6 to 50 seconds for the enhancement of the effect of the present invention.

Washing is not necessary at all after stabilization, but rinsing, surface washing, etc. with a small amount of water for a very short time may be carried out optionally. The presence of a soluble salt of iron in the stabilizing solution is preferred for the enhancement of the effect of the invention. Examples of soluble salts of iron include iron salts of inorganic acid such as ferric chloride, ferrous chloride, ferric phosphate, ferric bromide, ferric nitrate and ferrous nitrate and iron salts of organic acid such as ferric ethylenediaminetetraacetate, ferric 1-hydroxyethylidene-1,1-diphosphonate, ferrous 1-hydroxyethylidene-1,1-diphosphonate, ferrous ethylenediaminetetraacetate, ferric diethylenetriaminepentaacetate, ferrous diethylenetriaminepentaacetate, ferric citrate, ferrous citrate, ethylenediaminetetramethylenephosphonate, ferrous ethylenediaminetetramethylenephosphonate, ferric nitrilotrimethylenephosphonate, ferric nitrilotriacetate and ferrous nitrilotriacetate. These iron salts of organic acid may be used in the form of a free acid or sodium salt, potassium salt, ammonium salt, lithium salt, alkylammonium salt such as triethanolammonium salt, trimethylammonium salt or tetramethylammonium salt. These soluble salts of iron are used preferably at a concentration of at least 5 x 10^-3 mol/ℓ, more preferably 8 x 10^-3 to 150 x 10^-3 mol/ℓ, and still more preferably 12 x 10^-3 to 100 x 10^-3 mol/ℓ in the stabilizer. The addition of these soluble salts of iron to the stabilizer (tank solution) may be by adding them to the stabilizer replenisher, or by eluting them in the stabilizer from the light-sensitive material, or by introducing them while adhering to the light-sensitive material from the previous bath.

In the present invention, the stabilizer may be subjected to ion exchange resin treatment so that the calcium ion and magnesium ion concentration is below 5 ppm, and the antifungal agent and halogen ion releasing compound may be added to such a stabilizer.

The pH of the stabilizer is preferably 5.5 to 10.0. The pH regulator which may be added to the stabilizer may be any one of the commonly known alkali or acid agents.

From the viewpoint of rapid processing and dye image preservability, the amount of stabilizer replenisher is preferably 0.1 to 50 times the amount of processing solution carried from the previous bath (bleach-fixer), more preferably 0.5 to 30 times, per unit area of light-sensitive material.

The stabilizer tank preferably comprises 1 to 5 chambers, more preferably 1 to 3 chambers, and ideally 1 chamber from the viewpoint of silver removal efficiency and rapid processing.

Light-sensitive materials which are preferably used for the present invention are described below.

Examples of silver halide grains preferably used for the light-sensitive material include silver chloride grains and silver chlorobromide grains. It is preferable to use silver halide grains based mainly on silver chloride wherein the silver chloride content is at least 80 mol%, more preferably at least 90 mol%, still more preferably at least 95 mol%, and ideally at least 99 mol%. It is a preferred mode of the embodiment of the present invention to process a light-sensitive material incorporating a silver halide emulsion based mainly on such a silver chloride.

The silver halide emulsion based mainly on silver chloride may contain silver bromide and/or silver iodide in addition to silver chloride in the silver halide composition. In this case, the silver bromide content is preferably not more than 20 mol%, more preferably not more than 10 mol%, and still more preferably not more than 3 mol%. When silver iodide is contained, its content is preferably not more than 1 mol%, more preferably not more than 0.5 mol%, and ideally zero. Such silver halide grains based mainly on silver chloride having a silver chloride content of over 80 mol% are added to at least one silver halide emulsion layer, but it is preferable to add them to all silver halide emulsion layers.

The crystal configuration of the silver halide grains may be normal crystal, twin crystal or any other crystal, and any ratio of the [1.0.0] plane and the [1.1.1] plane is usable. With respect to the crystal structure of these silver halide grains, it may be uniform from the core to the outer portion and may be of the core shell type wherein the core and the outer portion are of different layer structures.

These silver halides may be of the type wherein latent images are formed mainly on the surface. Moreover, tabular grains of silver halide such as those described in Japanese Patent O. P. I. Publication No. 113934/1983 and Japanese Patent Application No. 170070/1984 may be used. Also usable are the silver halides described in Japanese Patent O. P. I. Publication Nos. 26837/1989, 26838/1989 and 77047/1989.

The silver halide grains may be prepared by any of the acid method, neutral method, ammoniacal method and other methods.

It is also possible to use the method in which seed grains are formed by the acid method and are grown to a given size by the ammoniacal method, which accelerates grain growth. In growing silver halide grains, it is preferable to control the pH, pAg and other factors in the reactor and to sequentially or simultaneously add and mix silver ions and halide ions in an amount according to the rate of growth of silver halide grains described in Japanese Patent O. P. I. Publication No. 48521/1979.

The silver halide emulsion layer of the light-sensitive material processed in accordance with the present invention contains color couplers. The color couplers form a non-diffusible dye upon reaction with the oxidation product of a color developing agent. The color couplers are bound together in, or in close contact with, the light-sensitive layer preferably in a non-diffusible form.

The red-sensitive layer may thus contain a non-diffusible color coupler which forms a cyan color image, normally a phenol or α-naphthol coupler. The green-sensitive layer may contain at least one non-diffusible color coupler which forms a magenta color image, normally a 5-pyrazolone color coupler and pyrazolotriazole.

The blue-sensitive layer may contain at least one non-diffusible color coupler which forms a yellow color image, normally a color coupler having an open chain ketomethylene group. The color coupler may be a 6-, 4- or 2-equivalent coupler, for instance.

A 2-equivalent coupler is particularly preferred for the present invention.

Appropriate couplers are disclosed in the following publications: W. Pelz, "Color Coupler" (Farbkuppler) in Mitteilunglnausden Forschungslaboratorien det Agfa, Leverkusen/Munchen, vol. III, p. 111 (1961); K. Venkataraman, "The Chemistry of Synthetic Dyes", vol. 4, pp. 341-387, Academic Press; "The Theory of the Photographic Processes", 4th edition, pp. 353-362; Research Disclosure No. 17643, Section VII.

