DE68927983T2 - Processing and bleaching process for color photographic light-sensitive silver halide materials - Google Patents

Description

FIELD OF INVENTION

The present invention relates to a treatment process for light-sensitive silver halide color photographic recording materials (hereinafter referred to as "light-sensitive recording materials" for the sake of simplicity) and a bleaching bath suitable for the treatment process, in particular a treatment process and a bleaching bath which allow sufficient desilvering within a short time and prevent bleach fogging. The process and the bleaching bath are also well suited for light-sensitive recording materials which are rich in silver and have a high sensitivity.

BACKGROUND OF THE INVENTION

The treatment of a light-sensitive recording material basically includes color development and desilvering processes. Desilvering is carried out by bleaching and fixing or by bleach-fixing. In addition, rinsing, stabilizing and other measures can also be carried out.

In treatment baths with bleaching ability used for desilvering light-sensitive recording materials, ferricyanates, bichromates and other inorganic oxidizing agents have been used on a large scale to bleach the image silver.

However, there are some critical disadvantages in these treatment baths containing inorganic oxidizing agents with bleaching ability. For example, ferricyanates and bichromates are undesirable for environmental pollution reasons despite their relatively high image silver bleaching power, as they can be decomposed by light to form harmful cyan ions or hexavalent chromium ions. A further disadvantage is the difficulty of reprocessing these treatment baths for recycling without removing the liquid waste after treatment.

In view of the need to reduce environmental pollution, rapid and simple treatment, reuse of liquid waste and the like, or the use of treatment baths with metal complex salts of organic acids, e.g. aminopolycarboxylic acid, as oxidizing agents were used. The disadvantage of such treatment baths, however, is that due to their weak oxidizing power, the bleaching rate (oxidation rate) of the image silver (metallic silver) formed during development is low. For example, the iron(III) complex salt of ethylenediaminetetraacetic acid, which exhibits a relatively strong bleaching power among metal complex salts of aminopolycarboxylic acids, is currently in use in bleaching baths and bleach-fixing baths, but it suffers from the fact that its bleaching power is still insufficient and that the bleaching measures take a relatively long time when carried out with a highly sensitive light-sensitive color photographic silver halide recording material containing mainly a silver bromide or silver iodobromide emulsion, in particular a silver-rich color paper for recording images and color negative and reversal films for recording images containing silver iodide.

In addition, development operations using an automatic developing device and the like for continuously processing large quantities of light-sensitive recording materials require a device for controlling the processing solution components within a given concentration range to avoid a reduction in bleaching performance due to changes in component concentrations. To meet this requirement, as well as to improve economy and prevent environmental pollution, various measures have been proposed. These include a method in which supplementary concentrates are added in small amounts and a method in which an overflow is supplemented with regenerant and then reused as a supplementary agent.

As far as bleaching agents are concerned, a process is currently used in practice in which an iron(II) complex salt of an organic acid, e.g. an iron(II) complex salt of ethylenediaminetetraacetic acid, formed during the bleaching of developed silver, is oxidized by aeration to an iron(III) complex salt of ethylenediaminetetraacetic acid, i.e. an iron(III) complex salt of an organic acid, a regenerating agent is added to replenish the used components and the solution is then reused as a replenishment solution.

In recent years, in order to save the processing time for silver halide color photographic light-sensitive materials and to save delivery costs, a large number of so-called compact laboratories or mini-laboratories have been set up. In these laboratories, there is a significant need for simplification of processes and reduction of the space required for the developing device, so that regeneration is not suitable. This requires laborious measures and maintenance as well as additional processing space.

Preferably, the supplementation measures should therefore be carried out without a regeneration process with small amounts of thick supplementary concentrates. However, if the amount of replenisher is extremely low, the concentration of color developer components carried over into the bleaching bath increases. In addition, the latter bath may also be affected by concentration due to evaporation. This leads to a (further) increase in the accumulation of color developer components. As already stated, an increase in the color developer component concentration in the bleaching bath increases the proportion of reducing contaminants, e.g. color developer compound and sulfites. This inhibits the bleaching reaction and leads to a phenomenon called desilvering failure. In order to counteract these disadvantages, it has already been proposed in Research Disclosure No. 24023 and in Japanese Patent Application Laid-Open 62-222252/1987 to use iron (III) complex salts of aminopolycarboxylic acids and mixtures thereof. However, these measures also have a variety of disadvantages. For example, iron(III) complex salts of 1,3-propanediaminetetraacetic acid (which is known from the literature references mentioned) suffer from the fact that when they are used to bleach silver-rich and highly sensitive light-sensitive recording materials, bleach fogging occurs over a long period of time. Consequently, the use of these salts or mixtures as bleaching agents leads to bleach fogging in color-sensitized high-sensitivity light-sensitive recording materials containing mainly silver chloroiodide or silver iodobromide emulsions, in particular ultra-high-sensitivity (for example 400 to 3200 ASA) color negative films for image recording with a silver-rich emulsion. However, they allow the desired bleaching or bleach-fixing of low-sensitivity light-sensitive recording materials with mainly a silver chlorobromide emulsion. The disadvantage described is even more pronounced when the amount of bleaching supplements is reduced. Furthermore, It has been found that this tendency becomes even more pronounced when the colour developing agent is present in the colour developing bath used in colour development prior to bleaching at a concentration exceeding 1.5 x 10⊃min;2 mol.

For these reasons, a desilvering process and a bleaching bath suitable for treating high-sensitivity, silver-rich photosensitive recording materials without bleach fog should be developed.

DE-A-35 18 257 describes a process for treating a light-sensitive color photographic recording material by developing an image-correctly exposed light-sensitive color photographic silver halide recording material with a color developer, then bleaching the light-sensitive recording material with a bleaching bath and finally treating the light-sensitive recording material with a bath with fixing ability in a separate stage. The light-sensitive color photographic silver halide recording material contains a coupler of the general formula (Ia) or (Ib) which forms a blue-green dye image. The bleaching bath contains a compound of the general formula (II-a) or (II-b). The treatment time with the bleaching bath is essentially no more than 2.30 minutes.

JP-A-62-222252 describes a method for treating a silver halide color photographic recording material with a bath having bleaching ability after its color development. The bath having bleaching ability contains at least one compound selected from the group consisting of an ethylenediaminetetraacetatoiron(III) complex salt, a diethylenetriaminepentaacetatoiron(III) complex salt and a cyclohexanediaminetetraacetatoiron(III) complex salt, and at least one compound selected from the group consisting of a 1,2-diaminopropanetetraacetatoiron(III) complex salt, a 1,3-diaminopropanetetraacetatoiron(III) complex salt and a 1,3-diamino-2-propanoltetraacetatoiron(III) complex salt.

SUMMARY OF THE INVENTION

The object of the present invention is to provide a treatment process with inhibited bleach fogging and a bleach bath with good function when carrying out the treatment process.

The above object of the invention can be achieved with a method for treating a light-sensitive silver halide color photographic recording material by developing the light-sensitive recording material with a color developer; bleaching the light-sensitive recording material immediately after the development step with a bleaching bath and treating the light-sensitive recording material after the bleaching step with a bath with fixing ability, wherein the bleaching bath contains at least one of the iron (III) complex salts of compounds of the following formulas A or B in an amount of at least 0.01 mol/l of bleaching bath and a buffer with the ability to adjust the pH to 3 to 7 of the following formula I, the pH of the bleaching bath is kept in the range of 3 to 7 and the bleaching bath is replenished with a bleaching bath replenisher solution in a quantity of 30 ml to 350 m¹/m² of the light-sensitive silver halide colour photographic recording material. Formula A

where:

A₁ to A₄, which may be the same or different, each represent a -CH₂OH-, -COOM- or -PO₃M₁M₂- group;

M, M₁ and M₂ each represent a hydrogen, sodium or potassium atom or an ammonium group and

X is an optionally substituted alkylene group having 3 to 6 carbon atoms; Formula B

wherein A₁ to A₄ have the meaning given for formula A, n is an integer from 1 to 8 and B₁ and B₂, which may be the same or different, each represent an optionally substituted alkylene group having 2 to 5 carbon atoms;

Formula I

A - COOH

where A represents a hydrogen atom or an organic group , acetic acid being excluded for the formula I.

According to the invention, a bleaching treatment is carried out. This is followed by a treatment with a fixing agent or bleach-fixing agent.

DETAILED DESCRIPTION OF THE INVENTION

In the relevant processes, the desired effect is achieved when the bleaching bath contains both a specific iron (III) complex salt of an organic acid and a buffer capable of adjusting the pH to 3 to 7 in such a way that the pH of the bath in question is maintained at 3 to 7. Failure to meet even one of these requirements interferes with the present invention.

The compound of formula A is described in detail below.

A₁ to A₄ independently represent -CH₂OH, -COOM or -PO₃M₁M₂ and are the same or different. M, M₁ and M₂ independently represent a hydrogen atom, sodium, potassium or ammonium. X represents an optionally substituted alkylene group having 3 to 6 carbon atoms, e.g. propylene, butylene, trimethylene, tetramethylene and pentamethylene. Suitable substituents are a hydroxyl group and alkyl groups having 1 to 3 carbon atoms.

