EP0217643B1

EP0217643B1 - Method for processing light-sensitive silver halide color photographic material

Info

Publication number: EP0217643B1
Application number: EP86307394A
Authority: EP
Inventors: Masayuki Kurematsu; Shigeharu Koboshi
Original assignee: Konica Minolta Inc
Current assignee: Konica Minolta Inc
Priority date: 1985-09-27
Filing date: 1986-09-25
Publication date: 1991-01-23
Anticipated expiration: 2006-09-25
Also published as: KR940002541B1; EP0217643A2; AU6309786A; EP0217643A3; JPS6275451A; DE3677120D1; AU596118B2; KR870003404A; CA1294814C

Description

This invention relates to a method for processing of a light-sensitive silver halide color photographic material (hereinafter called light-sensitive material) in which a water washing processing step is omitted, more particularly to a processing method without water washing of a light-sensitive material in which stain generation at an unexposed portion by continuous processing is substantially prevented.
Generally speaking, light-sensitive materials, after imagewise exposure, are processed according to processing steps such as color developing, bleaching, fixing, stabilizing, bleach-fixing, water washing, etc. In such processing steps, the increased cost for water washing due to exhaustion of water resources, and the rise in price of crude oil are becoming an increasingly serious problem.
For this reason, to omit the water washing processing step or to reduce significantly the amount of washing water, there have been proposed the multi-stage countercurrent stabilising processing technique as disclosed in Japanese Provisional Patent Publication No. 8543/1982 and the processing technique with a stabilizing solution substituting for water washing containing a bismuth complex as disclosed in Japanese Provisional Patent Publication No. 134636/1983.
However, in such processing with a stabilizing solution substituting for water washing, when continuous processing is continued for such a long term that the total amount of the supplementing solution relative to the stabilizing tank solution becomes 6 to 7 times or more the stabilizing tank volume, we have been found that color contamination is generated in the processed light-sensitive material which becomes conspicuous as stain. In particular, color contamination, namely stain, is conspicuous at an unexposed portion and, particularly in color paper, there is the problem that even a slight contamination may become a vital defect because the unexposed portion is white ground.
Also, it has been found that generation of such a stain worsens the storage durability particularly when the dye image is stored with irradiation of light.
Japanese Application No. 58189634 discloses a silver halide photosensitive material which contains a specific phenolic cyan coupler which possesses a substituted or condensed 4-cyanophenylureido group at the 2-position and a ballasting acylamino group at the 5-position. This material is imagewise exposed and developed with a color developing solution containing no benzyl alcohol.
Accordingly, an object of the present invention is to provide a method for processing in which contamination at the unexposed portion of a light-sensitive material generated in the case of continuous processing by use of a stabilizing solution substituting for water washing is largely prevented without a deterioration in storage stability, particularly deterioration of the light fading characteristic of the dye image.
As a result of extensive studies we have found, according to the present invention that this can be accomplished by a method for processing a light-sensitive silver halide color photographic material, which comprises subjecting a light-sensitive silver halide color photographic material having a total dried film thickness of the light-sensitive silver halide emulsion layers and the non-light-sensitive layers on one surface of a support of 10 µm or more, to imagewise exposure, then processing the expose material with a color forming developing solution containing at most 1 ml/l of benzyl alcohol, thereafter processing the material with a processing solution having fixing ability and subsequently for water washing having a surface tension of 8 to 50 dyne/cm (mN/m) at 20°C and containing at most 0.1 g/l of aldehyde compound, followed by drying.
The present inventors have also found that the effect of the present invention is more marked when the light-sensitive material contains a sensitizing dye represented by the formula (I) shown below:

