EP0312837A2 - Method of photographic processing without rinse water, and stabilizing bath used in this method - Google Patents

Abstract

A washing water-free processing method for producing color photographic images with the processing steps developing, bleaching, fixing and stabilizing, the bleaching and fixing steps for the bleach-fixing step being able to be contracted, leads to color images of perfect quality even after prolonged use, if the stabilizing bath used in the stabilizing step introduces an effective amount Contains pyrazole, which in one of the possible tautomeric formulas corresponds to the general formula <IMAGE>, in which X is OH or NH2, R1 is alkyl, substituted alkyl, aryl, substituted aryl or carboxyl, R2 is hydrogen, alkyl or substituted alkyl, R3 is hydrogen, alkyl, substituted alkyl, aryl or substituted aryl.

Description

The invention relates to a washing water-free photographic processing method and a stabilizing bath used in this method, with the aid of which it is possible to produce color images whose minimum densities are of excellent quality even under tropical storage conditions.

Color photographic processing methods for producing color images usually include the steps of developing, bleaching, fixing, washing, stabilizing and drying, the steps of bleaching and fixing being able to be combined into a single bleach-fixing step, since by washing, with which a number of chemicals from the processing material, a large amount of waste water is produced, there has been no lack of attempts to avoid this step and to carry out the stabilization in such a way that a qualitatively satisfactory image is produced is, although the chemicals in the material from the previous process steps are no longer removed. Such methods are described, for example, in the following European patent applications: 182 566, 185 371, 186 158, 186 169, 186 504 and 206 148. Although these previously known methods and in particular the stabilizing baths used therein, color images of satisfactory quality are produced, in particular also those which show no yellowing when stored in the tropics, but only as long as the stabilizing bath is fresh. If the stabilizing bath is used for a longer period of time, the color images produced show an increasingly greater yellowing under tropical storage. If one goes from the usual regeneration rate of the stabilizing bath of 250 ml / m² in a three-stage cascade to higher regeneration rates, e.g. 500 to 1000 ml / m², yellowing under tropical conditions can be reduced to a lesser extent, but it is now undesirable large amount of used stabilizing bath, so that the actual advantage of the washing water-free processing method by means of a special stabilizing bath is no longer given.

The object of the invention was therefore to propose a stabilizing bath which, at the usual regeneration rate, ensures that, even with prolonged use, the color images produced have a quality under tropical storage that can otherwise only be achieved in processes which still contain a washing step.

It has now been found that this object can be achieved by adding a special pyrazole compound to the stabilizing bath for a washing water-free processing method.

entspricht, worin
X OH oder NH₂,
R₁ Alkyl, substituiertes Alkyl, Aryl, substituiertes Aryl oder Carboxyl,
R₂ Wasserstoff, Alkyl oder substituiertes Alkyl,
R₃ Wasserstoff, Alkyl, substituiertes Alkyl, Aryl oder substituiertes Aryl bedeuten.The invention therefore relates to a washing water-free processing method for producing color photographic images with the processing steps developing, bleaching, fixing and stabilizing, the bleaching and fixing steps being able to be combined to form the bleach-fixing step, characterized in that the stabilizing bath used in the stabilizing step contains an effective amount of a pyrazole , in one of the possible tautomeric formulas of the general formula

corresponds to what
X OH or NH₂,
R₁ alkyl, substituted alkyl, aryl, substituted aryl or carboxyl,
R₂ is hydrogen, alkyl or substituted alkyl,
R₃ is hydrogen, alkyl, substituted alkyl, aryl or substituted aryl.

Carboxyl, sulfonyl and sulfonamide groups are particularly suitable as substituents for the alkyl and aryl radicals. The pyrazole compounds preferably contain at least one acidic group. The hydroxyl and amino groups in the 5-position can also be present in another tautomeric form as oxo or imino groups.