Examples of preferred compounds of formula A are:

These compounds (A-1) to (A-12) can be used in any way in the form of their sodium, potassium or ammonium salts. In order to achieve the desired result according to the invention and with regard to solubility, the ammonium salts of the iron (III) complex salts of these compounds are preferably used.

Of these compounds, the compounds (A-1), (A-4), (A-7) and (A-9), in particular (A-1) are preferred according to the invention.

The compounds of formula B are described in detail below.

A₁ to A₄ have the meaning given above. n represents any integer from 1 to 8. B₁ and B₂ independently represent an optionally substituted alkylene group having 2 to 5 carbon atoms, such as ethylene, propylene, butylene and pentamethylene. The substituent includes a hydroxyl group and lower alkyls having 1 to 3 carbon atoms, e.g. a methyl, ethyl or propyl group.

Examples of preferred compounds of formula B are:

These compounds (B-1) to (B-7) can be used in any way in the form of their sodium, potassium or ammonium salts. In order to achieve the desired result according to the invention and with regard to solubility, the ammonium salts of the iron (III) complex salts of these compounds are preferably used.

Of these compounds, compounds (B-1), (B-4) and (B-7), especially (B-1) are preferred.

According to the invention, the compounds of formula A or B can be used individually or in combination.

Iron(III) complex salts of these compounds of formula A or B are used per liter of bleaching bath in an amount of at least 0.1, preferably from 0.01 to 1.0, preferably from 0.1 to 1.0, ideally from 0.15 to 0.8 mol. For cost and solubility reasons, the amount of iron(III) complex salts of the compounds of formula A or B should preferably be limited to the ranges mentioned.

Examples of bleaching agents preferably used in combination with the compounds of formula A or B in the bleaching bath according to the invention are the following compounds:

(A'-1) Ethylenediaminetetraacetic acid or its salts (e.g. the ammonium, sodium, potassium or triethanolamine salts)

(A'-2) Trans-1,2-cyclohexanediaminetetraacetic acid or its salts (dto.)

(A'-3) Dihydroxyethylglycinic acid or its salts (dto.)

(A'-4) Ethylenediaminetetrakismethylenephosphonic acid or its salts (dto.)

(A'-5) Nitrilotrimethylenephosphonic acid or its salts (dto.)

(A'-6) Diethylenetriaminepentakismethylenephosphonic acid or its salts (dto.)

(A'-7) Diethylenetriaminepentaacetic acid or its salts (dto.)

(A'-8) Ethylenediaminedi-o-hydroxyphenylacetic acid or its salts (dto.)

(A'-9) Hydroxyethylethylenediaminetriacetic acid or its salts (dto.)

(A'-10) Ethylenediaminepropionic acid or its salts (dto.)

(A'-11) Ethylenediaminediacetic acid or its salts (dto.)

(A'-12) Glycol ether diaminetetraacetic acid or its salts (dto.)

(A'-13) Hydroxyethyliminodiacetic acid or its salts (dto.)

(A'-14) Nitrilotriacetic acid or its salts (dto.)

(A'-15) Nitrilotripropionic acid or its salts (dto.)

(A'-16) Triethylenetetraminehexaacetic acid or its salts (dto.)

(A'-17) Ethylenediaminetetrapropionic acid or its salts (dto.)

However, these connections are not limited to the examples given.

The compounds A'-1, A'-2, A'-7 and A'-12 are particularly preferred.

These aminopolycarboxylic acids can be used in the form of iron (III) complex salts or combined in a solution with iron (III) salts, for example iron (III) sulfate, iron (III) chloride, iron (III) acetate, iron (III) sulfate, iron (III) ammonium sulfate and iron (III) phosphate, to form iron (III) ion complex salts. When used in the form of complex salts, one or more complex salts can be used. When using iron (III) salts and an aminocarboxylic acid to form complex salts in a solution, one or more iron (III) salts can be used. Furthermore, one or more aminopolycarboxylic acids can also be used. In any case, the aminopolycarboxylic acids can be used in excess of the amount required to form iron (III) ion complex salts. Aminopolycarboxylic acids and iron complex salts can be used in the form of ammonium, sodium, potassium or triethanolamine salts or in combination.

The bleaching baths containing the iron(III) ion complex(es) mentioned may also contain metal ion complex salts of cobalt, copper, nickel, zinc and other metals.

The term "buffer capable of adjusting the pH to 3 to 7" here and hereinafter means a buffer which requires the addition of K₂CO₃ in an amount exceeding 5 g/l to adjust the pH of an aqueous solution containing a given amount of the buffer to 3 to 7.

Preferred buffers of formula I according to the invention are:

Examples of the preferred fatty acid compounds are acrylic, adipic, acetylenedicarbon, acetoacetic, azelaic, isocroton, isopropylmalonic, isobutter, itacone, isovalerian, ethylmalonic, caproic, formic, valerian, citric, Glycolic, glutaric, crotonic, chlorofumaric, α-chloropropionic, gluconic, glycerin, β-chloropropionic, succinic, cyanoacetic, diethylacetic, diethylmalonic, dichloroacetic, citraconic, dimethylmalonic, oxalic, d-tartaric, meso-tartaric, trichlorolactic, tricarbaryl, trimethylacetic, lactic, vinylacetic, pimelic, pyrowaric, racemic tartaric, fumaric, propionic, prapylmalonic, maleic, malonic, mesaconic, methylmalonic, monochloroacetic, n-butyric, malic and aspartic acid, DL-alanine, glutamic and 3,3-dimethylglutaric acid.

Examples of preferred acids with a cyclic structure are ascorbic, atropa, allocinnamic, benzoic, isophthalic, oxybenzoic (m-, p-), chlorobenzoic acid (o-, m-, p-), chlorophenylacetic (o-, m-, p-), cinnamic, salicylic, dioxybenzoic (2,3-, 2,4-, 2,5-, 2,6-, 3,4-, 3,5), cyclobutane-1,1-dicarbon, cyclobutane-1,2-dicarbon (trans-, cis-), cyclopropane-1,1-dicarbon, cyclopropane-1,2-dicarbon (trans-, cis-), cyclohexane-1,1-dicarbon, cyclohexane-1,2-dicarbon (trans-, cis-), cyclohexylacetic, Cyclopentane-1,1-dicarbon-, 3,5- dinitrobenzoic-, 2,4-dinitrophenoldiphenyl-, sulfanil terephthalic-, toluyl- (o-, m-, p-), naphthoe- (α-, β-), nicotine-, nitroanisole- (o-, m-, p-), nitrobenzoic-, nitrophenyl- (o-, m-, p-), p-nitrophnetol, pyroslummy-, urinary-, hippuric-, barbituric-, picoline-, violur-phenylacetic-, phenyl-, phthalic-, fluorobenzoic- (o-, m-, p-), bromobenzoic- (o-, m-, p-), hexahydrobenzoic-, benzyl-, dl-mandel-, mesitylene-, methoxybenzoic- (o-, m-, p-), Methoxycinnamic (o-, m-, p-), p- methoxyphenylacetic, gallic and aminobenzoic acid (o-, m-, p-).

Other preferred compounds are N-(2-acetamido)iminodiacetic acid, N-(2-acetamido)-2-aminoethanesulfonic acid, bis(2-hydroxyethyl)iminotris-(hydroxymethyl)methane, 2-(N-morpholino)ethanesulfonic acid, 3-(N-morpholino)-2-hydroxypropanesulfonic acid, piperazine-N,N-bis(2-ethanesulfonic acid), ethylenediaminediacetic acid, ethylenediamine-2-propionic acid, β- Aminoethyliminodiacetic acid and organic phosphoric acids, such as aminomethylphosphono-N,N-diacetic acid, 2-phosphonoethyliminodiacetic acid, 2-phosphonobutane-1,2,4-triacarboxylic acid and the following (acids):

Of these compounds, fatty acids and cyclic acids are preferred. Fatty acids are particularly preferred. Short-chain carboxylic acids are particularly suitable, especially those with 2 to 6 carbon atoms.

These buffer compounds should be added to the bleaching bath in an amount of 0.01 to 3.0, preferably 0.02 to 2.0, preferably 0.1 to 2.0 mol/l. For reasons of cost, solubility and bleaching performance, an upper limit should be set for the buffer amount within the specified ranges within the scope of the invention.

If an iron(III) complex salt of the compounds of formula A and B is used in an amount of 0.3 to 1.0 mol per 1 l of bleaching bath, the buffer should preferably be used in an amount of 0.1 to 2.0 mol/l.

Of the compounds mentioned, acetic acid, an organic acid, is somewhat inferior in its effectiveness.

However, it has been found that when an iron (III) complex salt of the compound of formula A or B is used in a molar proportion of 40%, preferably 50% of the iron (III) complex salts of aminopolycarboxylic (or phosphonic) acids present as bleaching agents, in the presence of an iron (III) complex salt of the compound of formula A or B in an amount of more than 0.2 mol/l, acetic acid in an amount of 0.5 to 3, preferably 0.8 to 2 mol/l is highly effective in stabilizing the solution or protecting the suspended solids.