wherein each of Z₁ and Z₂ independently represents a group of atoms to complete a benzoxazole
nucleus, naphthoxazole nucleus, benzothiazole
nucleus, naphthothiazole nucleus, benzoselenazole
nucleus, naphthoselenazole nucleus, benzoimidazole
nucleus, naphthoimidazole nucleus, pyridine nucleux
or quinoline nucleus, each of R₁ and R₂ independently represents an alkyl group, an alkenyl group or an aryl group, R₃ represents a hydrogen atom, a methyl group or an ethyl group and X₁^⊖ represents an anion and ℓ represents 0 or 1.
In the water washing processing step after developing, bleaching and fixing processing of the prior art, all of the emulsion compositions and processing solution compositions (including color developing agent, benzyl alcohol, bleaching agent, thiosulfate, etc.) or their reaction products oxodized materials, etc., are washed away from within the light-sensitive material and the surface of the light-sensitive material with a large amount of washing water. Accordingly, in the processing with a stabilizing solution which eliminates water washing processing, all of these components are dissolved out in the stabilizing solution and accumulate therein. Particularly, when the amount of the stabilizing solution supplemented is small, the accumulated concentration of the above materials be to washed is increased. Further, the stabilizing solution substitution for water washing will be stored over a long time due a reduction in the rate of renewal thereof, and the stabilizing solution is considerably colored due to the coloring components of the above substances in it. Accordingly, it may be estimated that these coloring components are adsorbed onto the light-sensitive material in the stabilizing solution substituting for water washing, or washing-out from the light-sensitive material is inhibited, whereby the unexposed portion of the light-sensitive material becomes stained.
Benzyl alcohol has been used for a long time in a color developing solution generally as a developing accelerator. Also, it is well known in the art that formalin which is an aldehyde compound has been used in the final stabilizing solution for the purpose of image stability in the final step of conventional color processing steps.
However, it is surprising that the above problem inherent in the stabilizing solution substituting for water washing can be solved by carrying out a combination of processings in which a light-sensitve material with a dried film thickness of 10 µm or more is subjected to color developing with a color developing solution containing substantially no benzyl alcohol, then processing the material with a processing solution having a fixing ability and further processing the material with a stabilizing solution substituting for water washing having a surface tension of 8 to 50 dyne/cm (mN/m) at 20°C and containing substantially no aldehyde compound. Further, it has been found that the present invention is very effective for light-sensitive material containing a sensitizing dye represented by the above formula (I).
In the present invention, processing with a processing solution having fixing ability after color developing refers to the step of using a fixing bath or a bleach-fixing bath for the purpose of fixing the light-sensitive material after processing with a conventional color developing solution. That is, the present invention has solved the problem with the stabilizing solution substituting for water washing after a processing in a bleaching bath _ fixing bath or a bleach-fixing bath after color developing. The present invention is particularly effective for the latter, namely processing in a bleach-fixing bath.
In the present invention, the color developing solution containing substantially no benzyl alcohol refers to a color developing solution containing benzyl alcohol in such an amount that the color developing solution has substantially no developing accelerating effect. This means that the color developing solution contains benzyl alcohol in an amount of 1 mℓ or less, especially 0.1 ml or less, per liter of the color developing solution, and more preferably it contains no benzyl alcohol.
In the present invention, when reference is made to the use of a processing solution having fixing ability and subsequently processing is conducted with a stabilizing solution substituting for water washing without substantial water washing, it indicates processing directly with the stabilizing solution following a fixing bath or a bleach-fixing bath ; this processing step is entirely different from the step known in the art in which water washing processing and then processing with a stabilizing solution are performed after a fixing bath or a bleach-fixing bath.
Thus, in the present invention, processing with a stabilizing solution substituting for water washing refers to a processing for stabilizing processing in which stabilizing processing is performed without substantial water washing processing, or without using flowing water immediately after processing with a processing solution having fixing ability. That is, while a large amount of water is required for conventional water washing using flowing or running water which is led into a processing machine, in the present invention, since the stabilizing solution substituting for water washing may be a stabilizing solution or water placed in a processing machine, its amount is extremely small. In the present invention, the processing solution used for said stabilizing processing is called "the stabilizing solution substituting for water washing" (or stabilizing solution for short) and the processing tank is called "a stabilizing bath" or "a stabilizing tank".
In the present invention, the effect of the present invention is great when the stabilizing solution is in 1 to 5 tanks, particularly preferably 1 to 3 tanks. That is, with the same amount of supplementing solution, the effect of the present invention becomes reduced as the number of tanks is increased, because the concentration of contaminating components in the final stabilizing tank is reduced.
The surface tension of the stabilizing solution substituting for water washing used in the processing of the present invention is measured according to the general measuring method as described in "Analysis and test Method of Surfactants" (written by Fumio Kitahara, Shigeo Hayano and Ichiro Hara, published by Kodansha K.K., March 1, 1982), in the present invention, the surface tension in the value measured according to the conventional general measuring method at 20°C.
The stabilizing solution of the present invention may contain any compound which can give a surface tension of 8 to 50 dyne/cm (mN/m) (20°C), but it is particularly preferable to use at least one compound selected from the compounds of the following formula (II), formula (III) and water-soluble organic siloxane type compounds,
In the above formula, A is a monovalent organic group, for example an alkyl group having 6 to 20, preferably 6 to 12, carbon atoms such as hexyl, heptyl, octyl, nonyl, decyl, undecyl or dodecyl. Alternatively, it may be an aryl group substituted with an alkyl group having 3 to 20 carbon atoms, and the substituent is preferably an alkyl group having 3 to 12 carbon atoms such as propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl or dodecyl. The aryl group may be, 29, phenyl, tolyl, xylyl, biphenyl or naphthyl, preferably phenyl or tolyl. The position at which the alkyl group is bonded to the aryl group may be either ortho-, meta-or para-position. B represents an ethylene oxide or propylene oxide mit, and m represents an integer of 4 to 50. X₂ represents a hydrogen atom, SO₃Y or PO₃Y₂, and Y represents a hydrogen atom, an alkali metal (eq. Na, K or Li) or an ammonium ion.
In the above formula, each of R₄, R₅, R₆ and R₇ represents a hydrogen atom, an alkyl group or a phenyl group, and the total number of carbon atom of R₄, R₅, R₆ and R₇ is 3 to 50. X₃ represents an anion such as a halogen atom, a hydroxyl group, a sulfate group, a carbonate group, a nitrate group, an acetate group or a p-toluenesulfonate group.
The water-soluble organic siloxane type compounds used in the present invention may be water-soluble organic siloxane type compounds as described in, for example, Japanese Provisional Patent Publication No. 18333/1972, Japanese Patent Publication No. 51172/1980, Japanese Patent Publication No. 37538/1976, Japanese Provisional Patent Publication No. 62128/1974 and U.S. Patent No. 3,545,970.
In the following, typical examples of the compounds represented by the formulae (II), (III) and water-soluble organic siloxane type compounds are set forth, but the present invention is not limited thereto.
Examples of compounds represented by the formula (II)
II-1 C₁₂H₂₅O(C₂H₄O)₁₀H
II-2 C₈H₁₇O(C₃H₆O)₁₅H
II-3 C₉H₁₉O(C₂H₄O)₄SO₃Na
II-4 C₁₀H₂₁O(C₂H₄O)₁₅PO₃Na₂
Examples of compounds represented by the formula (III)
Water-soluble organic siloxane type compounds
Of the above water-soluble organic siloxane type compounds, the compounds represented by the formula (IV) shown below are more preferably used, since they can exhibit well the effects of the present invention.
In the above formula, R₈ represents a hydrogen atom, a hydroxy group a lower alkyl group, an alkoxy group,