The following list shows particularly suitable compounds to be used according to the invention:

The invention furthermore relates to the stabilizing bath used in the process according to the invention, which in a preferred embodiment contains at least one sequestering agent in addition to the pyrazole compound and whose pH value is in the range from 3.0 to 7.8, preferably 5.0 to 6.0 lies. The desired pH is adjusted, for example, by appropriate neutralization of the acids (sequestering agents, complexing agents) present in the stabilizing bath with NaOH, KOH, MgO or ammonia. In addition to the Na ^⊕ , K ^⊕ , Mg² ^⊕ or ammonium ions, the stabilizing bath contains, in particular, sulfite ions, which are introduced, for example, as potassium, sodium or ammonium sulfite. The amounts are 0.1 to 10 g of sulfite, preferably 1.5 to 2.5 g / l. The pyrazole compound used is in particular 0.1 to 10 g, preferably 0.5 to 3 g / l; of sequestering agents, in particular 0.1 to 15 g, preferably 0.4 to 10 g, preferably aminopolycarboxylic acids, in particular ethylenediaminetetraacetic acid, and phosphonic acids of aliphatic alcohols, aliphatic amines or polyamines, in particular hydroxyethane diphosphonic acid, being used. Both types of sequestering agents can be used together or individually.

Finally, it is expedient to add a fungicide, in particular 5-chloro-3-methylisothiazolone, which is preferably used in an amount of 0.01 to 0.05 g / l.

The structure and composition of the photosensitive recording materials to be processed with the stabilizing bath according to the invention are not limited.

The light-sensitive silver halide emulsions used in the recording material can contain chloride, bromide and iodide or mixtures thereof as the halide. In a preferred embodiment, the halide content of at least one layer consists of 0 to 12 mol% of iodide, 0 to 50 mol% of chloride and 50 to 100 mol% of bromide. Emulsions with a very high chloride content (over 80 mol%) can also be used. As a rule, these are predominantly compact crystals that are, for example, cubic or octahedral or have transitional forms. They can be characterized in that they essentially have a thickness of more than 0.2 μm. The average ratio of diameter to thickness is preferably less than 5: 1, it being true that the diameter of a grain is defined as the diameter of a circle with a circle content corresponding to the projected area of the grain. In another preferred embodiment, all or individual emulsions can also have essentially tabular silver halide crystals in which the ratio of diameter to thickness is greater than 5: 1. The emulsions can be monodisperse or heterodisperse emulsions, which preferably have an average grain size of 0.2 μm to 2.0 μm.

The silver halide grains can also have a multi-layered grain structure, in the simplest case with an inner and an outer grain area (core / shell), the halide composition and / or other modifications, such as e.g. Doping of the individual grain areas are different. The grain size distribution can be both homodisperse and heterodisperse. In addition to the silver halide, the emulsions can also contain organic silver salts, e.g. Silver benzotriazolate or silver behenate.

Two or more kinds of silver halide emulsions, which are prepared separately, can be used as a mixture.

The photographic emulsions can be prepared using various methods (e.g. P. Glafkides, Chimie et Physique Photographique, Paul Montel, Paris (1967), GF Duffin, Photographic Emulsion Chemistry, The Focal Press, London (1966), VL Zelikman et al, Making and Coating Photographic Emulsion, The Focal Press, London (1966) from soluble silver salts and soluble halides.

The silver halide is preferably precipitated in the presence of the binder, for example the gelatin, and can be carried out in the acidic, neutral or alkaline pH range, silver halide complexing agents preferably being additionally used. The latter include, for example, ammonia, thioether, imidazole, ammonium thiocyanate or excess halide. The water-soluble silver salts and the halides are combined either in succession by the single-jet process or simultaneously by the double-jet process or by any combination of the two processes. Dosing with increasing inflow rates is preferred, the "critical" feed rate, at which no new germs are being produced, should not be exceeded. The pAg range can vary within wide limits during the precipitation, preferably the so-called pAg-controlled method is used, in which a certain pAg value is kept constant or a defined pAg profile is traversed during the precipitation. In addition to the preferred precipitation with an excess of halide, so-called inverse precipitation with an excess of silver ions is also possible. In addition to precipitation, the silver halide crystals can also grow through physical ripening (Ostwald ripening), in the presence of excess halide and / or silver halide complexing agent. The growth of the emulsion grains can even take place predominantly by Ostwald ripening, preferably a fine-grained, so-called Lippmann emulsion, mixed with a less soluble emulsion and redissolved on the latter.