The pH value of the bleaching bath according to the invention is, in view of the desired success, in the range from 3 to 7, expediently 4 to 6, preferably 4.5 to 5.8.

The bleaching bath according to the invention is used at a temperature of 5 to 80°C, conveniently 20 to 45°C, preferably 25 to 42°C.

The amount of supplementary agent for a bleach bath according to the invention is 30 to 350, preferably 40 to 300, preferably 50 to 250 ml per m² of light-sensitive recording material.

Preferably, halides such as ammonium bromide and ammonium chloride are added to the bleaching bath according to the invention. These halides are added in an amount of conveniently 0.1 to 5, preferably 0.3 to 3 mol/l.

The bleaching bath according to the invention can contain a wide variety of brighteners, defoamers and wetting agents.

The treatment baths with fixing ability according to the invention, namely the fixing bath and bleach-fixing bath, require the addition of a so-called fixing agent.

Fixing agents are compounds that react with silver halide to form a water-soluble complex salt, e.g. thiosulfates such as potassium thiosulfate, sodium thiosulfate and ammonium thiosulfate, thiocyanates such as potassium thiocyanate, sodium thiocyanate and ammonium thiocyanate, thioureas, thioethers and halides such as iodides.

The fixing or bleach-fixing bath may contain one or more pH buffers in the form of 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, as well as a fixing agent.

It is expedient to add a large amount of a rehalogenating agent including alkali halides and ammonium halides such as potassium bromide, sodium bromide, sodium chloride or ammonium bromide. Furthermore, if appropriate, known substances usually added to bleaching and bleach-fixing baths such as pH buffers, e.g. borates, oxalates, acetates, carbonates, phosphates, alkylamines and polyethylene oxides, can be used.

Preferably, the total treatment time with the bleach bath and the bath with fixing ability, e.g. the fixing or bleach-fixing bath, should in the context of the present invention be no more than 3 min 45 s, expediently 20 s to 3 min 20 s, preferably 40 s to 3 min, in particular 60 s to 2 min 40 s, so that the desired effect according to the invention is achieved.

The bleaching time can be chosen as desired from the stated time period. In view of the success sought according to the invention, the bleaching time should not be more than 1 minute 30 seconds, expediently 10 to 70 seconds, preferably 20 to 55 seconds. The treatment time with the treatment bath with fixative ability can be chosen as desired from the stated entire time range. However, it is not more than 3 minutes 10 seconds, expediently 10 seconds to 2 minutes 40 seconds, preferably 20 seconds to 2 minutes 10 seconds.

In the treatment process according to the invention, the bleach bath, the fixing bath and the bleach-fixing bath should preferably be forced to stir. This is not only because this increases the success sought according to the invention, but also because this facilitates rapid treatment.

Such forced stirring is explained in Japanese Patent Application No. 63-46919/1988, description pages 64-68.

Examples of preferred treatment measures within the framework of the inventive method are given below. However, the invention is not limited thereto.

(1) Colour development T Bleaching T Fixing T Washing

(2) Color development T Bleaching T Fixing T Washing T Stabilizing

(3) Color developing T bleaching T fixing T stabilizing

(4) Color development T bleaching T fixing T first stabilization T second stabilization

(5) Colour development T Bleaching T Bleach-fixing T Washing

(6) Color development T Bleaching T Bleach-fixing T Washing T Stabilizing

(7) Color development T Bleaching T Bleach-fixing T Stabilizing

(8) Color development T bleaching T bleach-fixing T first stabilization T second stabilization, then if necessary third stabilization

Of these measures, (3), (4), (7) and (8) are preferred. Measures (3) and (4) are particularly preferred.

A further preferred embodiment of the treatment method according to the invention consists in that the liquid overflow from the color developer bath partially or completely overflows into the bleaching bath. Sludge formation in the bleaching bath can be reduced if a given amount of the color developer bath flows into the bleaching bath.

The color developer bath used in the invention contains alkaline agents commonly used in developer baths, for example sodium hydroxide, potassium hydroxide, ammonium hydroxide, Sodium carbonate, potassium carbonate, sodium sulfate, sodium metaborate and borax. It can also contain a variety of additives such as benzyl alcohol, alkali metal halides such as potassium bromide and potassium chloride, development control agents such as citracic acid and preservatives such as hydroxylamine and sulfites.

A wide variety of defoamers, wetting agents and organic solvents, such as methanol, dimethylformamide and dimethyl sulfoxide, can be suitably contained therein.

The developer bath used according to the invention usually has a pH value above 7, preferably from about 9 to 13.

Furthermore, the color developer bath used in the present invention may contain antioxidants such as hydroxylamine, tetronic acid, tetronimide, 2-anilinoethanol, dihydroxyacetone, an aromatic secondary alcohol, hydroxamic acid, pentose or hexose and pyrogallol-1,3-dimethyl ether.

In the color developer bath used according to the invention, a wide variety of chelating agents can be contained in combination as sequestering agents. Examples of such chelating agents are aminopolycarboxylic acids, such as ethylenediaminetetraacetic acid and diethylenetriaminepentaacetic acid, organic phosphonic acids, such as 1-hydroxyethylidene-1,1-diphosphonic acid, aminopolyphosphonic acids, such as aminotri(methylenephosphonic acid) and ethylenediaminetetraphosphoric acid, oxycarboxylic acids, such as citric acid and gluconic acid, phosphonocarboxylic acids, such as 2- phosphonobutane-1,2,4-tricarboxylic acid, and polyphosphoric acids, such as tripolyphosphoric acid and hexametaphosphoric acid.

Preferably, the color developer bath used according to the invention should contain a color developer in an amount of not less than 1.5 x 10⁻², preferably not less than 2.0 x 10⁻² mol/l.

According to the invention, the desired result can be further enhanced if the treatment is followed by stabilization with a fixing or bleach-fixing bath.

The amount of stabilizing bath replenisher solution is 1 to 80, preferably 2 to 60 times the amount of solution carried over from the preceding bath per unit area of the light-sensitive color photographic recording material for image recording. Preferably, the preceding bath component (namely the bleach-fix or fix bath) in the last chamber of the stabilizing tank should be less than 1/500, preferably less than 1/1000 of the stabilizer concentration. For reasons of reducing environmental pollution and extending the shelf life of the solution, the stabilizer tank should preferably be designed so that the concentration (in question) is 1/500 to 1/100,000, preferably 1/2000 to 1/50,000.

Preferably, the stabilizer tank should consist of more than one chamber, preferably 2 to 6 chambers.

In view of the success sought according to the invention, in particular the reduction of environmental pollution, the stabilizer tank should preferably have 2 to 6 chambers and be operated in countercurrent. In this case, the solution is fed to the rear bath and the solution from the previous bath is allowed to overflow. The tank should expediently have 2 or 3 chambers, preferably 2 chambers.

The infeed quantity varies with the type of photosensitive recording material, the transport speed and the process and the squeezing of the surface of the light-sensitive recording material in the automatic developing device. In the case of light-sensitive color photographic recording materials for taking pictures or conventional roll-on color films, the amount of inflow is usually 50 to 150 ml/m². Under these conditions, the success achievable according to the invention is even more evident if the amount of supplementary agent is 50 ml to 4.0 l/m², preferably 200 to 1500 ml/m².

The treatment temperature with the stabilizing bath is 15 to 60, preferably 20 to 45ºC.

The stabilizing bath used in the invention can contain a wide variety of chelating agents, as described in detail in Japanese Patent Application 63-46919/1988 of the applicant of the present application, on pages 73-82.

In order to achieve the desired result according to the invention and to achieve better image durability, the stabilizing bath used according to the invention should have a pH value of 4.0 to 9.0, preferably 4.5 to 9.0, preferably 5.0 to 8.5.

All generally known alkalis or acids can be used to adjust the pH value in the stabilizing baths preferably used according to the invention.

Salts of organic acids, e.g. citric, acetic, succinic, oxalic or benzoic acid, pH adjusters, e.g. phosphates, borates, hydrochloric acid, sulfates, wetting agents, preservatives and salts of metals such as Bi, Mg, Zn, Ni, Al, Sn, Ti and Zr, can be incorporated into the stabilizing baths preferably used according to the invention. These substances can be used in any combination and in any amount, provided that the pH value of the stabilizing bath according to the invention used stabilizing bath remains constant and neither the stability of color photographic images is impaired nor precipitation occurs during storage.

The fungicides preferably used in the stabilizing baths according to the invention are hydroxybenzoic acid esters, phenol compounds, thiazole compounds, pyridine compounds, guanidine compounds, carbamate compounds, morpholine compounds, quaternary phosphonium compounds, ammonium compounds, urea compounds, isoxazole compounds, propanolamine compounds, sulfamide compounds, amino acid compounds, active halogen-releasing compounds and benzotriazole compounds.

These fungicides are described in detail in the specification of the applicant’s Japanese Patent Application 63-46919/1988 on pages 84-90.

In the treatment process according to the invention, silver can be recovered from the stabilizing bath in a similar manner to that from the fixing and bleach-fixing bath.

The stabilizing bath used in the invention can be treated by means of an ion exchange resin, by electrodialysis (see Japanese Patent Application No. 96352/1984), reverse osmosis (see Japanese Patent Application No. 96532/1984) and the like.