Each of R₉, R₁₀ and R₁₁ represents a lower alkyl group (preferably an alkyl group having 1 to 3 carbon atoms such as methyl, ethyl or propyl) and the above R₉, R₁₀ and R₁₁ may be either the same or different. n represents an integer of 1 to 4, and each of p and q represents an integer of 1 to 15.
In the present invention, of the compounds capable of giving a surface tension of 8 to 50 dyne/cm to the stabilizing solution, those capable of giving a surface tension of 15 to 40 dyne/cm are particularly preferred.
The compounds represented by the above formulae (II), (III) and water-soluble organic siloxane type compounds may be used either individually or as a combination. Further, the amounts used are typically within the range of from 0.01 to 20 g per 1 ℓ of the stabilizing solution to exhibit a good effect.
In the present invention, the stabilizing solution substituting for water washing contains 0.1 g/ℓ or less of the aldehyde which may have been added at a concentration of 1.5 to 2.0 g/ℓ for the purpose of improvement in storability of the dye image into the final stabilizing solution in the processing step accompanying water washing of the prior art. A concentration of about 0.02 g/ℓ can be regarded as substantially no aldehyde, but it is particularly preferred for there to be no aldehyde at all.
As the aldehyde to be used in the stabilizing bath in the processing step of the prior art, formaldehyde has been extensively used; other examples of aldehyde include glutaraldehyde, chloral, mucochloric acid, formaldehyde sodium bisulfite and glutaraldehyde sodium bisbisulfite; they will not only deteriorate the storability of the dye image but also give troubles such as precipitation formation in the stabilizing solution substituting for water washing of the present invention.
In the sensitizing dye represented by the above formula (I) which can be used in the present invention, the nucleus represented by Z₁ and Z₂ may be substituted, and examples of the substituent include halogen atoms, (e.g. chlorine) alkyl groups (e.g. methyl, ethyl) alkoxy groups (e.g. methoxy, ethoxy), alkoxycarbonyl groups (e.g. methoxycarbonyl, ethoxycarbonyl), aryl groups (e.g. phenyl) cyano group, etc.
The alkyl group and the alkenyl group represented by R₁ and R₂ may preferably have 5 or less carbon atoms, and R₁ and R₂ may preferably be alkyl goups
Specific compounds of the sensitizing dyes represented by the formula [I] are shown below.
The amount of the sensitizing dye reprsented by the above formula (I) added in the emulsion is suitably within the range of from 2 × 10^-6 to 1 × 10^-3 mole preferably from 5 × 10^-6 to 5 × 10^-4 mole per mole of silver halide.
Most of the above sensitizing dyes are sensitizing dyes having spectral sensitizing ability at the wavelength region which is called green-sensitive or blue-sensitive, and the light-sensitive material to be used in the present invention should desirably be spectrally sensitized with the above sensitizing dye within the limit afforded by spectral sensitizing ability ; it is preferred that the sensitizing dye in the sum of green-sensitive emulsion and the blue-sensitive emulsion represents the greater part (50 mole% or more) of the sensitizing dye.
It is preferable to incorporate a mildewproofing (fungicidal) agent in the stabilizing solution used in the present invention. Examples of mildewproofing agents preferably used are salicylic acid, sorbic acid, dehydroacetic acid, hydroxy benzoic acid type compounds, alkylphenol type compounds, thiazole type compounds, pyridine type compounds, guanidine type compounds, carbamate type compounds, morpholine type compounds, quaternary phosphonium type compounds, ammonium type compounds, urea type compounds, isoxazole type compounds, propanolamine type compounds, sulfamide derivatives and amino acid type compounds.
Examples of the above hydroxybenzoic acid type compounds include hydroxybenzoic acid and esters of hydroxybenzoic acid such as methyl ester, ethyl ester, propyl ester and butyl ester, preferably n-butyl ester, isobutyl ester and propyl ester of hydroxybenzoic acid, more preferably a mixture of the aforesaid three hydroxybenzoic acid esters.
The alkylphenol type compounds are compounds in which the alkyl group has, as the substituent, an alkyl group having 1 to 6 carbon atoms, preferably orthophenylphenol and ortho-cyclohexylphenol.
The thiazole type compound is preferably 1,2-benzisothiazolin-3-one, 2-methyl-4-isothiazolin-3-one, 2-octyl-4-isothiazolin-3-one, 5-chloro-2-methyl-4-isothiazolin-3-one or (2-(4-thiazolyl)-benzimidazole.
Specific examples of the pyridine compounds include 2,6-dimethylpyridine, 2,4,6-trimethylpyridine and sodium-2-pyridinethiol-1-oxide, preferably sodium-2-pyridinethiol-1-oxide.
The guanidine type compounds may be specifically cyclohexidine polyhexamethylenebiguanidine hydrochloride and dodecylguanidine hydrochloride, preferably dodecylguanidine and salts thereof.
The carbamate type compounds may be exemplified by methyl-1-(butylcabomoyl)-2-benzimidazolecarbamate and methylimidazolecarbamate.
Typical examples of the morpholine type compounds are 4-(2-nitrobutyl)morpholine and 4-(3-nitrobutyl)morpholine.
The quaternary phosphonium type compounds include tetraalkylphosphonium salt and tetraalkoxyphosphonium salt, preferably tetraalkylphosphonium salt, more preferably tributyl·tetradecylphosphonium chloride and triphenyl·nitrophenylphosphonium chloride.
Specific examples of the quaternary ammonium compounds include benzalkonium salt, benzetonium salt, tetraalkylammonium salt and alkylpyridinium salt, more specifically dodecyldimethylbenzylammonium chloride, dodecyldimethylammonium chloride and laurylpyridinium chloride.
Urea type compounds may be exemplified by N-(3,4-dichlorophenyl)-Nʹ-(4-chlorophenyl) urea and N-(3-trifluoromethyl-4-clorophenyl)-Nʹ-(4-chlorophenyl) urea.
A typical example of the isoxazole type compound is 3-hydroxy-5-methyl-isoxazole.
The propanolamine type compounds include amino n-propanols and isopropanols, specifically DL-2-benzylamino-1-propanol, 3-diethylamino-1-propanol, 2-dimethylamino-2-methyl-1-propanol, 3-amino-1-propanol, isopropanolamine, diisopropanolamine and N,N-dimethylisopropanol-amine.
Specific examples of the sulfamide derivatives include fluorinated sulfamide, 4-chloro-3,5-dinitrobenzenesulfamide sulfanylamide, acetosulfamine sulfapyridine, sulfaguanidine, sulfathiazole, sulfadiadine, sulfameladine, sulfamethadine, sulfaisooxazole homosulfamine, sulfisomidine, sulfaguanidine, sulfametizole, sulfapyrazine, phthalisosulfathiazole and succinylsufathiazole.
A typical example of the amino acid type compound is N-lauryl-β-alanine.
Of the above mildewproofing agents, the compounds preferably used in the present invention are pyridine type compounds, guanidine type compounds and quaternary ammonium type compounds.
The amount of the antifungal agent added in the stabilizing solution is typically from 0.002 g to 50 g, preferably from 0.005 to 10 g, per 1 ℓ of the stabilizing solution substituting for water washing.
The pH of the stabilizing solution substituting for water washing hard in the present invention, in order to accomplish more effectively the present invention, is preferably from 3.0 to 10.0, more preferably from 5.0 to 9.5, particularly preferably form 6.0 to 9.0. As the pH adjustor which can be present in the stabilizing solution substituting for water washing of the present invention, there may be employed any of the alkali agents or acid agents generally known in the art.
The present invention can exhibit great effect when the amount of the stabilizing solution added to the stabilizing bath is small, and it is preferred that said supplementd amount should be within the range of from 1 to 50 times the amount brought in from the previous bath per unit area of the light-sensitive material to be processed; the effect of the present invention is particularly marked when said amount is within the range of from 2 to 20 times.
The processing temperature for the stabilizing processing is typically 15°C to 60°C, preferably 20°C to 45°C. The processing time is preferably as short as possible from the standpoint of rapide processing, but is generally 20 seconds to 10 minutes, most preferably 1 minute to 3 minutes. In the cas of the stabilizing preferred that the processing time should be shorter for earlier stage tanks and longer for later stage tanks. Particularly it is desirable that processing should be successively performed in a processing time increased by 20 % to 50 % as compared with that in the tank of the preceding stage.
The method for feeding the stabilizing solution substituting for water washing in the stabilizing processing step according to the present invention, when a multi-tank countercurrent system is used, is preferably to feed the solution to the later bath and permit it to overflow to the earlier bath. Of course, it is possible to perform processing in a single tank. The above compounds can be added according to any desired addition method. For example, they can be added into the stabilizing solution as a concentrated solution. Alternatively the above compounds and other additives may be added to the stabilizing solution substituting for water washing to be fed into the stabilizing tank and this is used as the feed solution for supplementing the stabilizing solution substituting for water washing.
The bleaching solution or bleach-fixing solution to be used in the present invention should preferably contain an organic acid ferric complex salt as the bleaching agent.
The organic acid for forming the organic acid ferric complex salt includes those set forth below.