Salts or complexes of metals such as Cd, Zn, Pb, Tl, Bi, Ir, Rh, Fe can also be present during the precipitation and / or physical ripening of the silver halide grains.

The precipitation can also be carried out in the presence of sensitizing dyes. Complexing agents and / or dyes can be rendered ineffective at any time, e.g. by changing the pH or by an oxidative treatment.

Gelatin is preferably used as the binder. However, this can be replaced in whole or in part by other synthetic, semi-synthetic or naturally occurring polymers. Synthetic gelatin substitutes are, for example, polyvinyl alcohol, poly-N-vinylpyrolidone, polyacrylamides, polyacrylic acid and their derivatives, in particular their copolymers. Naturally occurring gelatin substitutes are, for example, other proteins such as albumin or casein, cellulose, sugar, starch or alginates. Semi-synthetic gelatin substitutes are generally modified natural products. Examples of these are cellulose derivatives such as hydroxyalkyl cellulose, carboxymethyl cellulose and phthalyl cellulose and gelatin derivatives which have been obtained by reaction with alkylating or acylating agents or by grafting on polymerizable monomers.

The binders should have a sufficient amount of functional groups so that enough resistant layers can be produced by reaction with suitable hardening agents. Such functional groups are in particular amino groups, but also carboxyl groups, hydroxyl groups and active methylene groups.

The gelatin which is preferably used can be obtained by acidic or alkaline digestion. The production of such gelatins is described, for example, in The Science and Technology of Gelatine, published by A.G. Ward and A. Courts, Academic Press 1977, page 295 ff. The gelatin used in each case should contain the lowest possible level of photographically active impurities (inert gelatin). High viscosity, low swelling gelatins are particularly advantageous.

After crystal formation has been completed or at an earlier point in time, the soluble salts are removed from the emulsion, e.g. by pasta and washing, by flakes and washing, by ultrafiltration or by ion exchangers.

The photographic emulsions may contain compounds to prevent fogging or to stabilize the photographic function during production, storage or photographic processing.
Azaindenes are particularly suitable, preferably tetra- and penta-azaindenes, in particular those which are substituted by hydroxyl or amino groups. Such connections are e.g. B. von Birr, Z. Wiss. Phot. 47 (1952), pp. 2-58. Salts of metals such as mercury or cadmium, aromatic sulfonic or sulfinic acids such as benzenesulfinic acid, or nitrogen-containing heterocycles such as nitrobenzimidazole, nitroindazole, (subst.) Benztria can also be used as antifoggants zoles or benzothiazolium salts are used. Heterocycles containing mercapto groups, e.g. B. mercaptobenzthiazoles, mercaptobenzimidazoles, mercaptotetrazoles, mercaptothiadiazoles, mercaptopyrimidines, these mercaptoazoles also containing a water-solubilizing group, for example a carboxyl group or sulfo group. Other suitable compounds are published in Research Disclosure No. 17643 (1978), Section VI.

The stabilizers can be added to the silver halide emulsions before, during or after their ripening. Of course, the compounds can also be added to other photographic layers which are assigned to a halogen silver layer.

Mixtures of two or more of the compounds mentioned can also be used.

The photographic emulsion layers or other hydrophilic colloid layers of the light-sensitive material produced according to the invention can contain surface-active agents for various purposes, such as coating aids, to prevent electrical charging, to improve the sliding properties, to emulsify the dispersion, to prevent adhesion and to improve the photographic characteristics ( eg acceleration of development, high contrast, sensitization etc.).

The photographic emulsions can be spectral using methine dyes or other dyes be sensitized. Particularly suitable dyes are cyanine dyes, merocyanine dyes and complex merocyanine dyes.

Sensitizers can be dispensed with if the intrinsic sensitivity of the silver halide is sufficient for a certain spectral range, for example the blue sensitivity of silver bromide.

Color photographic materials usually contain at least one red-sensitive, green-sensitive and blue-sensitive emulsion layer. These emulsion layers are assigned non-diffusing monomeric or polymeric color couplers, which can be located in the same layer or in a layer adjacent to it. Usually cyan couplers are assigned to the red-sensitive layers, purple couplers to the green-sensitive layers and yellow couplers to the blue-sensitive layers.