Deionized water is preferably used for the stabilizing bath used in the invention, since the anti-fungal properties, stability and image storage capacity of the stabilizing bath are improved. Any means can be used for deionization as long as the dielectric constant of the treated water is below 50 µs/cm or the Ca/Mg ion concentration is below 5 ppm. Preferably, individually or in Combination treatment with an ion exchange resin or a reverse osmosis membrane. Ion exchange resins and reverse osmosis membranes are described in detail in Kokai-giho No. 87-1984. Preferably, a strongly acidic H-type cation exchange resin and a strongly alkaline OH-type anion exchange resin are used in combination.

To enhance the washing effect, improve the whiteness and the anti-fungal properties, the salt concentration of the stabilizing bath should preferably be below 1000 ppm, especially below 800 ppm.

In view of the success sought according to the invention, the duration of treatment with the stabilizing bath should not be more than 1 minute, expediently not more than 1 minute 30 seconds, preferably not more than 1 minute.

In the processing method according to the invention, there are no specific restrictions on the halogen composition of the light-sensitive material. However, the average silver iodide content of the entire silver halide emulsion should be 0.1 to 15, preferably 0.5 to 12, and more preferably 3 to 10 mol%.

There are also no restrictions on the average grain size of the entire silver halide emulsion in the light-sensitive material. However, the average grain size should not be more than 2.0, preferably 0.1 to 1.0, and more preferably 0.2 to 0.6 µm.

In the processing method according to the invention, there is a lower limit for the total dry thickness of all hydrophilic colloid layers in the light-sensitive recording material (hereinafter referred to as "emulsion side thickness") depending on the silver halide emulsion, the couplers, the oils, the additives and the like in the layer. The thickness of the emulsion side should be 10 to 50, preferably 15 to 30 µm.

Furthermore, it is also preferable that the distance between the top of the layer on the emulsion side and the bottom of the emulsion layer closest to the support be not less than 14 µm. The distance between the top and bottom of the emulsion layer which differs in color sensitivity from the emulsion layer closest to the support and is the second closest to the support be not less than 10 µm.

The light-sensitive recording material according to the invention is of the coupler-in-emulsion type (cf. US-A-2 376 679 and 2 801 171). Here, the couplers are contained in the light-sensitive recording material (itself). The couplers can be any couplers known in the relevant field. Examples of cyan couplers are compounds with a naphthol or phenol structure as the basic structure, which form an indoaniline dye upon coupling. Examples of magenta couplers are compounds with a 5-pyrazolone ring with an active methylene group as the skeletal structure and pyrazoloazole compounds. Examples of yellow couplers are compounds with a benzoylacetanilide, pivalylacetanilide or acylacetanilide structure with an active methylene ring. These couplers can have a substituent at the coupling site. As already mentioned, both 2- and 4-equivalent couplers can be used.

The couplers preferably used to enhance the desired effect of the invention are described in detail below.

The blue-green couplings can be represented by the following formulas CA, CB and CC: Formula CA: Formula CB

In these formulas:

R₁ represents an alkyl group, alkenyl group, cycloalkyl group, aryl group or heterocyclic group;

Y a group of formulas: with R₂ being an alkyl group, alkenyl group, cycloalkyl group, aryl group or heterocyclic group, R₃ being a hydrogen atom or a group corresponding to R₂ and R₂ and R₃, which may be the same or different, together being a 5- or 6-membered heterocycle, and

Z is a hydrogen atom or a group which can be split off in the coupling reaction with the oxidation product of the primary aromatic amine colour developer. Formula CC

where:

R1; -COHR₄R₅, -NHCOR₄, -NHCOOR₆, -NHSO₂R₆, -HNCONR₄R₅ or -NHSO₂NR₄R₅;

R₂ is a monovalent group;

R₃ is a substituent;

X is a hydrogen atom or a group which can be split off upon reaction with the oxidation product of the primary aromatic amine colour developer;

l is an integer, namely 0 or 1;

m is an integer from 0 to 3;

R₄ and R₅ independently represent a hydrogen atom, an aromatic group, an aliphatic group or a heterocyclic group;

R₆ is an aromatic group, aliphatic group or heterocyclic group, it being understood that in the case that m = 2 or 3, the units R₃ may be the same or different and may be bonded together to form a ring; R₄ and R₅, R₂ and R₃, R₂ and X may be bonded together to form a ring, in the case that 1 = 0, m = 0, R₁ represents -CONHR₇ and R₇ represents an aromatic group.

The cyan couplers of the formula CD (following) are preferred according to the invention. Formula CD

In the formula CD, R₄ is an optionally substituted aryl group, preferably phenyl group. Substituents for the aryl group are -SO₂R₅, halogen atoms, e.g. fluorine, chlorine or bromine, -CF₃, -NO₂, -CN, -COR₅, -COOR₅, -SO₂OR₅,

In the formulas:

R₅ is an alkyl group, preferably one with 1 to 20 carbon atoms, e.g. methyl, ethyl, tert-butyl and dodecyl, an alkenyl group, preferably one with 2 to 20 carbon atoms, e.g. an allyl or heptadecenyl group, a cycloalkyl group, preferably one with 5 to 7 ring members, e.g. a cyclohexyl group, or an aryl group, e.g. a phenyl, tolyl or naphthyl group, and

R₆ is a hydrogen atom or a group corresponding to R₅.

The compounds of formula C-D preferred according to the invention as cyan couplers contain an optionally substituted phenyl group as the radical R4. The substituent of the phenyl group can be cyano, nitro, -SO2R7, with R7 being an alkyl group, a halogen atom or trifluoromethyl.

In the formula CD, the definitions for Z and R₁ correspond to the corresponding definitions in the formulas CA and CB. The preferred ballast groups for R₁ are represented by the following formula CE. Formula CE

where:

J is an oxygen or sulphur atom or a sulphonyl group;

K is an integer from 0 to 4;

1 = 0 or 1;

R�8 is a normal or branched alkylene group having 1 to 20 carbon atoms, which may have an aryl group and the like as a substituent, and

R�9 is a monovalent group, provided that in case k = 2 or more, the R�9 units may be identical or different.

The cyan coupler is used in an amount of normally 1 x 10⁻³ to 1 mol, preferably 5 x 10⁻³ to 1 to 8 x 10⁻¹ mol per mol of silver halide.

In order to achieve the desired result according to the invention as best as possible, preferably at least one of the photographic layer units of a light-sensitive recording material to be treated according to the invention, in particular at least one of the green-sensitive emulsion layers, contains a magenta coupler of the following formula M-1. Formula M-1

In the formula:

Z is a non-metallic atom necessary to form an optionally substituted, nitrogen-containing heterocyclic ring;

X is a hydrogen atom or a group that can be split off in the reaction with the oxidation product of the colour developing agent and

R is a hydrogen atom or a substituent.

The magenta couplers mentioned are used in an amount of usually 1 x 10⊃min;³ to 1, preferably 1 x 10⊃min;² to 8 x 10⊃min;¹ mol per mol of silver halide.

The couplers preferably used according to the invention to form a purple dye can be represented by the following formula I. Formula I

In the formula, Ar represents a phenyl group, in particular a substituted phenyl group.

Suitable substituents are halogen atoms, alkyl groups, alkoxy groups, aryloxy groups, alkoxycarbonyl groups, cyano groups, carbamoyl groups, sulfamoyl groups, sulfonyl groups, sulfoamide groups and acylamino groups. The phenyl group represented by Ar may contain two or more substituents.

Y represents a group which is cleaved during dye formation in the coupling reaction with the oxidation product of a p-phenylenediamine color developing agent.

R:

If R represents an acylamino group, it consists, for example, of an acetamido, isobutylamino, benzamido, 3-[α-(2,4-di-tert-amylphenoxy)butylamido]benzamido, 3-[α-(2,4-di-tert-amylphenoxy)acetamido]benzamido, 3-[α-(3-pentadecylphenoxy)butylamido]benzamido, α-(2,4-di-tert-amylphenoxy)butylamido, α-(3-pentadecylphenoxy)butylamido, hexadecanamido, isostearoylamino, 3-(3-octadecenylsuccinimide)benzamido and pivaloylamino group. If R represents an anilino group, this consists, for example, of an anilino, 2-chloroanilino, 2,4-dichloroanilino, 2,5-dichloroanilino, 2,4,5-trichloroanilino, 2-chloro-5-tetradecanamidoanilino, 2-chloro-5-(3-octadecenylsuccinimido)anilino, 2- chloro-5- [α-(3-tert.-butyl-4-hydroxy)tetradecanamido]anilino, 2-chloro-5-tetradecyloxycarbonylanilino, 2-chloro-5-(N- tetradecylsulfamoyl)anilino, 2,4-dichloro-5-tetradecyloxyanilino, 2-chloro-5-(tetradecyloxycarbonylamino)anilino, 2- Chloro-5-octadecylthioanilino and 2-chloro-5-(N-tetradecylcarbamoyl)anilino group. When R represents a ureido group, this consists, for example, of a 3-{(2,4-di-tert-aminophenoxy)acetamido}phenylureido, phenylureido, methylureido, octadecylureido, 3-tetradecanamidophenylureido and N,N-dioctylureido group.