(1) Diethylenetriaminepentaacetic acid (MW = 393.27)
(2) Diethylenetriaminepentamethylenephosphonic acid (MW = 573.12)
(3) Cyclohexanediaminotetraacetic acid (MW = 364.35)
(4) Cyclohexanediaminetetramethylenephosphonic acid (MW = 488.0)
(5) Triethylenetetraminehexaacetic acid (MW = 494.45)
(6) Triethylenetetraminehexamethylenephosphonic acid (MW = 710.72)
(7) Glycoletherdiaminetetraacetic acid (MW = 380.35)
(8) Glycoletherdiamine etramethylenephosphonic acid (MW = 524.23)
(9) 1,2-diaminopropanetetraacetic acid (MW = 306.27)
(10) 1,2-diaminopropanetetramethylenephosphonic acid (MW = 450.15)
(11) 1,3-diaminopropane-2-ol-tetraacetic acid (MW = 322.27)
(12) 13-diaminopropane-2-ol-tetramethylenephosphonic acid (MW = 466.15)
(13) Ethylenediaminediorthohydroxyphenylacetic acid (MW = 360.37)
(14) Ethylenediaminediorthohydroxyphenylmethylenephosphonic acid (MW = 432.31)
(15) Ethylenediaminetetramethylenephosphonic acid (MW = 436.13)
(16) Ethylenediaminetetraacetic acid (MW = 292.25)
(17) Nitrilotriacetic acid (MW = 191.14)
(18) Nitrilotrimethylenephosphonic acid (MW = 299.05)
(19) Iminodiacetic acid (MW = 133.10)
(20) Iminodimethylenephosphonic acid (MW = 205.04)
(21) Methyliminodiacetic acid (MW = 147.13)
(22) Methyliminodimethylenephosphonic acid (MW = 219.07)
(23) Hydroxyethyliminodiacetic acid (MW = 177.16)
(24) Hydroxyethyliminodimethylenephosphonic acid (MW = 249.10)
(25) Ethylenediaminetetrapropionic acid (MW = 348.35)
(26) Hydroxyethylglycidine (MW = 163.17)
(27) Nitrilotripropionic acid (MW = 233.22)
(28) Ethylenediaminediacetic acid (MW = 176.17)
(29) Ethylenediaminedipropionic acid (MW = 277.15)

The organic acid ferric complex salt is not limited to these; further a combination of two or more species can be used, if desired.
Of the organic acids for forming the organic acid ferric complex salt to be used in the present invention, particularly preferable ones include the following:

(1) Diethylenetriaminepentaacetic acid (MW = 393.27)
(3) Cyclohexanediaminotetraacetic acid (MW = 364.35)
(5) Triethylenetetraminehexaacetic acid (MW = 494.45)
(7) Glycoletherdiaminetetraacetic acid (MW = 380.35)
(9) 1,2-diaminopropanetetraacetic acid (MW = 306.27)
(11) 1,3-diaminopropane-2-ol-tetraacetic acid (MW = 322.27)
(19) Iminodiacetic acid (MW = 133.10)
(21) Methyliminodiacetic acid (MW = 147.13)
(23) Hydroxyethyliminodiacetic acid (MW = 177.16)
(28) Ethylenediaminediacetic acid (MW = 176.17)

The organic acid ferric complex salt to be used in the present invention may be used in the form of a free acid (hydroacid salt), an alkali metal salt such as a sodium salt, potassium salt or lithium salt, or an ammonium salt, or a water-soluble amine salt such as triethanol amine salt but is preferably a potassium salt, sodium salt or ammonium salt.
The bleaching agents are suitably used in amounts of 5 to 450 g/ℓ more preferably 20 to 250 g/ℓ. For a bleach-fixing solution, a solution having a composition containing a silver halide fixing agent other than the above bleaching agent and also containing a sulfite as the preservative, if desired, can be used. It is also possible to use a bleach-fixing solution such as a bleach-fixing solution comprising a composition in which a small amount of a halide such as ammonium bromide other than the organic acid iron (III) complex salt bleaching agent and the above silver halide fixing agent or a bleach-fixing solution comprising a composition in which a halide such as ammonium bromide is added in large amounts or further a special bleach-fixing solution comprising a composition in which the organic acid iron (III) complex salt bleaching agent is combined with a large amount of a halide such as ammonium bromide or the like. As the above halide, other than ammonium bromide, hydrochloric acid hydrobromic acid, lithium bromide, sodium bromide, potassium bromide sodium iodide, potassium iodide and ammonium iodide may be used.
As the silver halide fixing agent contained in the fixing solution or bleach-fixing solution, there may be employed compounds capable of forming water-soluble complex salts by reaction with silver halide as used in conventional fixing processing, including thiosulfates such as potassium thiosulfate, sodium thiosufate and ammonium thiosulfate, thiocyanates such as potassium thiocyanate, sodium thiocyanate and ammonium thiocyanate, thiourea and thioether. These fixing agents may be used in an amount of 5 g/ℓ or more within the range which can be dissolved but generally within the range of from 70 to 250 g/ℓ.
The bleach-fixing solution can contain various kinds of pH buffering agents such as boric acid, borax, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, acetic acid, sodium acetate and ammonium hydroxide, used either alone or in combination of two or more. Further, various fluorescent brighteners, defoaming agents or surfactants may be included. Also, organic chelating agents such as hydroxylamine, hydrazine and aminopolycarboxylic acid, stabilizers such as nitroalcohol or nitrate, or organic solvents such as methanol, dimethylsufonamide and dimethyl sulfoxide may be incorporated or appropriate.
In the bleach-fixing solution to be used in the present invention, various bleaching accelerators can be added as disclosed in Japanese Provisional Patent Publication No. 280/1971 Japanese Patent Publications No. 8506/1970 and No. 556/1971 Belgian Patent No. 770,910, Japanese Patent Publications No. 8836/1970 and No. 9854/ 1978 Japanese Provisional Patent Publications No. 71634/ 1979 and No. 42349/1974.
The bleach-fixing solution is generally used at a pH of 4.0 or higher, generally from pH 5.0 to pH 9.5, desirably from pH 6.0 to pH 8.5, most preferably at pH 6.5 to pH 8.5. The processing temperature is suitably 80°C or lower, and lower by 3°C or more, preferably 5°C or more than the processing solution temperature in the color developing tank, desirably 55°C or lower while suppressing evaporation etc.
The light-sensitive material to be used in the method of the present invention comprises silver halide emulsion layers and non-light-sensitive layers (non-emulsion layers) coated on a support. As the silver halide emulsion, any silver halide such as silver chloride, silver bromide, silver iodide, silver chlorobromide, silver chloroiodide, silver iodobromide or silver chloroiodobromide may be used. In these emulsion layers and non-light-sensitive layers, all couplers and additives known in the field of photography can be present. For example, there may be included as appropriate yellow dye forming couplers, magenta dye forming couplers cyan dye forming couplers stabilizers, sensitizing dyes, gold compounds, high boiling point organic solvents, antifoggants, dye image fading preventives, color staining preventives fluorescent brighteners, antistatic agents, film hardeners, surfactants, plasticizers, wetting agents and UV-ray absorbers, for example.
The light-sensitive material to be used in the method of the present invention can be prepared by coating the respective constituent emulsion layers and non-light-sensitive layers, containing various additives for photography as mentioned above, if necessary, on a support, for example one treated with a corona discharging treatment, flame treatment or UV-ray irradiation treatment, or alternatively through an intermediary subbing layer or intermediate layer on the support. The support advantageously used is, for example, baryta paper, polyethylene coated paper, polypropylene synthetic paper, glass plate, cellulose acetate, cellulose nitrate or polyester film such as polyethylene terephthalate, polyamide film, polycarbonate film or polystyrene film.
The above silver halide emulsion layers and non-light-sensitive layers are generally in the form of hydrophilic colloid layers containing a hydrophilic binder. As the hydrophilic binder, gelatin or gelatin derivatives such as acylated gelatin, guanidylated gelatin, phenylcarbamylated gelatin, phthalated gelatin, cyanoethanolated gelatin and esterified gelatin may be used.
As the film hardening agent for hardening the hydrophilic colloid layer, it is possible to use, for example, chromium salts (chrome alum, chromium acetate) aldehydes (formaldehyde, glyoxal, glutaraldehyde), N-methylol compounds (dimethylolurea, methylol-dimethylhydantoin), dioxane derivatives (2,3-dihydroxydioxane), active vinyl compounds (1,3,5-triacryloyl-hexahydro-s-triazine, 1,3-vinylsulfonyl-2-propanol), active halide compounds (2,4-dichloro-6-hydroxy-s-triazine) and mucohalogenic acid (mucochloric acid, mucophenoxychloric acid), either alone or in combination.
Also, the present invention is particularly effective in the case of the so-called oil protect type in which a dispersion of a coupler in a high boilling point organic solvent is present. The effect of the present invention is great when using, as such a high boiling point organic solvent, organic acid amides, carbamates, esters, ketones and urea derivatives, particularly phthalic acid esters such as dimethyl phthalate, diethyl phthalate, dipropyl phthalate, dibutyl phthalate, di-n-octyl phthalate, diisooctyl phthalate, diamyl phthalate, dinonyl phthalate and diisodecyl phthalate ; phosphoric acid esters such as tricresyl phosphate, triphenyl phosphate, (tri-(2-ethylhexyl)phosphate and trinonyl phosphate; sebacic acid esters such as dioctyl sebacate, di-(2-ethylhexyl)sebacate and diisodecyl sebacate; glycerine esters such as glycerol tripropionate and glycerol tributylate; or adipic acid esters, maleic acid esters, fumaric acid esters, citric acid esters and phenol derivatives such as di-tert-amylphenol and n-octylphenol.
The layer constitution of the light-sensitive material to be used in the present invention can be one known in color negative film, color paper and reversal color film. For example, it can be in the form of a blue-sensitive silver halide emulsion layer containing a yellow dye forming coupler, a green-sensitive silver halide emulsion layer containing a magenta dye forming coupler and a red-sensitive silver halide emulsion layer containing a cyan dye forming coupler on one surface of a support (these respective color-sensitive layers may consist of one layer or two or more layers).
In the light-sensitive material to be used in the present invention, it is preferable to use a yellow coupler represented by the following formula (V).
In the above formula, R¹ represents an alkyl group, an alkenyl group, an aryl group or a heterocyclic group, each of which may have a substituent, R² represents a cyano group or an N-phenylcarbamyl group which may have a substituent, Y represents -CO-, -SO₂-, a nitrogen atom, an oxygen atom, a sulfur atom, a carbon atom having no oxygen atom bonded with a double bond, and Z represents a group of non-metallic atoms necessary for the completion of a 4- to 6-membered nitrogen containing heterocyclic nucleus.
In the present invention, specific examples of the yellow coupler represented by the above formula (V) which can be used include those as described in Japanese Provisional Patent Publications No. 85426/1978, No. 102636/1976 and No. 2613/1972.
Specific examples are shown below, but these are not limitative of the present invention.