From the viewpoint of enhancement of the desired effect of the invention, it is preferable to use the magenta coupler represented by the formula M-1 described in Japanese Patent O. P. I. Publication No. 106655/1988, p. 26 (exemplified by Magenta Coupler Nos. 1 through 77 described in Japanese Patent O. P. I. Publication No. 106655/1988, pp. 29-34), the cyan coupler represented by the formula C-I or C-II described in Japanese Patent O. P. I. Publication No. 106655/1988, p. 34 (exemplified by Cyan Coupler Nos. C'-1 through C'-82 and C"-1 through C"-36 described in Japanese Patent O. P. I. Publication No. 106655/1988, pp. 37-42) and the rapid yellow coupler described in Japanese Patent O. P. I. Publication No. 106655/1988, p. 20 (exemplified by Cyan Coupler Nos. Y'-1 through Y'-39 described in Japanese Patent O. P. I. Publication No. 106655/1988, pp. 21-36.

It is a more preferred mode of the embodiment of the present invention to use a nitrogen-containing heterocyclic mercapto compound in the light-sensitive material incorporating an emulsion based mainly on silver chloride, since it not only enhances the desired effect of the invention but also serves to minimize the influence on field immersion performance due to contamination of color developer with bleach-fixer.

Examples of these nitrogen-containing heterocyclic mercapto compounds include Compound Nos. I'-1 through I'-87 exemplified in Japanese Patent O. P. I. Publication No. 106655/1988, pp. 42-45.

A silver halide emulsion based mainly on silver chloride can be prepared by a conventional method such as single or double feeding of the starting materials at constant or accelerated rate. It is preferable to prepare it by double feeding while regulating the pAg (cf. Research Disclosure No. 17643, Sections I and II.

The emulsion based mainly on silver chloride may be chemically sensitized. A sulfur-containing compound such as allylisothiocyanate, allylthiourea or thiosulfate is particularly preferred as a chemical sensitizer. Reducing agents can also be used as chemical sensitizers, including the silver compounds described in Belgian Patent Nos. 493,464 and 568,687 and polyamine or aminomethylsulfinic acid derivatives such as the diethylenetriamine in accordance with Belgian Patent No. 547,323. Noble metals such as gold, platinum, palladium, iridium, ruthenium and rhodium and noble metal compounds also serve as appropriate sensitizers.

This chemical sensitization procedure is described by R. Kosiovsky in "Zeitschrift für Wissenschaftliche Photographie", 46, 65-72 (1951) (cf. Research Disclosure No. 17643, Section III).

The emulsion based mainly on silver chloride may be optically sensitized by a known method using, for example, an ordinary polymethine dye such as neutrocyanine, basic or acidic carbocyanine, rhodacyanine or hexacyanine, or a styryl dye, oxonol or related substance (cf. F. M. Hamer, "The Cyanine Dyes and Related Compounds", Ullmanns Enbzyklpadie der Technischen Chemie, 4th edition, vol. 18, p. 431 (1964); Research Disclosure No. 17643, Section IV.

The emulsion based mainly on silver chloride may incorporate an ordinary anti-fogging agent and stabilizer. Azaindene is particularly suitable as a stabilizer, with preference given to tetra- and penta-azaindenes and more preference given to those substituted by a hydroxyl group or amino group. Such compounds are described in Zeitschrift für Wissenschaftliche Photographie by Birr, 47, 2-58 (1952) and Research Disclosure No. 17643, Section IV.

Additives can be added to the light-sensitive material by known methods such as those described in US Patent Nos. 2,322,027, 2,533,514, 3,689,271, 3,764,336 and 3,765,897.

Of the components of the light-sensitive material, a coupler and UV absorbent can be incorporated in the form of a charged latex (cf. German Patent Publication No. 2,541,274 and European Patent Application No. 14,924). These components can also be immobilized as polymers in the light-sensitive material (cf. German Patent Publication No. 2,044,992 and US Patent Nos. 3,370,952 and 4,080,211).

An ordinary support can be used for the light-sensitive material, but a reflective support such as a paper support is most suitable, which can be coated with polyolefin, particularly polyethylene or polypropylene (cf. Research Disclosure No. 17643, Sections V and VI).

Any light-sensitive material can be used, as long as it contains a coupler therein and is processed by so-called internal development, such as a color paper, color negative film, color positive film, color reversal film for slide, color reversal film for movie, color reversal film for TV and reversal color paper, with most preference given to a color paper based mainly on silver chloride.

The stabilizer which contains the water-soluble surfactant of the present invention and which is brought into contact with the ion exchange resin or adsorbent of the invention is normally used to process light-sensitive materials for color paper. However, from the viewpoint of size reduction for automatic developing machines, a mixed processing system is very useful, since it permits mixed processing of two different light-sensitive materials such as a combination of a light-sensitive material for films and a light-sensitive material for paper. It is therefore a preferred mode of embodiment of the present invention to subject at least two different light-sensitive materials, namely a silver halide color photographic light-sensitive material comprising a support and a silver halide emulsion having an average silver iodide content of not less than 2 mol% coated thereon and another silver halide color photographic light-sensitive material comprising a support and a silver halide emulsion having a silver chloride content of not less than 80 mol% coated thereon to mixed processing wherein a part or all of the overflow from the stabilizing bath used to process the former silver halide colour photographic light-sensitive material is allowed to enter the stabilizing bath used to process the latter silver halide color photographic light-sensitive material, since the stabilizer of the invention described above, in comparison with the conventional method in which a light-sensitive material for films and a light-sensitive material for paper are processed separately, permits reduction in the amount of stabilizer replenisher and offers improvements in the prevention of staining, crystal deposition on the processing tanks and rollers and other problems to enhance the effect of the invention by allowing the overflow from the stabilizing bath used to process the light-sensitive material for films to enter the stabilizing bath used to process the light-sensitive material for paper.

EXAMPLES Example 1

Layers with the following compositions were formed on a paper support laminated with polyethylene on one face and titanium oxide-containing polyethylene on the first layer side of the other face to yield a multiple layer silver halide color photographic light-sensitive material 1. The coating solutions were prepared as follows:
First layer coating solution

26.7 g of a yellow coupler Y-1, 10.0 g of a dye image stabilizer ST-1, 6.67 g of a dye image stabilizer ST-2, 0.67 g of an additive HQ-1 and 6.67 g of a high boiling organic solvent DNP were dissolved in 60 mℓ of ethyl acetate. This solution was emulsified and dispersed in 220 mℓ of a 10% aqueous solution of gelatin containing 7 mℓ of 20% surfactant SU-1 using an ultrasonic homogenizer to yield a yellow coupler dispersion. This dispersion was mixed with a blue-sensitive silver halide emulsion containing 10 g of silver prepared as follows to yield a first layer coating solution.

Second through seventh coating solutions were prepared in the same manner as with the first layer coating solution.