Of the compounds of formula I, those of the following formula II are preferred. Formula II

In the formula, Y and Ar have the meanings given in connection with Formula I.

X represents a halogen atom, an alkoxy group or an alkyl group.

Examples of the halogen atom, the alkoxy group and the alkyl group X are:

Halogen atom: chlorine, bromine, fluorine;

Alkoxy groups:

Alkoxy groups with 1 to 5 carbon atoms are preferred. Examples of these are the methoxy, ethoxy, butoxy, sec-butoxy and isopentyloxy groups.

Alkyl groups:

Alkyl groups with 1 to 5 carbon atoms are preferred. Examples of these are methyl, ethyl, isopropyl, butyl, tert-butyl and tert-pentyl groups.

Halogen atoms, especially chlorine, are particularly preferred.

R₁ represents a group capable of being bonded to a benzene ring as a substituent. n represents an integer, namely 1 or 2. When n = 2, the R₁ units may be the same or different.

These magenta couplers are added in an amount of preferably 0.005 to 2, more preferably 0.01 to 1 mol per mol of silver halide.

The cyan or magenta couplers mentioned can be used alone or in combination. They can also be used in combination with one or more other cyan or magenta couplers.

If the light-sensitive recording material has two or more light-sensitive emulsion layers of different sensitivities, one or more cyan or magenta couplers can be added to one or more of the emulsion layers. Preferably, the silver halide emulsions that can be used according to the invention contain tabular grains. Any silver halide can be used, including silver chloride, silver bromide, silver iodide, silver chlorobromide, silver chloroiodide, silver iodobromide and silver chloroiodobromide. A wide variety of substances are suitable as protective colloids for these silver halides, as well as naturally occurring substances such as gelatin.

The silver halide emulsion may contain conventional photographic additives such as stabilizers, sensitizers, hardeners, sensitizing dyes and wetting agents.

Color negative films, color paper, color reversal films, color reversal paper and other light-sensitive recording materials can be used in the present invention.

The present invention provides a treatment process free from bleach fog and a bleach bath that works well in the treatment process.

EXAMPLES

The present invention is explained in more detail using the following, but in no way limiting, examples.

example 1

The amounts of additives incorporated in the light-sensitive silver halide photographic recording material are given in 9 per m² (support material). The amounts of silver halide and colloidal silver are given as silver amounts.

By applying the following layers of the respective compositions to a cellulose triacetate film support, a highly sensitive multilayer light-sensitive color photographic recording material is produced.

Layer 1: Antihalation layer

Black colloidal silver 0.2

Gelatin 1.7

UV absorber (UV-1) 0.3

Colored coupler (CM-1) 0.2

Solvent for UV absorber dispersion (oil-1) 0.15

Solvent for UV absorber dispersion (oil-2) 0.15

Solvent for the colored coupler dispersion (oil-3) 0.2

Layer 2: Intermediate layer

Gelatin 1.2

Layer 3: First red sensitive emulsion layer

Silver iodobromide emulsion (Em-1) 1,

Silver iodobromide emulsion (Em-2) 0.5

Gelatin 1.3

Sensitizing dye (S-1) 0.5 x 10⊃min;⊃4; (mol/mol silver)

Sensitizing dye (S-2) 2 x 10⊃min;⊃4; (mol/mol silver)

Sensitizing dye (S-3) 2 x 10⊃min;⊃4; (mol/mol silver)

Blue-green coupler (C-1) 0.07

Cyan coupler (C-2) 0.3

Blue-green coupler (C-4) 0.3

Coloured cyan coupler (CC-1) 0.07

DIR connection (D-1) 0.005

Solvent for (C-1), (C-2), (C-4), (CC-1) and (D-1) (Oil-1) 0.2

Layer 4: Intermediate layer

Gelatin 0.8

Layer 5: First green-sensitive emulsion layer

Silver iodobromide emulsion (Em-1) 1.0

Silver iodobromide emulsion (Em-2) 0.5

Gelatin 1.4

Sensitizing dye (S-4) 1.8 x 10⊃min;⊃4; (mol/mol silver)

Sensitizing dye (S-5) 1.3 x 10⊃min;⊃4; (mol/mol silver)

Sensitizing dye (S-6) 9.2 x 10⊃min;⊃5; (mol/mol silver)

Sensitizing dye (S-7) 6.8 x 10⊃min;⊃5; (mol/mol silver)

Sensitizing dye (S-8) 6.2 x 10⊃min;⊃4; (mol/mol silver)

Purple coupler (M1) 0.15

Colored magenta coupler (CM-1) 0.08

Solvent for (M-1), (CM-1) dispersion (oil-3) 0.23

Layer 6: Intermediate layer

Gelatin 0.8

Anti-stain agent (SC-1) 0.05

Solvent for (SC-1) dispersion (Oil-3) 0.05

Layer 7: First blue-sensitive emulsion layer

Silver iodobromide emulsion (Em-1) 0.8

Gelatin 0.6

Sensitizing dye (S-9) 3 x 10⊃min;⊃4; (mol/mol silver)

Sensitizing dye (S-10) 1 x 10⊃min;⊃4; (mol/mol silver)

Yellow coupler (Y-1) 0.3

Solvent for (Y-1) dispersion (oil-3) 0.3

Layer 8: Intermediate layer

Gelatin 0.8

Anti-stain agent (SC-1) 0.05

Solvent for (SC-1) dispersion (Oil-3) 0.05

Layer 9: second red-sensitive emulsion layer

Silver iodobromide emulsion (Em-1) 1,

Silver iodobromide emulsion (Em-3) 2,

Fine-grained AgX emulsion (average grain size: 0.08 µm silver iodobromide with 1 mol% AgI) 0.5

Gelatin 2.4

Sensitizing dye (S-1) 0.2 x 10⊃min;⊃4; (mol/mol silver)

Sensitizing dye (S-2) 1.0 x 10⊃min;⊃4; (mol/mol silver)

Cyan coupler (C-1) 0.2

Blue-green coupler (C-3) 0.05

Blue-green coupler (C-4) 0.10

Anti-stain agent (SC-1) 0.05

Solvent for (C-1), (C-3), (C-4), (SC-1) Dispersion (Oil-1) 0.4

Layer 10: Intermediate layer

Gelatin 0.8

Anti-stain agent (SC-1) 0.07

Colored magenta coupler (CM-1) 0.04

Solvent for (SC-1), (CM-1), Dispersion (Oil-3) 0.25

Layer 11: Second green-sensitive emulsion layer

Silver iodobromide emulsion (Em-1) 0.8

Silver iodobromide emulsion (Em-3) 1.6

Gelatin 1.6

Sensitizing dye (S-4) 6.8 x 10⊃min;⊃5; (mol/mol silver)

Sensitizing dye (S-5) 6.7 x 10⊃min;⊃5; (mol/mol silver)

Sensitizing dye (S-6) 2.1 x 10⊃min;⊃6; (mol/mol silver)

Purple coupler (M-1) 0.2

Colored magenta coupler (CM-1) 0.02

Solvent for (M-1), (CM-1), Dispersion (Oil-4) 0.2

Layer 12: Intermediate layer

Fine-grained AgX emulsion (average grain size: 0.08 µm; silver iodobromide with 2 mol% AgI) 0.3

Gelatin 0.8

Anti-stain agent (SC-1) 0.05

Solvent for (SC-1) dispersion (Oil-3) 0.05

Layer 13: Second blue-sensitive emulsion layer

Silver iodobromide emulsion (Em-1) 0.7

Silver iodobromide emulsion (Em-4) 1.4

Fine-grained AgX emulsion (avg. Grain size: 0.08 µm; silver iodobromide with 2 mol% AgI) 0.1

Fine-grained AgX emulsion (average grain size: 0.03 µm; silver iodobromide with 2 mol% AgI) 0.1

Gelatin 2.1

Sensitizing dye (S-10) 0.4 x 10⊃min;⊃4; (mol/mol silver)

Sensitizing dye (S-11) 1.2 x 10⊃min;⊃4; (mol/mol silver)

Yellow coupler (Y-1) 0.8

Solvent for (Y-1) dispersion (Oil-3) 0.8

Layer 14: First protective layer

Gelatin 1.5

UV absorber (UV-1) 0.1

UV absorber (UV-2) 0.1

Formalin scavenger (HS-1) 0.5

Formalin scavenger (HS-2) 0.2

Solvent for UV absorber dispersion (oil-1) 0.1

Solvent for UV absorber dispersion (oil-2) 0.1

Layer 15: Second protective layer

Gelatin 0.6

Alkali-soluble roughening agent (average grain size: 2 µm) 0.12

Polymethyl methacrylate (average grain size: 3 µm) 0.02

Lubricant (WAX-1) 0.04

Antistatic agent (W-1) 0.004

The individual layers were also treated with the coating aid Su-1, the dispersing aids Su-2 and Su-3, Hardeners H-1 and H-2, stabilizer ST-1 and antifogging agents AF-1 and AF-2 are added.