Y-1 α-(4-carboxyphenoxy)-α-pivalyl-2-chloro-5-[γ-(2,4-di-t-amylphenoxy)butyramide]acetanilide
Y-2 α-pivalyl-2-chloro-5-[γ-(2,4-di-t-amylphenoxy)butyramide]acetanilide
Y-3 α-(4-carboxyphenoxy)-α-pivalyl-2-chloro-5-[α-(3-pentadecylphenoxy)butyramido]acetanilide
Y-4 α-(1-benzyl-2,4-dioxo-3-imidazolidinyl)-α-pivalyl-2-chloro-5-[γ-(2,4-di-t-amylphenoxy)butyramido]acetanilide
Y-5 α-[4-(1-benzyl-2-phenyl-3,5-dioxo-1,24-triazolidinyl)]-α-pivalyl-2-chloro-5-[γ-(2,4-di-t-amylphenoxy)butyramido]acetanilide
Y-6 α-[4-(4-benzyloxyphenylsulfonyl)phenoxy]-α-pivalyl2-chloro-5-[γ-(2,4-di-t-amylphenoxy)butyramido]acetanilide
Y-7 α-pivalyl-α-(4,5-dichloro-3(2H)-pyridazo-2-yl)-2chloro-5-[(hexadecyloxycarbonyl)methoxycarbonyl]acetanilide
Y-8 α-pivalyl-α-[4-(p-chlorophenyl)-5-oxo-Δ²-tetrazolin-1-yl]-2-chloro-5-[α-dodecyloxycarbonyl)ethoxycarbonyl]acetanilide
Y-9 α-(2,4-dioxo-5,5-dimethyloxazolidin-3-yl)-α-pivalyl-2-chloro-5-[α-2,4-di-t-amylphenoxy)butyramido]acetanilide
Y-10 α-pivalyl-α-[4-(1-methyl-2-phenyl-3,5-dioxo-1,2,4triazolidinyl)]-2-chloro-5-[γ-(2,4-di-t-amylphenox )butyramido]acetanilid
Y-11 α-pivalyl-α-[4-(p-ethylphenyl)-5-oxo-Δ²-tetrazolin-1-yl]-2-chloro-5-[γ-(2,4-di-t-amylphenoxy)butyramido]acetanilide
Y-12 α-(4-nitrophenoxy)-α-pivalyl-2-chloro-5-[γ-(2,4-di t-amylphenoxy)butyramido]acetanilide