Layer	Composition	Amount of addition (g/m2)
Layer 7	Protective layer
	Gelatin	1.0
Layer 6	Ultraviolet absorbing layer
	Gelatin	0.4
	UV absorbent UV-1	0.10
	UV absorbent UV-2	0.04
	UV absorbent UV-3	0.16
	Antistaining agent HQ-1	0.01
	DNP	0.2
	PVP	0.03
	Anti-irradiation dye AI-2	0.02
Layer 5	Red-sensitive layer
	Gelatin	1.30
	Red-sensitive silver chlorobromide emulsion EmC (as silver)	0.21
	Cyan coupler C-1	0.17
	Cyan coupler C-2	0.25
	Dye image stabilizer ST-1	0.20
	Antistaining agent HQ-1	0.01
	HBS-1	0.20
	DOP	0.20
Layer 4	Ultraviolet absorbing layer
	Gelatin	0.94
	UV absorbent UV-1	0.28
	UV absorbent UV-2	0.09
	UV absorbent UV-3	0.38
	Antistaining agent HQ-1	0.03
	DNP	0.40
Layer 3	Green-sensitive layer
	Gelatin	1.40
	Green-sensitive silver chlorobromide emulsion EmB (as silver)	0.17
	Magenta coupler M-1	0.35
	Dye image stabilizer ST-3	0.15
	Dye image stabilizer ST-4	0.15
	Dye image stabilizer ST-5	0.15
	DNP	0.20
	Anti-irradiation dye AI-1	0.01
Layer 2	Interlayer
	Gelatin	1.20
	Antistaining agent HQ-1	0.12
	DIDP	0.15
Layer 1	Blue-sensitive layer
	Gelatin	1.20
	Blue-sensitive silver chlorobromide emulsion EmA (as silver)	0.26
	Yellow coupler Y-l	0.80
	Dye image stabilizer ST-1	0.30
	Dye image stabilizer ST-2	0.20
	Antistaining agent HQ-1	0.02
	Anti-irradiation dye AI-3	0.01
	DNP	0.20
Support
	Polyethylene-laminated paper

DOP:

Dioctyl phthalate

DNP:

Dinonyl phthalate

DIDP:

Diisodecyl phthalate

PVP:

Polyvinylpyrrolidone

The following compound H-1 was used as a hardener.

Preparation of blue-sensitive silver halide emulsion

To 1000 mℓ of a 2% aqueous solution of gelatin incubated at 40°C, the following solutions A and B were simultaneously added over a period of 30 minutes while maintaining a pAg of 6.5 and a pH of 3.0, after which the following solutions C and D were simultaneously added over a period of 180 minutes while maintaining a pAg of 7.3 and a pH of 5.5.

pAg was regulated by the method described in Japanese Patent O. P. I. Publication No. 45437/1984, and pH was regulated using an aqueous solution of sulfuric acid or sodium hydroxide.

solution A
Sodium chloride	3.42 g
Potassium bromide	0.03 g

Water was added to make a total quantity of 200 ml.

Solution B
Silver nitrate	10 g

Water was added to make a total quantity of 200 ml.

Solution C
Sodium chloride	102.7 g
Potassium bromide	1.0 g

Water was added to make a total quantity of 600 ml.

Solution D
Silver nitrate	300 g

Water was added to make a total quantity of 600 mℓ.

After completion of the addition, the mixture was desalted with a 5% aqueous solution of Demol N, a product of Kao Atlas and a 20% aqueous solution of magnesium sulfate and then mixed with an aqueous solution of gelatin to yield a monodispersed emulsion EMP-1 comprising cubic grains having an average grain size of 0.85 µm, a coefficient of variance (σ/r) of 0.07 and a silver chloride content of 99.5 mol%.

The emulsion EMP-1 was chemically ripened with the following compounds at 50°C for 90 minutes to yield a blue-sensitive silver halide emulsion EmA.

Sodium thiosulfate	0.8 mg/mol AgX
Chloroauric acid	0.5 mg/mol AgX
stabilizer SB-5	6 x 10-4 mol/mol AgX
Sensitizing dye D-l	5 x 10 -4 mol/mol AgX

Preparation of green-sensitive silver halide emulsion

A monodispersed emulsion EMP-2 comprising cubic grains having an average grain size of 0.43 µm, a coefficient of variance (σ/r) of 0.08 and a silver chloride content of 99.5 mol% was prepared in the same manner as with EMP-1 except that the addition time for Solutions A and B and the addition time for Solutions C and D were changed.

The emulsion EMP-2 was chemically ripened with the following compounds at 55°C for 120 minutes to yield a green-sensitive silver halide emulsion EmB.

Sodium thiosulfate	1.5 mg/mol AgX
Chloroauric acid	1.0 mg/mol AgX
Stabilizer SB-5	6 x 10-4 mol/mol AgX
Sensitizing dye D-2	4 x 10-4 mol/mol AgX

Preparation of red-sensitive silver halide emulsion

A monodispersed emulsion EMP-3 comprising cubic grains having an average grain size of 0.50 µm, a coefficient of variance (σ/r) of 0.08 and a silver chloride content of 99.5 mol% was prepared in the same manner as with EMP-1 except that the addition time for Solutions A and B and the addition time for Solutions C and D were changed.

The emulsion EMP-3 was chemically ripened with the following compounds at 60°C for 90 minutes to yield a red-sensitive silver halide emulsion EmC.

Sodium thiosulfate	1.8 mg/mol AgX
Chloroauric acid	2.0 mg/mol AgX

The samples thus obtained were subjected to exposure in accordance with a conventional method and then processed using the following procedures and processing solutions.

Procedures
(1)	Color development	35.0 ± 0.3°C	45 seconds
(2)	Bleaching	35.0 ± 0.5°C	20 seconds
(3)	Fixation	35.0 ± 0.5°C	20 seconds
(4)	Stabilization (3-tank cascade)	30 to 34°C	90 seconds
(5)	Drying	60 to 80°C	30 seconds

Color developer tank solution
Triethanolamine	10 g
Ethylene glycol	1 g
N,N-diethylhydroxylamine	3.6 g
Hydrazinodiacetic acid	5.0 g
Potassium bromide	20 mg
Potassium chloride	2.5 g
Diethylenetriaminepentaacetic acid	5 g
Potassium sulfite	5.0 x 10-4 mol
Color developing agent 3-methyl-4-amino-N-ethyl-N-(β-methanesulfonamidoethyl)-aniline sulfate	5.5 g

Stabilizer SB-5	6 x 10-4 mol/mol AgX
Sensitizing Dye D-3	1.0 x 10-4 mol/mol AgX

Potassium carbonate	25 g
Potassium hydrogen carbonate	5 g

Water was added to make a total quantity of 1 ℓ, and potassium hydroxide or sulfuric acid was added to obtain a pH of 10.10.