Em-1

Monodisperse emulsion with relatively low silver iodide content in the surface part of the silver halide grains with an average grain size of 0.8 µm and an average silver iodide content of 8.0%.

Em-2

Monodisperse emulsion with relatively low silver iodide content in the surface part of the silver halide grains with an average grain size of 0.4 µm and an average silver iodide content of 7.0%.

Em-3

Monodisperse emulsion with relatively low silver iodide content in the surface part of the silver halide grains with an average grain size of 1.6 µm and an average silver iodide content of 6.4%.

Em-4

Monodisperse emulsion with a relatively low silver iodide content in the surface part of the silver halide grains with an average grain size of 2.0 µm and an average silver iodide content of 7.0%.

The test specimen prepared in the manner described was exposed to white light through a step wedge and then developed as follows: (Treatment regimen)

The treatment baths used had the following composition:

(color developer bath)

Potassium carbonate 30 g

Sodium hydrogen carbonate 2.5 g

Potassium sulphite 49

Sodium bromide 1.3 g

Potassium iodide 1.2 mg

Hydroxylamine sulfate 2.5 g

Sodium chloride 0.6 g 4-Amino-3-methyl-N-ethyl-N-(β- hydroxyethyl)aniline sulfate 4.8 g

Potassium hydroxide 1.2 g

Filled with water to 1 l

The pH value is adjusted to 10.06 with potassium hydroxide or 50% sulfuric acid.

(bleach bath)

Iron(III)ammonium salt of example compound A-1 150 g

Compound according to Table 1 (hereinafter referred to simply as compound) 0.4 mol

Ammonium bromide 150 g

Filled with water to 1 l

The pH value is adjusted to 5.2 with aqueous ammonia or glacial acetic acid.

(Fixing bath)

Ammonium thiosulfate 250 g

Ammonium sulphite 20 g

Example compound A-7 (ammonium salt) 2 g

Filled with water to 1 l

The pH value is adjusted to 6.8 with acetic acid and aqueous ammonia.

(Stabilizing bath)

Formaldehyde (37% solution) 2 ml

5-Chloro-2-methyl-4-isothiazolin-3-one 0.05 g

Emulgen 810 (wetting agent) 1 ml

Addition product of formaldehyde and sodium bisulfite 2 g

Filled with water to 1 l

The pH value is adjusted to 7.0 with aqueous ammonia and 50% sulfuric acid.

The compound shown in Table 1 was added to the bleaching bath and then treated. The minimum density values for B (blue), G (green) and R (red) were determined using an optical densitometer PDA-65A (from Konica Corporation).

For comparison purposes, a treatment was carried out using Bleaching Bath No. 23 in the presence of a ferric ammonium salt of Example A'-1 instead of the ferric ammonium salt of Example A-1 and in the absence of any compounds according to Table 1. The time of bleaching was extended from 45 s to 6 min.

For further comparison, treatment was carried out under the following conditions (using bleach bath No. 24).

The stop bath used was one with the following composition:

(Stop bath)

Acetic acid 20 g

Filled with water to 1 l

The pH is adjusted to 4.0 with sodium hydroxide used.

The bleaching bath was the same as the bleaching bath mentioned above, but without the addition of any compound according to Table 1. The color developer bath, the fixer bath and the stabilizer bath were the same as the baths indicated.

The results can be found in Table 1.

A 5-fold concentrate of the respective color developer was prepared and added to the bleach bath used in the described experiment in a quantity of 50 ml/l. This mixture was left to stand for 1 day and then visually assessed by 3 people for the presence of solids floating on the surface. The results are shown in Table 2. Table 1 (1/2) Table 1 (2/2) Table 2

- : No suspended solids

+ : Floating solids were found on less than 1/5 of the area

++ : Floating solids were found on 1/5 to 1/2 of the surface

+++ : Floating solids were found on more than 1/2 of the area

The symbols for the floating solids in the following tables correspond to the indicated rating.

As can be seen from Table 1, bleach fogging can be effectively prevented by adding to the bleaching bath both an iron(III) complex salt of an organic acid according to invention as well as a buffer capable of adjusting the pH value to 3 to 7.

It also turns out that the absence of even one of these conditions leads to a loss of the anti-bleaching fog effect.

Similar results were obtained when experiments were carried out using iron(III) salts of B-1 instead of iron(III) salts of A-1.

Example 2

Tests were carried out using varying amounts of citric acid and acetic acid as in Example 1. The results are shown in Tables 3 and 4. Table 3 Table 4

Similar results were obtained when experiments were carried out using iron(III) salts of B-1 instead of iron(III) salts of A-1.

Example 3

A bleach fogging test was carried out, whereby the pH of the bleach bath was varied by adding 0.3 mol/l citric acid and 0.3 mol/l 1-(N-morpholino)ethanesulfonic acid. The results are shown in Table 5. Table 5

Tables 3 to 5 show that the addition of a buffer according to the invention capable of adjusting the pH to 3 to 7 has proven effective. Tables 3 and 4 also show that acetic acid is required in a larger amount because it is weaker than other compounds. It is recommended that the acetic acid be used in an amount of more than 0.5, preferably more than 0.7. Table 5 shows that the bleaching bath according to the invention works well at pH values of 3 to 7.

Similar results were obtained when experiments were carried out using iron(III) salts of B-1 instead of those of A-1.

Example4

Tests were carried out using ferric ammonium salts of chelating agents other than the example chelating agent A-1 in the presence/absence of citric acid. The bleaching time was set at 6 minutes so that bleaching was achieved even when the bleaching power of the chelating agent was low. The results are shown in Table 6. Table 6

It is clear from Table 6 that iron(III) complex salts of organic acids other than Example Compound A-1 according to the invention also exhibit an anti-bleaching fogging effect when used according to the invention.

Similar results were obtained when the example compounds A-1 and B-1 were used together in a ratio of 1/1.

Example 5

By applying the following layers to a triacetyl cellulose film support in the order given A multilayer light-sensitive color photographic recording material (test specimen 2) was produced from the layer carrier.

Candidate 2

Layer 1: Antihalation layer (HC-1)

Black colloidal silver 0.22

UV absorber (UV-1) 0.20

Coloured copper (CC-1) 0.05

Coloured copper (CM-2) 0.05

High boiling solvent (oil-1) 0.20

Gelatin 1.4

Layer 2: Intermediate layer (IL-1)

UV absorber (UV-1) 0.01

High boiling solvent (oil-1) 0.01

Gelatin 1.4

Layer 3: Low-sensitivity red-sensitive emulsion layer (RL)

Silver iodobromide emulsion (Em-5) 1.0

Silver iodobromide emulsion (Em-6) 0.5

Sensitizing dye (S-1) 2.5 x 10⊃min;⊃4; (mol/mol silver)

Sensitizing dye (S-3) 2.5 x 10⊃min;⊃4; (mol/mol silver)

Sensitizing dye (S-2) 0.5 x 10⊃min;⊃4; (mol/mol silver)

Blue-green coupler (C-4) 1.2

Blue-green coupler (C-1) 0.06

Coloured cyan coupler (CC-1) 0.05

DIR connection (D-2) 0.002

High boiling solvent (oil-1) 0.5

Gelatin 1.4

Layer 4: Highly sensitive red-sensitive emulsion layer (RH)

Silver iodobromide emulsion (Em-7) 2.0

Sensitizing dye (S-1) 2.0 x 10⊃min;⊃4; (mol/mol silver)

Sensitizing dye (S-3) 2.0 x 10⊃min;⊃4; (mol/mol silver)

Sensitizing dye (S-2) 1.0 x 10⊃min;⊃4; (mol/mol silver)

Blue-green coupler (C-2) 0.15

Blue-green coupler (C-1) 0.018

Blue-green coupler (C-3) 1.15

Coloured cyan coupler (CC-1) 0.015

DIR connection (D-3) 0.05

High boiling solvent (oil-4) 0.5

Gelatin 1.4

Layer 5: Intermediate layer (IL-2)

Gelatin 0.5

Layer 6: Low-sensitivity green-sensitive emulsion layer (GL)

Silver iodobromide emulsion (Em-5) 1.0

Sensitizing dye (S-8) 5.0 x 10⊃min;⊃4; (mol/mol silver)

Sensitizing dye (S-7) 1.0 x 10⊃min;⊃4; (mol/mol silver)

Purple coupler (M-1) 0.5

Colored magenta coupler (CM-1) 0.05

DIR connection (D-4) 0.015

DIR connection (D-5) 0.020

High boiling solvent (oil-2) 0.5

Gelatin 1.0

Layer 7: Intermediate layer (IL-3)

Gelatin 0.8

High boiling solvent (oil-1) 0.2

Layer 8: Highly sensitive green-sensitive emulsion layer (GH)

Silver iodobromide emulsion (Em-7) 1.3

Sensitizing dye (S-5) 1.5 x 10⊃min;⊃4; (mol/mol silver)

Sensitizing dye (S-4) 2.5 x 10⊃min;⊃4; (mol/mol silver)

Sensitizing dye (S-6) 0.5 x 10⊃min;⊃4; (mol/mol silver)