These yellow couplers can be synthesized according to the general synthetic methods described in West German OLS's No. 20 57 941 and No. 21 63 812, Japanese Provisional Patent Publications No. 26133/1972, No. 29432/1973, No. 65231/1975, No. 3631/1976, No. 50734/ 1976, No. 102636/1976, No. 66834/1973, No. 66835/1973, No. 94432/1973, No. 1229/1974, No. 10739/1974 and Japanese Patent Publication No. 25733/1976.
In the light-sensitive material to be used in the present invention, the effect of the present invention can be exhibited when the total dried film thickness of the light-sensitive silver halide emulsion layers on one surface of a support is 10 µm or more, and the effect of the present invention is particularly remarkable when it is 30 µm or less, particularly within the range of from 15 to 25 µm. If the total dried film thickness is less than 10 µm, the improve went in staining becomes small.
For color developing in the present invention, aromatic primary amine color forming agents are normally used and various known compounds widely used in color photographic process can be included in said developing agent. These developing agents include aminophenol type and p-phenylenediamine type derivatives. These compounds are used generally in the form of a salt such as hydrochloride or sulfate, since they are more stable than in the free state. These compounds are used generally at a concentration of 0.1 g to 30 g per 1 ℓ of the color developing solution, preferably at a concentration of 1 g to 1.5 g per 1 ℓ of color developing solution.
Examples of the aminophenol type developing agent include o-aminophenol, p-aminophenol, 5-amino-2-hydroxytoluene, 2-amino-3-hydroxytoluene and 2-hydroxy-3-amino-1,4-dimethylbenzene.
Particularly useful aromatic primary amine type color developing agents are N,Nʹ-dialkyl-p-phenylenediamine type compounds of which the alkyl group and phenyl group may be substituted with any desired substituent. Among them, examples of particularly useful compounds include N,Nʹ-diethyl-p-phenylenediamine hydrochloride, N-methyl-p-phenylenediamine hydrochloride, N,N-dimethyl-p-phenylenediamine hydrochloride, 2-amino-5-(N-ethyl-N-dodecylamino)-toluene, N-ethyl-N-β-methanesulfoneamidoethyl-3-methyl-4-aminoaniline sulfate, N-ethyl-N-β-hydroxyethylaminoaniline, 4-amino-3-methyl-N,Nʹ-diethylaniline and 4-amino-N-(2-methoxyethyl)-N-ethyl-3-methylaniline-p-toluenesulfonate.
In the present invention, the color developing solution contains substantially no benzyl alcohol, i.e. at a concentration of 1 mℓ/ℓ or less; it is usually present concentration of 10 to 20 mℓ/ℓ in a conventional color developing solution. Of course, a concentration of about 05. mℓ/ℓ comes within the region containing substantially no benzyl alcohol, but it is particularly preferred for there to be no benzyl alcohol at all.
In the color developing solution, in addition to the above aromatic primary amine type color developing agent, various components generally added to color developing solutions, for example, alkali agents such as sodium hydroxide, sodium carbonate and potassium carbonate, alkali metal thiocyanates, alkali metal halides, water softeners and thickeners, can be incorporated as desired. The pH value of the color developing solution using the aromatic primary amine type color developing agent as the color developing agent is usually 7 or more, most generally 10 to 13.
The soluble silver complex salt contained in the stabilizing solution substituting for water washing and the bleach-fixing solution to be used in the processing method of the present invention may be subjected to silver recovery according to a known method. For example, it is possible to utilize the electrolytic method (disclosed in French Patent No. 2,299,667), the precipitation method (disclosed in Japanese Provisional Patent Publication No. 73037/1977 and West German Patent No. 23 31 220), the ion exchange method (disclosed in Japanese Provisional Patent Publication No. 17114/1976 and West German Patent No. 25 48 237) and the metal substitution method (disclosed in U.K. Patent No. 1,353,805).
The processing method of the present invention is advantageously applied for processing color negative film, reversal color film, color negative paper, color positive paper and reversal color paper.
The processing steps to which the present invention can be applied particularly effectively include the following (1) and (2):

(1) Color developing _ bleach-fixing _ stabilizing processing substituting for water washing
(2) Color developing _ bleaching _ fixing _ stabilizing processing substituting for water washing.

EXAMPLES

The present invention is described in more detail by referring to the following non-limiting Examples.

Example 1

Experiments were carried out with the use of the color paper, the processing solutions and the processing steps as described below. [Color paper]
On a polyethylene coated paper support, the respective layers shown below were coated successively from the support side to prepare a light-sensitive material.
The polyethylene coated paper used was prepared by forming a coated layer of a composition comprising a mixture of 200 parts by weight of a polyethylene having an average molecular weight of 100,000 and a density of 0.95 and 20 parts by weight of a polyethylene having an average molecular weight of 2,000 and a density of 0.80 mixed with 6.8% by weight of an anatase type titanium oxide according to the extrusion coating method to a thickness of 0.035 mm onto the surface of a pure paper with a weight of 170 g/m² and providing a coated layer with a thickness of 0.040 mm only of polyethylene on the back surface. After application of a pre-treatment by corona discharging on the polyethylene coated surface on the support surface, the respective layers were coated successively.

First layer:

This is a blue-sensitive silver halide emulsion layer comprising a silver chlorobromide emulsion containing 80 mole % of silver bromide; said emulsion contains 450 g of gelatin per mole of silver halide, is sensitized with 2.5 × 10^-3 mole of a sensitizing dye of the present invention (exemplary compound I-12) per mole of silver halide (isopropyl alcohol is used as the solvent), contains 200 mg/m² of 2,5-di-t-butyl hydroquinone dispersed by dissolving it dibutylphthalate and 2 × 10^-3 mole per mole of silver halide of Y - 5 as the yellow coupler, and is coated to a silver quantity of 500 mg/m².

Second layer:

This is a gelatin layer containing 300 mg/m² of di-t-octylhydroquinone dispersed by dissolving it in dibutyl phthalate and 200 mg/m² of a mixture of 2-(2ʹ-hydroxy-3ʹ,5ʹ-di-t-butylphenyl)benzotriazole, 2-(2ʹ-hydroxy-5ʹ-t-butylphenyl)benzotriazole, 2-(2ʹ-hydroxy-3ʹ-t-butyl-5ʹ-methylphenyl)-5-chlorobenzotriazole and 2-(2ʹ-hydroxy-3ʹ,5ʹ-di-t-butylphenyl)-5-chloro-benzotriazole as UV-absorber and is coated to a gelatin content of 2000 mg/m².

Third layer:

This is a green-sensitive silver halide emulsion layer comprising a silver chlorobromide emulsion containing 85 mole % of silver bromide, and said emulsion contains 450 g of gelatin per mole of silver halide, is sensitized with 2.5 × 10^-3 mole of a sensitizing dye having the following structure:
per mole of silver halide, contains 150 mg/m² of 2,5-di-t-butylhydroquinone dispersed by dissolving it in a solvent comprising a mixture of 2:1 of dibutylphthalate and tricresyl phosphate and 1.5 × 10^-1 mole of 1-(2,4,6-trichlorophenyl)-3-(2-chloro-5-octadecenylsuccinimidoanilino)-5-pyrazolone per mole of silver halide as the magenta coupler, and is coated to a silver quantity of 400 mg/m². Also, as the antioxidant, 0.3 mole of 2,2,4-trimethyl-6-lauryloxy-7-t-octylchroman per mole of the coupler is incorporated.

Fourth layer:

This is a gelatin layer containing 30 mg/m² of di-t-octylhydroquinone dispersed by dissolving it in dioctyl phthalate and 500 mg/m² of a mixture (2: 1.5: 1.5: 2) of 2-(2ʹ-hydroxy-3ʹ,5ʹ-di-t-butylphenyl)benzotriazole, 2-(2ʹ-hydroxy-5ʹ-t-butylphenyl)benzotriazole, 2-(2ʹ-hydroxy-3ʹ-t-butyl-5ʹ-methylphenyl)-5-chlorobenzotriazole and 2-(2ʹ-hydroxy-3ʹ,5ʹ-t-butylphenyl)-5-chlorobenzotriazole as the UV-ray absorber, and is coated to a gelatin quantity of 2000 mg/m².

Fifth layer:

This is a red-sensitive silver halide emulsion layer comprising a silver chlorobromide emulsion containing 85 mole % of silver bromide, and said emulsion contains 500 g of gelatin per mole of silver halide, is sensitized with 2.5 × 10^-3 mole of a sensitizing dye having the following structure:

per mole of silver halide, contains 55 mg/m² of 2,5-di-t-butylhydroquinone dispersed by dissolving it in dibutyl phthalate and 3.5 × 10^-1 mole of 2,4-dichloro-3-methyl-6-[y-(2,4-diamylphenoxy)butyramido]phenol per mole of silver halide as the cyan coupler, and is coated to a silver quantity of 400 mg/m².