Color developer replenisher
Triethanolamine	14.0 g
Ethylene glycol	8.0 g
N,N-diethylhydroxylamine	5 g
Hydrazinodiacetic acid	7.5 g
Potassium bromide
	8 mg
Potassium chloride	0.3 g
Diethylenetriaminepentaacetic acid	7.5 g
Potassium sulfite	7.0 x 10-4 mol
Color developing agent 3-methyl-4-amino-N-ethyl-N-(β-methanesulfonamidoethyl)-aniline sulfate	8 g
Potassium carbonate	30 g
Potassium hydrogen carbonate	1 g

Water was added to make a total quantity of 1 ℓ, and potassium hydroxide or sulfuric acid was added to obtain a pH of 10.40.

Bleacher tank solution
Ferric ammonium 1,3-propylenediaminetetraacetate mol	0.32
Disodium ethylenediaminetetraacetate	10 g
Ammonium bromide	100 g
Glacial acetic acid	40 g
Ammonium nitrate	40 g

Water was added to make a total quantity of 1 ℓ, and aqueous ammonia was added to obtain a pH of 4.5.

Bleacher replenisher
Ferric ammonium
1,3-propylenediaminetetraacetate	0.35 mol
Disodium ethylenediaminetetraacetate	2 g
Ammonium bromide	120 g
Glacial acetic acid	68.9 g
Ammonium nitrate	80 g

Water was added to make a total quantity of 1 ℓ, and aqueous ammonia was added to obtain a pH of 3.5.

Fixer tank solution and fixer replenisher
Ammonium thiosulfate	180 g
Ammonium sulfite	20 g
Urea	1 g
Imidazole	4 g
Disodium ethylenediaminetetraacetate	1 g
Ammonium thiocyanate	150 g

Water was added to make a total quantity of 1 ℓ, and aqueous ammonia was added to obtain a pH of 7.5.

Stabilizer tank solution and stabilizer replenisher
Orthophenyl phenol	0.1 g
Uvitex (Ciba Geigy)	1.0 g
ZnSO4 .7H2O	0.1 g
Ammonium sulfite (40% solution)	5.0 mℓ
l-hydroxyethylidene-1,1-diphosphonic acid (60% solution)	30 g
Ethylenediaminetetraacetic acid	1.5 g

Water-soluble surfactant added in an amount shown in Table 1

Water was added to make a total quantity of 1 ℓ, and aqueous ammonia or sulfuric acid was added to obtain a pH of 7.8.

The color paper sample was subjected to running processing using the processing solutions thus prepared.

Running processing was carried out by filling an automatic developing machine with the color developer tank solution and bleach-fixer tank solution and stabilizer tank solution, and the color paper sample was processed therein while supplying the color developer replenisher, bleach-fixer replenisher and stabilizer replenisher using a fixation pump at 3-minute intervals.

To bring into contact the stabilizer with ion exchange resin or adsorbent, the filter portion of the stabilizing bath was equipped with a small bag, like a tea bag, containing ion exchange resin or adsorbent.

The amounts of replenishment were 100 mℓ per m² of color paper for the color developer tank, 220 mℓ per m² of color paper for the bleach-fixer tank and 250 mℓ per m² of color paper for the stabilizer tank.

Running processing was continued at 0.05 R every day until the amount of the color developer replenisher added to the color developer tank solution reached 3 times the capacity of the color developer tank, wherein 1 R corresponds to the addition of the color developer replenisher in an amount equal to the capacity of the color developer tank.

After completion of the continuous processing, the spectral reflective density at 640 nm in the unexposed portion was determined and the stain was evaluated. Also evaluated was the crystal deposition on the rollers and tank wall in the stabilizing bath.

The evaluation criteria are as follows:

o ○:

No deposition on the rollers or tank wall.

○:

Slight deposition on the rollers and tank wall.

Δ:

Small amount of deposition on the rollers and tank wall.

x:

Much deposition on the rollers and tank wall.

xx:

Much deposition on the rollers and tank wall, with precipitation on the tank bottom.

The results are given in Table 1.

Experiment number	Water-soluble surfactant	Stabilizer surface tension (dyne/cm)	Adsorbent to be brought into contact with stabilizer	Crystal deposition on the rollers and tank wall in the stabilizing bath	Stain in the unexposed portion at 640 nm
1-1	-	72	-	XX	0.133
1-2	-	72	III-1	X	0.120
1-3	1-5	63	III-I	X	0.120
1-4	1-5	58	III-1	Δ	0.102
1-5	1-5	35	III-I	o ○	0.095
1-6	1-5	27	III-1	o ○	0.092
1-7	1-5	20	III-I	o ○	0.089
1-8	I-14	62	III-I	X	0.119
1-9	I-14	55	III-I	Δ	0.099
1-10	I-14	30	III-I	o ○	0.093
1-11	I-14	20	III-I	o ○	0.088
1-12	1-14	19	III-1	o ○	0.084
1-13	1-17	61	III-1	X	0.118
1-14	1-17	49	III-1	Δ	0.098
1-15	1-17	27	III-1	o ○	0.090
1-16	1-17	20	III-1	o ○	0.086
1-17	1-17	18	III-1	o ○	0.084
1-18	II-3	68	III-1	X	0.120
1-19	II-3	54	III-I	Δ	0.103
1-20	II-3	25	III-1	o ○	0.097

Experiment number	Water-soluble surfactant	Stabilizer surface tension (dyne/cm)	Adsorbent to be brought into contact with stabilizer	Crystal deposition on the rollers and tank wall in the stabilizing bath	Stain in the unexposed portion at 640 nm
1-21	II-3	20	III-1	o ○	0.093
1-22	II-3	18	III-1	o ○	0.091
1-23	II-4	68	III-1	X	0.121
1-24	II-4	55	III-1	Δ	0.101
1-25	II-4	24	III-1	o ○	0.098
1-26	II-4	20	III-1	o ○	0.095
1-27	II-4	18	III-1	o ○	0.092
1-28	II-13	69	III-1	X	0.119
1-29	II-13	53	III-1	Δ	0.102
1-30	II-13	24	III-1	o ○	0.098
1-31	II-13	20	III-1	o ○	0.094
1-32	II-13	19	III-1	o ○	0.091
1-33	II-14	68	III-1	X	0.120
1-34	II-14	55	III-1	Δ	0.104
1-35	II-14	25	III-1	o ○	0.097
1-36	II-14	20	III-1	o ○	0.095
1-37	II-14	18	III-1	o ○	0.093
The amount of addition of the water-soluble surfactant is such that thestabilizer surface tension reaches a level shown in Table 1.

From Table 1, it is evident that stain in the unexposed portion and crystal deposition on the rollers and tank wall in the stabilizing bath are significantly improved by adding an appropriate amount of water-soluble surfactant to the stabilizer so that the stabilizer surface tension becomes 15 to 60 dyne/cm and bringing an adsorbent into contact with the stabilizer.