Color couplers for producing the blue-green partial color image are usually couplers of the phenol or α-naphthol type; suitable examples of this are known in the literature.

Color couplers for producing the yellow partial color field are usually couplers with an open-chain catomethylene grouping, in particular couplers of the α-acylacetamide type; Suitable examples of this are α-benzoylacetanilide couplers and α-pivaloylacetanilide couplers, which are also known from the literature.

Color couplers for producing the purple partial color image are generally couplers of the 5-pyrazolone, indazolone or pyrazoloazole type; Suitable examples of this are described in large numbers in the literature.

The color couplers can be 4-equivalent couplers, but also 2-equivalent couplers. The latter are derived from the 4-equivalent couplers in that they contain a substituent in the coupling site which is split off during the coupling. The 2-equivalent couplers include those that are colorless, as well as those that have an intense intrinsic color that disappears when the color is coupled or is replaced by the color of the image dye produced (mask coupler), the white couplers that react with Color developer oxidation products result in essentially colorless products. The 2-equivalent couplers also include those couplers that contain a cleavable residue in the coupling point, which is released upon reaction with color developer oxidation products and thereby either directly or after one or more further groups have been cleaved from the primarily cleaved residue ( eg DE-A-27 03-145, DE-A-28 55 697, DE-A-31 05 026, DE-A-33 19 428), a certain desired photographic activity unfolds, for example as a development inhibitor or accelerator. Examples of such 2-equivalent couplers are the known DIR couplers as well as DAR or. FAR coupler.

Since with DIR, DAR or FAR couplers the effectiveness of the residue released during coupling is mainly desired and the color-forming properties of these couplers are less important, such DIR, DAR or FAR couplers are also suitable, which give essentially colorless products on coupling (DE-A-1 547 640).

The cleavable residue can also be a ballast residue, so that upon reaction with color developer oxidation products coupling products are obtained which are diffusible or at least have a weak or restricted mobility (US Pat. No. 4,420,556).

High molecular weight color couplers are described, for example, in DE-C-1 297 417, DE-A-24 07 569, DE-A-31 48 125, DE-A-32 17 200, DE-A-33 20 079, DE-A-33 24 932, DE-A-33 31 743, DE-A-33 40 376, EP-A-27 284, US-A-4 080 211. The high molecular weight color couplers are usually produced by polymerizing ethylenically unsaturated monomeric color couplers. However, they can also be obtained by polyaddition or polycondensation.

The couplers or other compounds can be incorporated into silver halide emulsion layers by first preparing a solution, a dispersion or an emulsion of the compound in question and then adding it to the casting solution for the layer in question. Choosing the right one Solvents or dispersants depend on the solubility of the compound.

Methods for introducing compounds which are essentially insoluble in water by grinding processes are described, for example, in DE-A-2 609 741 and DE-A-2 609 742.

Hydrophobic compounds can also be introduced into the casting solution using high-boiling solvents, so-called oil formers. Corresponding methods are described for example in US-A-2 322 027, US-A-2 801 170, US-A-2 801 171 and EP-A-0 043 037.

Instead of the high-boiling solvents, oligomers or polymers, so-called polymeric oil formers, can be used.

The compounds can also be introduced into the casting solution in the form of loaded latices. Reference is made, for example, to DE-A-2 541 230, DE-A-2 541 274, DE-A-2 835 856, EP-A-0 014 921, EP-A-0 069 671, EP-A-0 130 115, U.S.-A-4,291,113.

The diffusion-resistant incorporation of anionic water-soluble compounds (eg dyes) can also be carried out with the aid of cationic polymers, so-called pickling polymers.

Suitable oil formers are e.g. Alkyl phthalates, phosphoric acid esters, citric acid esters, benzoic acid esters, alkylamides, fatty acid esters and trimesic acid esters.