Purple coupler (M-2) 0.06

Purple coupler (M-3) 0.18

Colored magenta coupler (CM-2) 0.05

DIR connection (D-4) 0.01

High boiling solvent (oil-3) 0.5

Gelatin 1.0

Layer 9: Yellow filter layer (YC)

Yellow colloidal silver 0.1

Anti-stain agent (SC-2) 0.1

High boiling solvent (oil-3) 0.1

Gelatin 0.8

Layer 10: Low-sensitivity blue-sensitive emulsion layer (BL)

Silver iodobromide emulsion (Em-5) 0.25

Silver iodobromide emulsion (Em-6) 0.25

Sensitizing dye (S-9) 7.0 x 10⊃min;⊃4; (mol/mol silver)

Yellow coupler (Y-1) 0.6

Yellow coupler (Y-2) 0.12

DIR connection (D-3) 0.01

High boiling solvent (oil-3) 0.15

Gelatin 1.0

Layer 11: Highly sensitive blue-sensitive emulsion layer (BH)

Silver iodobromide emulsion (Em-8) 0.50

Silver iodobromide emulsion (Em-5) 0.20

Sensitizing dye (S-10) 1.0 x 10⊃min;⊃4; (mol/mol silver)

Sensitizing dye (S-9) 3.0 x 10⊃min;⊃4; (mol/mol silver)

Yellow coupler (Y-1) 0.36

Yellow coupler (Y-2) 0.06

High boiling solvent (oil-3) 0.07

Gelatin 1.1

Layer 12: First protective layer (Pro-1)

Fine-grained silver iodobromide emulsion (average grain size: 0.08 µm; AgI = 2 mol%) 0.4

UV absorber (UV-1) 0.10

UV absorber (UV-2) 0.05

High boiling solvent (oil-1) 0.1

High boiling solvent (oil-1) 0.1

Formalin scavenger (HS-1) 0.5

Formalin scavenger (HS-2) 0.2

Gelatin 1.0

Layer 13: Second protective layer (Pro-2)

Antistatic agent (W-1) 0.005

Alkali-soluble roughening agent (average grain size: 2 µm) 0.10

Blue-green dye (AIC-1) 0.005

Purple dye (AIM-1) 0.01

Lubricant (WAX-1) 0.04

Gelatin 0.8

The coating agent Su-1, the dispersing agent Su-2, the hardening agents H-1 and H-2, the preservative DI-1, the stabilizer ST-1 and the antifogging agents AF-1 and AF-2 were also added to the individual layers.

Em-5

Monodisperse emulsion with a relatively low silver iodide content in the surface part of the silver halide grains with an average grain size of 0.46 µm and an average silver iodide content of 7.5%

Em-6

Monodisperse emulsion of uniform composition with an average grain size of 0.32 µm and an average silver iodide content of 2.0%

Em-7

Monodisperse emulsion with a relatively low silver iodide content in the surface part of the silver halide grains with an average grain size of 0.78 µm and an average silver iodide content of 6.0%

Em-8

Monodisperse emulsion with a relatively low silver iodide content in the surface part of the silver halide grains with an average grain size of 0.95 µm and an average silver iodide content of 8.0%

Emulsions Em-5, Em-7 and Em-8 consisted of silver iodobromide emulsions mainly of octahedral grains of multilayered structures prepared according to Japanese Patent Application Laid-Open Nos. 60-138538/1985 and 61-245151/1986.

In the individual emulsions Em-5 to Em-8, the average grain diameter/grain thickness was 1.0 with a scatter in the grain (size) distribution of 14, 10, 12 and 12%, respectively.

The test specimen prepared in the manner described was exposed to white light through a step wedge and then developed as follows:

The tank baths used had the same compositions as in Example 1. For the continuous treatment, supplementary solutions with the following compositions were used:

(Color developer replenisher)

Potassium carbonate 40 g

Sodium hydrogen carbonate 3 g

Potassium sulphite 79

Sodium bromide 0.5 g

Hydroxylamine sulphate 3.1 g

4-Amino-3-methyl-N-ethyl-N-(β-hydroxyethyl) aniline sulfate 6.0 g

Potassium hydroxide 2 g

Filled up to 1 l with water The pH value is adjusted to 10.12 with potassium hydroxide or 20% sulfuric acid.

(bleach bath)

The bleaching bath of Example 1 was used, but after adjusting its pH to 4.8.

The fixer replenisher and stabilizer replenisher were the same as those in Example 1.

The treatment measures, treatment time, treatment temperature and supplementary solution amount in the continuous treatment were as follows:

The amount of supplementary solution is given in ml per 100 cm² of the light-sensitive recording material.

Fixation treatment was carried out using the double-tank countercurrent method (45 s, 2 tanks) and stabilization was carried out using the 3-tank countercurrent method (20 s, 3 tanks).

The run-through treatment was carried out until the amount of bleaching bath replenisher solution reached twice the capacity of the bleaching tank in 40 days. After completion of the run-through treatment, the film sample was measured as in Example 1. However, the run-through treatment was carried out in the absence/presence of 0.4 mol/l citric acid or 1.5 mol/l acetic acid, with the amount of bleaching bath replenisher solution being changed to 0.75, 1.5, 5 or 10 ml per 100 cm².

Further tests were carried out in accordance with Example 1, except that the color developer tank, bleach tank, fixer tank and stabilizer tank were each provided with a vinyl chloride nozzle with an opening of 0.5 mm in diameter. An Iwake MD-15 magnetic pump was used to spray the processing baths onto the surface of the light-sensitive emulsion. Only the bleach tank was ventilated in such a way that the air volume corresponded to the capacity of the bleach tank in 2 minutes. With the ventilation continued when the light-sensitive material was introduced into the automatic developing device.

The results are summarized in Table 7. Table7

Footnote: The evaluation criteria for the appearance of the tank bath surface were the same as those of Example 1.

It can be seen from Table 7 that the treatment process according to the invention is beneficial both for preventing bleach fogging and for the appearance of the solution.

Example 6

Tests were carried out in accordance with Example 1, but the color developing compound 4-amino-3-methyl-N-ethyl-N-(β-hydroxyethyl) aniline sulfate was contained in the color developing bath in the amounts indicated in Table 8 and the treatment time was varied in accordance with Table 8. The treatment time was adjusted so that the sensitometric results agreed with each other.

Bleaching was carried out in the absence/presence of 0.8 mol/l citric acid in the bleaching bath.

For comparison purposes, tests were carried out with a (switched on) stopping procedure according to test No. 24 of Example 1. The results are also given in Table 8. Table 8

Example 7

The various samples were continuously treated - with and without aeration as in Example 5 - with the addition of the same amount of replenisher solution of 1.5 ml/100 cm² as in Experiments 52, 56 and 60. After the maximum cyan density achieved was measured, the sample was treated again with a freshly prepared bleach bath. A phenomenon of non-recurrence on the cyan image due to the continuous treatment was determined by comparing the maximum density values obtained before and after the re-treatment. Table 9 shows the respective non-recurrence ratio (%), which is defined as the ratio (%) of a difference between the maximum density values before and after the re-treatment with the fresh bleach bath to the maximum density value before the re-treatment. Table 9

Lower values for the poor color recovery ratio for cyan Dmax indicate lower levels of non-color recovery.

Table 9 shows that ventilation is effective.

Example 8

The treatment and evaluation were carried out according to Experiment No. 13 (succinic acid was used as pH buffer) and 20 (no pH buffer was used) of Example 1. Instead of the cyan couplers C-1 and C-4, the cyan couplers listed in Table 10 were used in molar amounts corresponding to those of C-1 and C-4.

The results of the minimum density of the blue-green dye determined using red light are shown in Table 10. Table 10

As shown in Table 10, cyan bleach fog was alleviated by replacing the cyan couplers with the cyan couplers preferred in the present invention.

The cyan couplers listed in Table 10 have the following formulas:

Example 9

The treatment and evaluation were carried out according to Experiment No. 13 (succinic acid was used as pH buffer) or 20 (no pH buffer was used) of Example 1, but instead of the magenta coupler M-1, the magenta couplers listed in Table 11 were used in molar amounts corresponding to the molar amount of M-1.

The results for the minimum density of the magenta dye determined with green light are given in Table 11. Table 11

As shown in Table 1, the magenta bleach fog was alleviated by replacing the magenta couplers with the magenta couplers preferred in the present invention.

The magenta couplers listed in Table 11 have the following formulas: Purple coupler 1 for comparison purposes Purple coupler 2 for comparison purposes

Example 10

The light-sensitive recording material (test specimen 1 of Example 1) was developed and bleached in the absence/presence of 1.5 mol/l acetic acid or 0.8 mol/l citric acid, the amount of iron(III) complex salts of an aminopolycarboxylic acid used as bleaching agent in the bleaching baths being varied according to Table 12 and bleaching was carried out for 3 minutes. The results can be found in Tables 12 and 13. Table 12 Table 13

Footnote: Evaluation criteria for the solution surface corresponded to those of Example 1.

As is clear from Tables 12 and 13, the present invention has been found to be very effective when a ferric complex salt of A-1 is present as a bleaching agent in an amount of more than 0.2 mol/l or when the molar ratio of a ferric complex salt of an aminopolycarboxylic acid used as a bleaching agent with respect to A'-1 not representable by the formula A exceeds 40%.