A similar effect was confirmed when the water-soluble surfactant specified in Table I was replaced with Exemplified Compound I-6, 12, 15, 16, 18, 19, II-9 or 10. When a large amount of water-soluble surfactant was added to the stabilizer so that the stabilizer surface tension was reduced to 13 dyne/cm, collapse occurred in the edge of the light-sensitive material.

Example 2

An experiment was carried out in the same manner as in Example 1 except that Exemplified Compound I-17 was added as a water-soluble surfactant to the stabilizer so that the stabilizer surface tension was 20 dyne/cm and the ion exchange resin or adsorbent to be brought into contact with the stabilizer in the stabilizing bath were changed as shown in Table 2. The obtained samples were evaluated with respect to stain in the unexposed portion and crystal deposition on the rollers and tank wall in the stabilizing bath. The results are shown in Table 2.

Experiment number	Adsorbent to be brought into contact with stabilizer	Crystal deposition on the rollers and tank wall in the stabilizing bath	Stain in the unexposed portion at 640 nm
2-1	-	X	0.120
2-2	III-1	o ○	0.088
2-3	III-2	o ○	0.087
2-4	III-6	o ○	0.088
2-5	III-7	o ○	0.086
2-6	III-13	o ○	0.085
2-7	III-17	o ○	0.086
2-8	III-25	o ○	0.086
2-9	III-26	o ○	0.087
2-10	III-28	o ○	0.086
2-11	Activated charcoal powder	o ○	0.090
2-12	Activated charcoal grains	o ○	0.090
2-13	Coconut shell activated charcoal	o ○	0.089
2-14	Molecular sieving carbon (produced by Takeda Chemical Industries Ltd.)	o ○	0.088
2-15	Bentonite (clay substance)	o ○	0.090
2-16	Silica gel (clay substance)	o ○	0.090
2-17	Synthetic zeolite Molecular Sieve BX, pelletized (produced by Takeda Chemical Industries Ltd.)	o ○	0.091
2-18	Synthetic zeolite Molecular Sieve SA, pelletized (produced by Takeda Chemical Industries Ltd.)	o ○	0.089
2-19	Nylon-6 fiber (polyamide polymer compound)	o ○	0.090
2-20	Neolon (produced by Teijin Ltd.) (polyurethane polymer compound)	o ○	0.088
2-21	Kainol (phenol resin) (produced by Nippon Kainol)	o ○	0.091
2-22	Duolite S-761 (phenol resin) (produced by Sumitomo Chemical Co., Ltd.)	o ○	0.092
2-23	Ebicuron-4050 (phenol resin) (produced by Dainippon Ink and Chemicals Inc.)	o ○	0.091
2-24	Hydrazine adduct of Amberlite IRC-50 (polymer compound having a hydrazine group) (produced by Rohm & Haas Co.)	o ○	0.090
2-25	Porous Teflon tube (polymer compound having polytetrafluoroethylene)	o ○	0.092
2-26	Amberlite XAD-7 (copolymer of methacrylic acid monoester of monohydric or polyhydric alcohol and methacrylic acid polyester of polyhydric alcohol) (methacrylate resin) (produced by Rohm & Haas Co.)	o ○	0.089
2-27	Amberlite XDA-8 (copolymer of methacrylic acid monoester of monohydric or polyhydric alcohol and methacrylic acid polyester of polyhydric alcohol) (methacrylate resin) (produced by Rohm & Haas Co.)	o ○	0.090
2-28	Amberlite XDA-8 (copolymer of methacrylic acid monoester of monohydric or polyhydric alcohol and methacrylic acid polyester of polyhydric alcohol) (methacrylate resin) (produced by Rohm & Haas Co.)	o ○	0.089

From Table 2, it is evident that stain in the unexposed portion and crystal deposition on the rollers and tank wall in the stabilizing bath are significantly improved by using water-soluble surfactant and bringing into contact ion exchange resin or adsorbent to the stabilizer.

A similar effect was confirmed even when the water-soluble surfactant listed in Table 2 was replaced with Exemplified Compound I-5, 6, 12, 14, 16, 18, 19, II-3, 4, 9, 10, 13 or 14 so that the stabilizer surface tension was 20 dyne/cm.

Example 3

An experiment was carried out in the same manner as in Example 1 except that the adsorbent to be brought into contact with the stabilizer, the water-soluble surfactant added to the stabilizer and the amount of stabilizer replenisher were changed as shown in Table 3.

The results are shown in Table 3.

Experiment number	Water-soluble surfactant	Stabilizer surface tension (dyne/cm)	Adsorbent to be brought into contact with stabilizer (ml/m2)	Amount of stabilizer replenisher	Crystal deposition on the rollers and tank wall in the stabilizing bath	Stain in the unexposed portion at 640 nm
3-1	-	72	-	350	x	0.120
3-2	250	xx	0.133
3-3	150	xx	0.140
3-4	100	xx	0.144
3-5	60	xx	0.148
3-6	-	72	-	350	Δ	0.105
3-7	250	x	0.120
3-8	150	x	0.125
3-9	100	x	0.128
3-10	60	x	0.131
3-11	1-5	20	III-1	350	o ○	0.083
3-12	250	o ○	0.088
3-13	150	o ○	0.090
3-14	100	o ○	0.091
3-15	60	o	0.093
3-16	1-17	20	-	350	o ○	0.084
3-17	250	o ○	0.086
3-18	150	o ○	0.089
3-19	100	o ○	0.091
3-20	60	o	0.092
3-21	II-3	20	-	350	o ○	0.089
3-22	250	o ○	0.093
3-23	150	o ○	0.093
3-24	100	o ○	0.095
3-25	60	o	0.095

From Table 3, it is evident that stain in the unexposed portion and crystal deposition on the rollers and tank wall in the stabilizing bath are significantly improved by adding water-soluble surfactant and bringing an adsorbent into contact with the stabilizer even when the amount of stabilizer replenisher was small.

A similar effect was confirmed even when the water-soluble surfactant listed in Table 3 was replaced with Exemplified Compound I-6, 12, 14, 16, 18, 19, II-4, 9, 10, 13 or 14 so that the stabilizer surface tension was 20 dyne/cm.

Example 4

Figure 4 is a cross-sectional view of a mode of the automatic developing machine for use in the method of the present invention. Figure 2 is a plane view of the automatic developing machine.

In Figure 1, the symbol 1 denotes the main body of the developing machine, in front of which a supply part 4 is furnished to supply an undeveloped color negative light-sensitive material 2 or color positive paper light-sensitive material 3 and in the rear of which a take-out portion 5 is furnished where the processed light-sensitive materials 2 and 3 are taken out.