Sixth layer:

This is a gelatin layer and is coated to a gelatin quantity of 1000 mg/m².
The silver halide emulsions used for the respective light-sensitive emulsion layers (the first, third and fifth layers) were prepared according to the method described in Japanese Patent Publication No. 7772/ 1971, and each of them was chemically sensitized with sodium thiosulfate pentahydrate and incorporated with 4-hydroxy-6-methyl-1,3,3a,7-tetrazaindene as the stabilizer, bis(vinylsulfonylmethyl)ether as the film hardener and saponin as the coating aid.
The film thickness after coating and drying as described above was measured to be 17 µm.
The color paper prepared according to the above method was exposed to light and then the experiments were conducted with the use of the following processing steps and processing solutions.
Standard processing steps
Processing solution compositions
<Color developing tank solution>

(made up to 1 liter with addition of water, and adjusted to pH 10.20 with potassium hydroxide or sulfuric acid).
<Color developing supplementing solution>

(made up to 1 liter with addition of water, and adjusted to pH 10.70 with potassium hydroxide).
<Bleach-fixing tank solution>

<Bleach-fixing supplementing solution A>

(made up to the total amount of 1 liter with addition of water; this solution has a pH of 6.7 ± 0.1).
<Bleach-fixing supplementing solution B>

(made up to the total amount of 1 liter with addition of water; this solution has a pH of 5.3 ± 0.1).
<Stabilizing tank solution substituting for water washing and supplementing solution>

(made up to 1 liter with addition of water, and adjusted to pH 7.0 with sulfuric acid).

Experiment C (control experiment by washing with running water)

An automatic developing machine was filled with the above color developing tank solution, bleach-fixing tank solution and the stabilizing tank with tap water and continuous processing was performed by processing color paper while supplementing the color developing supplementing solution and the bleach-fixing supplementing solutions A and B as described above through quantitating cups at intervals of 3 minutes. The amounts supplemented were, per 1 m² of color paper, 190 mℓ for the color developing tank, and 50 mℓ each for the bleach-fixing supplementing solutions A and B for the bleach-fixing tank, and 20 ℓ of tap water were added (run in) to the stabilizing processing bath per 1 m².

Experiment 1 to Experiment 9

Using the above color paper, processing was performed in the same manner as the above Experiment C using the above color developing tank solution and the color developing supplementing solution as such or a formulation in which only benzyl alcohol was removed from the above color developing solution formulation for the color developing solution as shown in Table 1, and by using a formulation in which the compound as indicated in Table 1 was added for the stabilizing solution substituting for water washing (Experiments 1 to 9). The supplementing amount of the stabilizing supplementing solution substituting for water washing into the stabilizing tank solution was 250 mℓ per 1 m² of color paper.
For the stabilizing processing tank in the automatic developing machine the first tank to the third tank in the direction of the flow of the light-sensitive material constituted the stabilizing tank, and an multitank countercurrent system was employed in which supplementing was conducted in the final tank, the overflow from the final tank was permitted to flow into the tank in the preceding stage, and further the overflow from this stage was permitted to flow into the tank in the stage preceding thereto.

Experiments 10 and 11

A light-sensitive material was prepared in entirely the same manner except for removing the sensitizing dye (exemplary compound I-12) added in the first layer; using this light-sensitive material, processing as shown in Table 1 was conducted similarly to Experiments 1 to 9.
Also, for the stabilizing solution substituting for water washing containing the compound in Table 1 in the above stabilizing solution formulation substituting for water washing, surface tension was measured in a conventional manner to obtain the results as shown in Table 1.
The white grounds of the unexposed portions of the samples obtained by processing in Experiment C to Experiment 11 were observed. Further, the spectral reflective densities at 440 nm of the white grounds of the unexposed portions were measured by means of a color analyzer (produced by Hitachi Ltd.).
Also, for the yellow portion of the samples obtained by processing, a light resistance test using a xenon arc lamp was performed for 300 hours, and the densities of the dye images before and after the light resistance test were measured with the blue light of an optical densitometer (PDA - 65, produced by Konishiroku Photo Industry Co.) to determine the fading percentage. These results are shown in Table 2.
From Table 2, it can be seen that, in the case of the processing methods of Comparative examples No. 1 to No. 4, stain is worse with a bad white ground of unexposed portion by visual observation and higher spectral reflective density value as compared with running water washing (Experiment C). Also, the same is the case for color fading. In contrast, in N°. 5 to N° 9 of the present invention, it can be appreciated that the white ground of the unexposed portion as well as light fading percentage of yellow dye are much better, exhibiting values similar to those in running water washing. Also, it can be seen that the effect of the present invention is higher in No. 5, No. 8 and No. 9 where the surface tension of the stabilizing solution substituting for water washing is low.
Further, from No. 1, No. 9, No. 10 and No. 11, it can be seen that the present invention is particularly effective when the light-sensitive materials contain a sensitizing dye represented by the formula (I).

Example 2

In the light-sensitive material of Example 1, the sixth layer was coated after coating of the first layer to prepare a light-sensitive material in which the second layer to the fifth layer were omitted. Similarly, light-sensitive materials were prepared by varying the amount of the first layer coated to 2-fold, 3-fold, 4-fold, 5-fold and 6-fold. These dried film thicknesses were found to be 7.1 µm, 12.8 µm, 18.4 µm, 24.2 µm, 29.9 µm and 35.7 µm, respectively.
These light-sensitive materials were subjected to processing with the use of the processing solutions after continuous processing of Experiment 1 and Experiment 9.
After processing, the respective grounds were measured visually and by spectral reflective density (440 nm) as in Example 1. The results are shown in Table 3.
As is apparent from Table 3, the present invention is effective when the light-sensitive material has a dried film thickness of 10 µm or more, particularly effective in the range from about 10 µm to 30 µm and most effective in the range from about 15 µm to 25 µm.

Example 3

On a triacetate film base, a halation preventive layer and a gelatin layer were provided, and a red-sensitive silver halide emulsion layer, a green-sensitive silver halide emulsion layer, a filter layer containing yellow colloidal silver and a blue-sensitive silver halide emulsion layer were coated thereon to a total silver quantity of 70 mg/100 cm².
The above emulsion layers comprise a silver iodobromide containing about 4.5 mole % of silver iodide and, in this case, Y - 12 was employed as the yellow coupler in the blue-sensitive silver halide emulsion layer; 1-(2,4,6-trichlorophenyl)-3-{[α-(2,4-di-t-amylphenoxy)acetamido]-benzamido}-3-pyrazolone and 1-(2,4,6-trichlorophenyl)-3-{[α-(2,4-di-t-amylphenoxy)acetamido]benzamido}-4-(4-methoxyphenylazo)-5-pyrazolone were employed as the magenta coupler in the green-sensitive silver halide emulsion layer; 1-hydroxy-N-{α-(2,4-t-amylphenoxy)butyl}-2-naphthoamide was employed as the cyan coupler in the red-sensitive silver halide emulsion layer ; sensitizing dye, film hardener and extender were added in the respective emulsion layers. However, in the blue-sensitive silver halide emulsion layer, the exemplary compound (I-16) was used as the sensitizing dye.
The color negative film thus obtained was found to have a dried film thickness of 23 µm.