Example 11

The light-sensitive recording material of Example 1 was developed according to the following treatment scheme and using the following treatment baths.

The treatment baths used had the following composition:

(color developer bath)

Potassium carbonate 30 g

Sodium hydrogen carbonate 2.5 g

Potassium sulphite 4 g

Diethylenetriaminepentaacetic acid 3.0 g

Sodium bromide 1.3 g

Potassium iodide 1.2 mg

Hydroxylamine sulfate 2.5 g

Sodium chloride 0.6 g

4-Amino-3-methyl-N-ethyl-N-(β-hydroxyethyl)aniline sulfate 15.0 g

Potassium hydroxide 1.2 g

Filled with water to 1 l

The pH value is adjusted to 10.20 with potassium hydroxide or 50% sulfuric acid.

(bleach bath)

Iron(III)ammonium salt of Example A-1 (for the quantity see Table 14)

The compound listed in Table 14 (for the amount see Table 14)

Ammonium bromide 150 g

Filled with water to 1 l

The pH value is adjusted to 4.4 with aqueous ammonia or glacial acetic acid.

(Fixing bath)

Ammonium thiosulfate 180 g

Ammonium sulphite 15 g

Ammonium thiocyanate 180 g

Ammonium carbonate 20 g

Filled with water to 1 l

The pH value is adjusted to 7.5 with acetic acid and aqueous ammonia.

(Stabilizing bath)

5-Chloro-2-methyl-4-isothiazolin-3-one 0.05 g

2-Methyl-4-isothiazolin-3-one 0.05 g

Emergen 810 (wetting agent) 4 ml

Filled with water to 1 l

The test specimen treated in the manner described was measured for the minimum density values for B (blue), G (green) and R (red) using an optical densitometer PDA-65A (Konica Corporation). Table 14

It can be seen from Table 14 that a buffer according to the invention should preferably be present in amounts of more than 0.1 mol/l when an iron (III) salt of a compound of formula A or B is present in an amount of 0.3 to 1 mol per 1 liter of bleaching bath.

Claims (20)

1. Process for treating a light-sensitive colour photographic silver halide recording material by Developing the light-sensitive recording material with a color developer; Bleaching the light-sensitive recording material immediately after the development stage with a bleach bath and Treating the light-sensitive recording material after the bleaching step with a bath with fixing ability, the bleaching bath containing at least one of the iron (III) complex salts of compounds of the following formulas A or B in an amount of at least 0.01 mol/l of bleaching bath and a buffer with the ability to adjust the pH to 3 to 7 of the following formula I, the pH of the bleaching bath is kept in the range of 3 to 7 and the bleaching bath is supplemented with a bleaching bath refresher solution in an amount of 30 ml to 350 ml/m² of the light-sensitive color photographic silver halide recording material 5: Formula A where: A₁ to A₄, which may be the same or different, each represent a -CH₂OH-, -COOM- or -PO₃M₁M₂- group; M, M₁ and M₂ each represent a hydrogen, sodium or potassium atom or an ammonium group and X is an optionally substituted alkylene group having 3 to 6 carbon atoms; Formula B wherein A₁ to A₄ have the meaning given for formula A, n is an integer from 1 to 8 and B₁ and B₂, which may be the same or different, each represent an optionally substituted alkylene group having 2 to 5 carbon atoms; Formula I A - COOH where A represents a hydrogen atom or an organic group , acetic acid being excluded for the formula I. 2. The method according to claim 1, wherein the buffer is selected from the group: Acrylic acid, adipic acid, acetylenedicarboxylic acid, acetoacetic acid, azelaic acid, isocrotonic acid, isopropylmalonic acid, isobutyric acid, itaconic acid, isovaleric acid, ethylmalonic acid, caproic acid, formic acid, valeric acid, citric acid, glycolic acid, glutaric acid, crotonic acid, chlorofumaric acid, α-chloropropionic acid, gluconic acid, glyceric acid, β-chloropropionic acid, succinic acid, cyanoacetic acid, diethylacetic acid, Dimethylmalonic acid, dichloroacetic acid, citraconic acid, dimethylmalonic acid, oxalic acid, d-tartaric acid, meso-tartaric acid, trichloromuchic acid, tricarballylic acid, trimethylacetic acid, lactic acid, vinylacetic acid, pimelic acid, pyrowaric acid, racemic tartaric acid, fumaric acid, propionic acid, propylmalonic acid, maleic acid, malonic acid, mesaconic acid, methylmalonic acid, monochloroacetic acid, n-butyric acid, malic acid, aspartic acid, DL-alanine, glutamic acid, 3,3-dimethylglutaric acid, ascorbic acid, atropic acid, allocinnamic acid, benzoic acid, isophthalic acid, oxybenzoic acid (m-, p-), chlorobenzoic acid (o-, m-, p-), chlorophenylacetic acid (o-, m-, p-), cinnamic acid, salicylic acid, dioxybenzoic acid (2,3-, 2,4-, 2,5-, 2,6-, 3,4-, 3,5), cyclobutane-1,1-dicarboxylic acid, cyclobutane-1,2-dicarboxylic acid (trans-, cis-), cyclopropane-1,1-dicarboxylic acid; Cyclopropane-1,2-dicarboxylic acid (trans-, cis-), cyclohexane-1,1-dicarboxylic acid, cyclohexane-1,2-dicarboxylic acid (trans-, cis-), cyclohexylacetic acid, cyclopentane-1,1-dicarboxylic acid, 3,5-dinitrobenzoic acid, 2,4-dinitrophenoldiphenyl acid, terephthalic acid, toluic acid (o-, m-, p-), naphthoic acid (α-,β-), nicotinic acid, nitrobenzoic acid, nitrophenyl acid (o-, m-, p-), pyrosmucous acid, hippuric acid, picolinic acid, phenylacetic acid, phenyl acid, phthalic acid, fluorobenzoic acid (o-, m-, p-), bromobenzoic acid (o-, m-, p-), hexahydrobenzoic acid, benzylic acid, dl-mandelic acid, mesitylenic acid, Methoxybenzoic acid (o-, m-, p-), methoxycinnamic acid (o-, m-, p-), p-methoxyphenylacetic acid, gallic acid and aminobenzoic acid (o-, m-, p-), N-(2-acetamido)iminodiacetic acid, ethylenediaminediacetic acid, ethylenediamine-2-propionic acid, β-aminoethyliminodiacetic acid and organic phosphoric acids such as aminomethylphosphono-N,N-diacetic acid, 2-phosphonoethyliminodiacetic acid, 2-phosphonobutane-1,2,4-tricarboxylic acid and the following (Acids): is selected. 3. The method according to claim 2, wherein the buffer is selected from the group consisting of acrylic acid, adipic acid, acetoacetic acid, isopropylmalonic acid, isobutyric acid, itaconic acid, formic acid, valeric acid, citric acid, glutaric acid, succinic acid, diethylmalonic acid, oxalic acid, d-tartaric acid, fumaric acid, malonic acid, n-butyric acid, malic acid and glutamic acid. 4. The method according to claim 1, wherein the bleaching bath contains the iron (III) complex salt in an amount of 0.01 to 1.0 mol/l bleaching bath. 5. The method according to claim 4, wherein the bleaching bath contains the iron (III) complex salt in an amount of 0.1 to 1.0 mol/l bleaching bath. 6. The method according to claim 5, wherein the bleaching bath contains the iron (III) complex salt in an amount of 0.15 to 0.8 mol/l bleaching bath. 7. The method according to claim 1, wherein the bleaching bath contains the buffer in an amount of 0.01 to 3.0 mol/l bleaching bath. 8. The method of claim 7, wherein the bleaching bath contains the buffer in an amount of 0.02 to 2.0 mol/l of bleaching bath. 9. The method according to claim 8, wherein the bleaching bath contains the buffer in an amount of 0.1 to 2.0 mol/l bleaching bath. 10. The process of claim 1, wherein the bleaching bath contains the iron(III) complex salt and the buffer in amounts of 0.3 to 1.0 mol or 0.1 to 2.0 mol (respectively) per litre of bleach bath. 11. The method according to claim 11, wherein the pH of the bleaching bath is maintained in the range of 4 to 6. 12. The method of claim 11, wherein the pH of the bleaching bath is maintained in the range of 4.5 to 5.8. 13. The method of claim 1, wherein the bleaching bath contains a halide compound. 14. The method according to claim 12, wherein the bleaching bath contains a halide compound in an amount of 0.1 to 5 mol/l bleaching bath. 15. The method according to claim 14, wherein the bleaching bath contains a halide compound in an amount of 0.3 to 3 mol/l bleaching bath. 16. The method according to claim 1, wherein the bath having fixing ability consists of a fixing bath. 17. The method according to claim 1, wherein the bath having fixing ability consists of a bleach-fix bath. 18. The process of claim 1, wherein the bleaching step lasts no longer than 1 min 30 s. 19. The method according to claim 1, wherein the treatment with the bath having fixing ability lasts not longer than 3 min 10 s. 20. The method according to claim 1, wherein the total time for bleaching and treatment with the bath with fixability is not longer than 3 min 45 s.