Between the supply portion 4 and take-out portion 5, i.e., inside the main body of the developing machine 1, there are a developer tank 6, bleacher tank 7, fixer tank 8, stabilizer tanks 9, 10 and 11 and a drying portion 12 in sequential arrangement from the supply portion side to the take-out portion side.

The developer tank 6, bleacher tank 7, fixer tank 8, first stabilizer tanks 9 and 10 and second stabilizer tank 11 are configured as shown in Figure 1. The developer tank 6 is configured with a negative developer tank 6a and a positive developer tank 6b, each of which is filled with a dedicated developer. The negative light-sensitive material 2 and positive light-sensitive material 3 are separately processed in the negative developer tank 6a and positive developer tank 6b, respectively, so that the photographic performance is maximized.

The processing tanks located in the rear of the developer tank 6, i.e., the bleacher tanks 7a and 7b and fixer tanks 8a and 8b are filled with a bleacher and fixer of the same composition, respectively. With respect to the stabilizer tank combinations of 9a, 10a and 11a and 9b and 10b, they may be filled with differently composed stabilizers, and 9a, 10a, 11a, 9b and 10b may all be filled with a stabilizer of the same composition. As stated above, stabilization of the light-sensitive material does not use water but uses the stabilizer, thus requiring no water. In addition, no drain piping is necessary, so there is no limitation as to the site of installation.

As shown in Figure 2, between the first stabilizer tanks 9a and 10a, between 10a and 11a, and between 9b and 10b, there are cascade pipings 14, 15 and 16, respectively, and upon overflow of the replenisher supplied to the stabilizer tank lla or 10b, the overflow enters in the first stabilizer tank 10a, 9a or 9b, which permits recycled use of the stabilizer overflow, thus increasing the stabilization efficiency.

With respect to the color developer replenisher, negative developer and positive developer replenishers with different compositions may be used. With respect to the bleacher replenisher, fixer replenisher and stabilizer replenisher, a single replenisher may be used commonly for negative and positive development.

The following layers with the compositions shown below were sequentially formed on a triacetyl cellulose film support in the order from the support side to yield a color negative film sample No. 1

Layer 1: Anti-halation layer HC
Black colloidal silver	0.15
UV absorbent UV-1	0.20
Colored cyan coupler CC-1	0.02
High boiling solvent Oil-1	0.20
High boiling solvent Oil-2	0.20
Gelatin	1.6

Layer 2: Interlayer IL-1
Gelatin	1.3

Layer 3: Low speed red-sensitive emulsion layer RL
Silver iodobromide emulsion Em-1	0.4
Silver iodobromide emulsion Em-2	0.3
Sensitizing dye S-1	3.2 x 10-4 mol/mol silver
Sensitizing dye S-2	3.2 x 10-4 mol/mol silver
Sensitizing dye S-3	0.2 x 10-4 mol/mol silver
Cyan coupler C-1	0.50
Cyan coupler C-2	0.13
Colored cyan coupler CC-1	0.07
DIR compound D-1	0.006
DIR compound D-2	0.01
High boiling solvent Oil-1	0.55
Additive SC-1	0.003
Gelatin	1.0

Layer 4: High speed red-sensitive emulsion layer RH
Silver iodobromide emulsion Em-3	0.9
Sensitizing dye S-1	1.7 x 10-4 mol/mol silver
Sensitizing dye S-2	1.6 x 10-4 mol/mol silver
Sensitizing dye S-3	0.1 x 10-4 mol/mol silver
Cyan coupler C-2	0.23
Colored cyan coupler CC-1	0.03
DIR compound D-2	0.02
High boiling solvent Oil-1	0.25
Additive SC-1	0.003
Gelatin	0.1

Layer 5: Interlayer IL-2
Gelatin	0.8

Layer 6: Low speed green-sensitive emulsion layer GL
Silver iodobromide emulsion Em-1	0.6
Silver iodobromide emulsion Em-2	0.2
Sensitizing dye S-4	6.7 x 10-4 mol/mol silver
Sensitizing dye S-5	0.8 x 10-4 mol/mol silver
Magenta coupler M-1	0.17
Magenta coupler M-2	0.43
Colored magenta coupler CM-1	0.10
DIR compound D-3	0.02
High boiling solvent Oil-2	0.70
Additive SC-1	0.003
Gelatin	1.0

Layer 7: High speed green-sensitive emulsion layer GH
Silver iodobromide emulsion Em-3	0.9
Sensitizing dye S-6	1.1 x 10-4 mol/mol silver
Sensitizing dye S-7	2.0 x 10-4 mol/mol silver
Sensitizing dye S-8	0.3 x 10-4 mol/mol silver
Magenta coupler M-l	0.03
Magenta coupler M-2	0.13
Colored magenta coupler CM-1	0.04
DIR compound D-3	0.004
High boiling solvent Oil-2	0.35
Additive SC-1	0.003
Gelatin	1.0

Layer 8: Yellow filter layer YC
Yellow colloidal silver	0.1
Additive HS-1	0.07
Additive HS-2	0.07
Additive SC-2	0.12
High boiling solvent Oil-2	0.15
Gelatin	1.0

Layer 9 Low speed blue-sensitive emulsion layer BL
Silver iodobromide emulsion Em-1	0.25
Silver iodobromide emulsion Em-2	0.25
Sensitizing dye S-9	5.8 x 10-4 mol/mol silver
Yellow coupler Y-1	0.60
Yellow coupler Y-2	0.32
DIR compound D-1	0.003
DIR compound D-2	0.006
High boiling solvent Oil-2	0.18
Additive SC-1	0.004
Gelatin	1.3

Layer 10: High speed blue-sensitive emulsion layer BH
Silver iodobromide emulsion Em-4	0.5
Sensitizing dye S-10	3.0 x 10-4 mol/mol silver
Sensitizing dye S-11	1.2 x 10-4 mol/mol silver
yellow coupler Y-1	0.18
yellow coupler Y-2	0.10
High boiling solvent Oil-2	0.05
Additive SC-1	0.002
Gelatin	1.0

Layer 11: First protective layer PRO-1
Silver iodobromide emulsion Em-5	0.3
UV absorbent UV-1	0.07
UV absorbent UV-2	0.1
Additive HS-1	0.2
Additive HS-2	0.1
High boiling solvent Oil-1	0.07
High boiling solvent Oil-3	0.07
Gelatin	0.8

Layer 12: Second protective layer PRO-2
Alkali-soluble matting agent (average grain size 2 µm)	0.13
Polymethyl methacrylate (average grain size 3 µm)	0.02
Lubricant WAX-1	0.04
Charge controlling agent SU-1	0.004
Charge controlling agent SU-2	0.02
Gelatin	0.5

In addition to these compositions, a coating aid SU-4, a dispersing agent SU-3, hardeners H-1 and H-2, a stabilizer ST-1, a preservative D1-1, antifogging agents AF-1 and AF-2 and dyes AI-1 and AI-2 were added to appropriate layers.