Experiment 12

The above light-sensitive material was exposed in a conventional manner and then an experiment was conducted with the use of the following processing steps and processing solutions.

<Color developing tank solution>

(made up to 1 liter with addition of water and adjusted to pH 10.06 with potassium hydroxide).
<Color developing supplementing solution>

(made up to 1 liter with addition of water and adjusted to pH 10.35 with potassium hydroxide).
<Bleach-fixing tank solution and supplementing solution>

(made up to 1 liter with addition of water and adjusted to pH 7.0 with aqueous ammonia (28% solution)).
<Stabilizing tank solution and supplementing solution>
Formalin (35% aqueous solution) 7.0 mℓ

(made up to 1 liter with addition of water).
An automatic developing machine was filled with the above color developing tank solution, the bleach-fixing tank solution, the washing water and the stabilizing tank solution, and continuous processing was performed by processing the color negative film while supplementing the above color developing supplementing solution, the bleach-fixing supplementing solution and the stabilizing supplementing solution through a quantitating cup at intervals of 3 minutes. The amounts supplemented were, per 1 m² of the color negative film, 1475 mℓ for the color developing tank, 926 mℓ for the bleach-fixing tank and 926 mℓ of the stabilizing supplementing solution for the stabilizing processing tank, respectively.
The amount of the washing water in the washing step was 30 ℓ/m².

Experiment 13 to Experiment 16

Using the above color negative film, experiments were conducted with the following steps and processing solutions.
In the stabilizing step substituting for water washing, a multi-tank countercurrent system was used, in which the first tank to the third tank in the direction of the flow of the light-sensitive material constituted the stabilizing tank, and supplementing was performed from the final tank, with the overflow from the final tank flowing into the tank in the preceding stage and further the overflow from this stage flowing into the tank in the stage preceding thereto.
Both the color developing solution and the bleach-fixing solution were the same as in Experiment 12, and the stabilizing solution substituting for water washing employed was prepared by adding the compound as indicated in Table 4 to the formulation shown below, and continuous processing was performed as in Experiment 12 (Experiments 13 to 16).
The amount supplemented of the stabilizing solution substituting for water washing was the same as the stabilizing solution in Experiment 12.
<Stabilizing tank solution substituting for water washing and supplementing solution>

(made up to 1 liter with water, and adjusted to pH 7.0 with sulfuric acid or potassium hydroxide).
The surface tensions of the stabilizing solution and the stabilizing solution substituting for water washing employed in the Experiments were measured in a conventional manner and the results are shown in Table 4.
Also, for the yellow image portions of the samples obtained in the respective experiments, a light resistance test with a xenon arc lamp was conducted for 200 hours, and the density before and after the test were measured with the blue light of an optical densitometer (PDA - 65, produced by Konishiroku Photo Industry Co., Ltd.) to determine a fading percentage. These results are shown in Table 4.
From Table 4, it can be seen that water washing-stabilizing processing (containing formalin) generally practiced at present as in the Experiment 12 can be replaced with stabilizing processing substituting for water washing after bleach-fixing by practicing the present invention, whereby elimination of water washing is rendered possible.

Claims

1. A method of processing a light-sensitive silver halide color photographic material, which comprises subjecting to imagewise exposure a light-sensitive silver halide colour photographic material having a total dried film thickness of the light-sensitive silver halide emulsion layers and the non-light sensitive layers (s) on one surface of a support of 10 µm or more, processing the exposed material with a color forming developer containing at most 1 ml/l of benzyl alcohol, thereafter processing the material with a processing solution having fixing ability and subsequently instead of water washing, processing the material with a stabilizing solution having a surface tension of 8 to 50 dyne/cm (mN/m) at 20°C and containing at most 0.1 g/g of aldehyde compound, followed by drying.

2. A method of processing a light-sensitive silver halide color photographic material according to claim 1, wherein said light-sensitive silver halide color photographic material contains a sensitizing dye represented by the following formula:

where each Z₁ and Z₂ independently represents a group of atoms necessary to complete a benzoxazole, naphthoxazole, benzothiazole, naphthothiazole, benzoselenazole, naphthoselenazole, benzoimidazole, naphthoimidazole, pyridine or quinoline nucleus, each of R¹ and R₂ independently represents an alkyl group, an alkenyl group or an aryl group, R₃ represents a hydrogen atom, a methyl group or an ethyl group and X₁⁻ represents an anion and ℓ represents 0 or 1.

3. A method of processing a light-sensitive silver halide color photographic material according to claim 2, wherein the amount of the sensitizing dye of formula (I) added in the emulsion is from 2 × 10^-6 to 1 × 10^-3 mole per mole of the silver halide.

4. A method of processing a light-sensitive silver halide color photographic material according to claim 3, wherein the amount of the sensitizing dye of formula (I) added in the emulsion is from 5 × 10^-6 to 5 × 10^-4 mole per mole of the silver halide.

5. A method of processing a light-sensitive silver halide color photographic material according to any one of claims 1 to 4, wherein said stabilizing solution is present in 1 to 5 tanks.

6. A method of processing a light-sensitive silver halide color photographic material according to any one of claims 1 to 5, wherein said stabilizing solution has a surface tension of 15 to 40 dyne/cm (mN/m).

7. A method of processing a light-sensitive silver halide color photographic material according to any one of claims 1 to 6, wherein said stabilizing solution contains at least one compound of formula (II) or (III) or a water soluble organic siloxane type compound:

wherein A is an alkyl group having 6 to 20 carbon atoms or an aryl group substituted with an alkyl group having 3 to 20 carbon atoms; B represents an ethylene oxide or propylene oxide unit; m represents an integer of 4 to 50; and X₂ represents a hydrogen atom, SO₃Y or PO₃Y₂ and Y represents a hydrogen atom, an alkali metal or ammonium ion,

wherein each of R₄, R₅, R₆ and R₇ independently represents a hydrogen atom, an alkyl group or a phenyl group, and the total number of carbon atoms of R₄, R₅, R₆ and R₇ is 3 to 50; X₃ represents an anion of a halogen atom, a hydroxyl group, a sulfate group, a carbonate group, a nitrate group, an acetate group or a p-toluenesulfonate group.

8. A method of processing a light-sensitive silver halide color photographic material according to claim 7, wherein the amount of said compound is from 0.01 to 20 g per 1 ℓ of the stabilizing solution.

9. A method of processing a light-sensitive silver halide color photographic material according to any one of claims 1 to 8 wherein said color developing solution contains no benzyl alcohol.

10. A method of processing a light-sensitive silver halide color photographic material according to any one of claims 1 to 9, wherein said stabilizing solution contains no aldehyde.

11. A method of processing a light-sensitive silver halide color photographic material according to any one of claims 1 to 10 wherein the amount of the stabilizing solution added to the stabilizing bath is from 1 to 50 times the amount brought in from a previous bath per unit area of the light-sensitive material to be processed.

12. A method of processing a light-sensitive silver halide color photographic material according to claim 11, wherein said amount is from 2 to 20 times.

13. A method for processing a light-sensitive silver halide color photographic material according to any one of claims 1 to 12, wherein processing is performed in a succession of tanks, the processing time being increased by 20% to 50% as compared with that in the preceding tank.