The emulsions used to prepare the sample described above are as follows, all of which are monodispersed emulsions having a high inside iodide content.

Em-1

Octahedral grains having an average AgI content of 7.5 mol% and an average grain size of 0.55 µm.

Em-2

Octahedral grains having an average AgI content of 2.5 mol% and an average grain size of 0.36 µm.

Em-3

Octahedral grains having an average AgI content of 8.0 mol% and an average grain size of 0.84 µm.

Em-4

Octahedral grains having an average AgI content of 8.5 mol% and an average grain size of 1.02 µm.

Em-5

Octahedral grains having an average AgI content of 2.0 mol% and an average grain size of 0.08 µm.

H - 2    [(CH₂=CHSO₂CH₂)₃CCH₂SO₂(CH₂)₂]₂N(CH₂)₂SO₃K

The color films thus prepared and the color paper sample used in Example 1 were subjected to exposure by a conventional method and then processed as follows:

(Color negative processing)
Procedure	Processing time	Processing temperature	Amount of replenisher
Color development
	3 minutes 15 seconds	38°C	750 mℓ
Bleaching	45 seconds	38°C	190 mℓ
Fixation	90 seconds	38°C	750 mℓ
Stabilization (3-tank cascade)	1 minute	38°C	750 mℓ
Drying
	1 minute
(Figures for the amount of replenisher are values per m2 of light-sensitive material.)

(Color paper processing)
Procedure	Processing time	Processing temperature	Amount of replenisher
Color development	20 seconds	38°C	60 ml
Bleaching	20 seconds	35°C	30 ml
Fixation	20 seconds	35°C	60 ml
Stabilization (2-tank cascade)	40 seconds	35°C	100 ml
Drying	30 seconds	60 to 80°C	-
(Figures for the amount of replenisher are values per m2 of light-sensitive material.)

Color developer tank solution for color negative films
Potassium carbonate	30 g
Sodium hydrogen carbonate	2.5 g
Potassium sulfite	3.0 g
Sodium bromide	1.2 g
Potassium iodide	0.6 mg
Hydroxylamine sulfate	2.5 g
Sodium chloride	0.6 g
4-amino-3-methyl-N-ethyl-N-(β-hydroxylethyl)aniline sulfate	4.6 g
Diethylenetriaminepentaacetic acid	3.0 g
Potassium hydroxide	1.2 g

Water was added to make a total quantity of 1 ℓ, and potassium hydroxide or 20% sulfuric acid was added to obtain a pH of 10.01.

Color developer replenisher for color negative films
Potassium carbonate	40 g
Sodium hydrogen carbonate	3.0 g
Potassium sulfite	7.0 g
Sodium bromide	0.5 g
Hydroxylamine sulfate	3.1 g
Sodium chloride	0.6 g
4-amino-3-methyl-N-ethyl-N-(β-hydroxylethyl)aniline sulfate	6.0 g
Diethylenetriaminepentaacetic acid	3.0 g
Potassium hydroxide	2.0 g

Water was added to make a total quantity of 1 ℓ, and potassium hydroxide or 20% sulfuric acid was added to obtain a pH of 10.12.

Color developer tank solution for color paper
Diethylene glycol	10 g
Potassium bromide	0.01 g
Potassium chloride	2.3 g
Potassium sulfite (50% solution)	0.5 mℓ
Color developing agent 3-methyl-4-amino-N-ethyl-N-(β-methanesulfonamidoethyl)-aniline sulfate	7.0 g
Diethylhydroxylamine (85%)	5.0 g
Triethanolamine	10.0 g
Potassium carbonate	30 g
Sodium diethylenetriaminepentaacetate	2.0 g
Fluorescent brightening agent (Uvitex CK, produced by Ciba Geigy)	2.0 g

Water was added to make a total quantity of 1 ℓ, and potassium hydroxide or sulfuric acid was added to obtain a pH of 10.15.

Color developer replenisher for color paper
Diethylene glycol	10 g
Potassium chloride	3.0 g
Potassium sulfite (50% solution)	0.5 mℓ
Color developing agent
3-methyl-4-amino-N-ethyl-N-(β-methanesulfonamidoethyl)-aniline sulfate	8.0 g
Diethylhydroxylamine (85%)	7.0 g
Triethanolamine	10.0 g
Potassium carbonate	30 g
Sodium diethylenetriaminepentaacetate	2.0 g
Fluorescent brightening agent (Uvitex CK, produced by Ciba Geigy)	2.5 g

Water was added to make a total quantity of 1 ℓ, and potassium hydroxide or sulfuric acid was added to obtain a pH of 10.40.

Bleacher tank solution
Ferric ammonium 1,3-propylenediaminetetraacetate mol	0.32
Disodium ethylenediaminetetraacetate	10 g
Ammonium bromide	100 g
Glacial acetic acid	40 g
Ammonium nitrate	40 g

Water was added to make a total quantity of 1 ℓ, and aqueous ammonia was added to obtain a pH of 4.5.

Bleacher replenisher
Ferric ammonium
1,3-propylenediaminetetraacetate mol	0.35
Disodium ethylenediaminetetraacetate	2 g
Ammonium bromide	120 g
Glacial acetic acid	68.9 g
Ammonium nitrate	80 g

Water was added to make a total quantity of 1 ℓ, and aqueous ammonia was added to obtain a pH of 3.5.

Fixer tank solution and fixer replenisher
Ammonium thiosulfate	180 g
Ammonium sulfite	20 g
Urea	1 g
Imidazole	4 g
Disodium ethylenediaminetetraacetate	1 g
Ammonium thiocyanate	150 g

Water was added to make a total quantity of 1 ℓ, and aqueous ammonia was added to obtain a pH of 7.5.

Stabilizer tank solution and stabilizer replenisher
1,2-benzothiazolin-3-one	0.2 g

Water-soluble surfactant added in an amount shown in Table 4

Water was added to make a total quantity of 1 ℓ, and aqueous ammonia or 50% sulfuric acid was added to obtain a pH of 7.0.

The processing solutions thus obtained were added to the automatic developing machine illustrated in Figures 1 and 2. To bring the stabilizer into contact with ion exchange resin or absorbent in the stabilizing bath for paper (9b and 10b in figures 1 and 2), the filter portion of the stabilizing bath was equipped with a small bag, like a tea bag, containing ion exchange resin or adsorbent, and continuous running processing was carried out at a daily processing rate of 2.0 m² for the color negative film and 12 m² for the color paper for 30 days.

The method was also tested in which the overflow from the stabilizer for negative films is allowed to enter in the stabilizer for paper via the cascade piping 13 shown in Figure 2.

After completion of the continuous processing, the spectral reflective density at 640 nm in the unexposed portion was determined and the stain was evaluated. Also evaluated was crystal deposition on the rollers and tank wall in the stabilizing bath for paper using the evaluation criteria shown below. The results are given in Table 4.

o ○:

No deposition on the rollers or tank wall.

○:

Slight deposition on the rollers and tank wall.

Δ:

Small amount of deposition on the rollers and tank wall.

x:

Much deposition on the rollers and tank wall.

xx:

Much deposition on the rollers and tank wall, with precipitation on the tank bottom.

From Table 4, it is evident that stain in the unexposed portion and crystal deposition on the rollers and tank wall in the stabilizing bath are significantly improved by adding an appropriate amount of the water-soluble surfactant used in the present invention to the stabilizer so that the stabilizer surface tension becomes not more than 60 dyne/cm, bringing an ion exchange resin or adsorbent into contact with the stabilizer and allowing the overflow from the stabilizing bath for negative films to enter in the stabilizing bath for paper.

A similar effect was confirmed when the water-soluble surfactant used above was replaced with Exemplified Compound I-6, 12, 14, 15, 16, 18, 19, II-4, 9, 10, 13 or 14.

Example 5

An experiment was carried out in the same manner as in Example 4 except that the ion exchange resin or adsorbent described in Example 2 was brought into contact with the stabilizer for paper, and the obtained sample was evaluated with respect to stain in the unexposed portion of paper and crystal deposition on the rollers and tank wall in the stabilizing bath. Good results were obtained like in Example 3.

Example 6

An experiment was carried out in the same manner as in Example 4 except that the water soluble surfactant to be added to the stabilizer and the amount of stabilizer replenisher for paper processing were changed as shown in Table 5, and the obtained sample was evaluated with respect to stain in the unexposed portion and crystal deposition on the rollers and tank wall in the stabilizing bath. The results are given in Table 5.

From Table 5, it is evident that stain in the unexposed portion and crystal deposition on the rollers and tank wall in the stabilizing bath are significantly improved by adding water-soluble surfactant to the stabilizer, bringing an ion exchange resin into contact with the stabilizer for paper and allowing the overflow from the stabilizing bath for negative films to enter in the stabilizing bath for paper even when the amount of stabilizer replenisher for paper processing is small.

The present invention has provided a silver halide color photographic light-sensitive material processing method which prevents stain attributable to residual pigments and dyes in color printing paper and crystal deposition on the processing tanks and rollers and which permits rapid processing and reduction in the amount of replenisher.

Claims (7)

1. A method of processing a silver halide colour photographic light-sensitive material comprising a support having coated thereon a silver halide emulsion containing silver halide grains having an average silver chloride content of not less than 80 mol% of silver chloride to total silver halide comprising steps of:

   developing, bleaching, fixing and stabilizing the material in a stabilizing bath, wherein

   a stabilizing solution contained in the stabilizing bath having a surface tension of from 15 to 60 dyne/cm, comprises a surface active agent, and an ion exchange resin or an adsorbent being brought into contact with the stabilizing solution in the stabilizing bath, wherein the surface active agent is represented by formula I or II,

   

   wherein R represents a hydrogen atom, a linear or branched alkyl group having a carbon number of from 4 to 25 which may have a substituent, or

   

   wherein R₁ and R₂ independently represent a hydrogen atom or an alkyl group having a carbon number of from 1 to 20 which may have a substituent, 1 represents from 0 to 4,

   n and m independently represent from 0 to 200, but are not 0 concurrently; A and B, which may be the same or different, independently represent

   

   wherein n₁, m₁, and l₁, independently represent 0, 1, 2 or 3, and n₁, m₁ and l₁, are not 0 concurrently; D represents a hydrogen atom or -SO₃M or -PO₃M group, wherein M represents a hydrogen atom, alkali metal or ammonium;

   

   wherein R₃ represents a hydrogen atom, hydroxyl group, lower alkyl group, alkoxy group,

   

   R₄, R₅ and R₆, which may be the same or different, independently represent a lower alkyl group, having a carbon number of from 1 to 3; l₁, l₂, l₃ independently represent from 0 to 4; and p, q₁ and q₂ independently represent from 1 to 15.
2. A method according to claim 1, wherein a replenishing solution to the stabilizing solution is a part or the whole of the overflowing solution from a bath having a stabilizing solution used for processing a different kind of silver halide colour photographic material which has a silver iodide content of more than 2 mol %.
3. A method according to any of claims 1 or 2, wherein the ion exchange resin is an anion exchanger.
4. A method according to claim 3, wherein the anion exchanger is represented by formula III,

   

   wherein A represents a monomer having more than two ethylene radicals which are capable of copolymerizing and at least one of which radicals forms a branch, B represents an ethylene group monomer which is capable of copolymerizing, R₁₃ represents a hydrogen atom, lower alkyl group, or aralkyl group,

   Q represents a single bond, alkylene, phenylene, aralkylene,

   

   wherein L represents an alkylene, arylene, or aralkylene group, R is an aralkyl group,

   G represents

   

   wherein R₁₄, R₁₅, R₁₆, R₁₇, R₁₈, R₁₉, R₂₀ and R₂₁, which may be the same or different each independently represents a hydrogen atom, or an optionally substituted alkyl, aryl, or aralkyl group, and X is a negative ion;

   more than two groups of Q, R₁₄, R₁₅, R₁₆, or Q, R_17' R₁₈, R₁₉, R₂₀ and R₂₁, may form a heterocyclic group with a nitrogen atom;

   x, y and z indicate mol percent, x is from 0 to 60, y is from 0 to 60 and z is from 30 to 100.
5. A method according to claim 3, wherein the anion exchanger is represented by formula IV,

   

   wherein A, B, x, y, z, R₁₃, R₁₄, R₁₅, R₁₆, X^- are as defined for Formula III.
6. A method according to any preceding claim, wherein the adsorbent is an activated charcoal, a clay substance, a polyamide polymer compound, a polyurethane polymer compound, a phenol resin, a polymer compound having a hydrazide group, or a polymer compound having polytetrafluoroethylene; or a copolymer of methacrylic acid monoester of monohydric or polyhydric alcohol and methacrylic acid polyester of polyhydric alcohol.
7. A method according to claim 6, wherein the adsorbent is an activated charcoal, or a polymer compound having polytetrafluoroethylene; or a copolymer of methacrylic acid monoester of monohydric or polyhydric alcohol and methacrylic acid polyester of polyhydric alcohol.

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