Color photographic material typically comprises at least one red-sensitive emulsion layer, at least one green-sensitive emulsion layer and at least one blue-sensitive emulsion layer on a support. The order of these layers can be varied as desired. Couplers which form blue-green, purple and yellow dyes are usually incorporated into the red, green or blue-sensitive emulsion layers. However, different combinations can also be used.

Each of the light-sensitive layers can consist of a single layer or can also comprise two or more silver halide emulsion partial layers (DE-C-1 121 470). Red-sensitive silver halide emulsion layers are often arranged closer to the support than green-sensitive silver halide emulsion layers and these are in turn closer than blue-sensitive layers, with a non-light-sensitive yellow filter layer generally being located between green-sensitive layers and blue-sensitive layers.

With a suitably low intrinsic sensitivity of the green or red-sensitive layers, other layer arrangements can be chosen without the yellow filter layer, in which, for example, the blue-sensitive, then the red-sensitive and finally the green-sensitive layers follow on the support.

The non-light-sensitive intermediate layers, which are generally arranged between layers of different spectral sensitivity, can contain agents which prevent undesired diffusion of developer oxidation products from one light-sensitive layer into another light-sensitive layer with different spectral sensitization.

If there are several sub-layers of the same spectral sensitization, these can differ with regard to their composition, in particular with regard to the type and amount of the silver halide grains. In general, the sublayer with higher sensitivity will be located further from the support than the sublayer with lower sensitivity. Partial layers of the same spectral sensitization can be adjacent to one another or through other layers, e.g. separated by layers of other spectral sensitization. For example, all highly sensitive and all low-sensitive layers can be combined to form a layer package (DE-A 1 958 709, DE-A 2 530 645, DE-A 2 622 922).

The photographic material may further contain compounds absorbing UV light, whiteners, spacers, filter dyes, formalin scavengers and others.

Compounds that absorb UV light are intended on the one hand to protect the image dyes from fading by UV-rich daylight and, on the other hand, as filter dyes to absorb the UV light in daylight upon exposure and thus improve the color rendering of a film. Connections of different structures are usually used for the two tasks. Examples are aryl-substituted benzotriazole compounds (US-A 3 533 794), 4-thiazolidone compounds (US-A 3 314 794 and 3 352 681). Benzophenone compounds (JP-A 2784/71), cinnamic acid ester compounds (US-A 3 705 805 and 3 707 375), butadiene compounds (US-A 4 045 229) or benzoxazole compounds (US-A 3 700 455).

Ultraviolet absorbing couplers (such as α-naphthol type cyan couplers) and ultraviolet absorbing polymers can also be used. These ultraviolet absorbents can be fixed in a special layer by pickling.

Filter dyes suitable for visible light include oxonol dyes, hemioxonol dyes, styrene dyes, merocyanine dyes, cyanine dyes and azo dyes. Of these dyes, oxonol dyes, hemioxonol dyes and merocyanine dyes are used particularly advantageously.

Suitable whiteners are described, for example, in Research Disclosure December 1978, page 22 ff, Unit 17 643, Chapter V.

Certain binder layers, in particular the most distant layer from the support, but also occasionally intermediate layers, especially if they are the most distant layer from the support during manufacture, may contain photographically inert particles of inorganic or organic nature, e.g. as a matting agent or as a spacer (DE-A 3 331 542, DE-A 3 424 893, Research Disclosure December 1978, page 22 ff, Unit 17 643, Chapter XVI).

The average particle diameter of the spacers is in particular in the range from 0.2 to 10 μm. The spacers are water-insoluble and can be alkali-insoluble or alkali-soluble, the alkali-soluble ones generally being removed from the photographic material in the alkaline development bath. Examples of suitable polymers are polymethyl methacrylate, copolymers of acrylic acid and methyl methacrylate and hydroxypropyl methyl cellulose hexahydrophthalate.

The binders of the material according to the invention, in particular if gelatin is used as the binder, are hardened with suitable hardeners, for example with hardeners of the epoxy type, the ethyleneium type, the acryloyl type or the vinylsulfone type. Diazine, triazine or 1,2-dihydroquinoline series hardeners are also suitable.

The binders of the material according to the invention are preferably hardened with instant hardeners.

Immediate hardeners are understood to mean compounds which crosslink suitable binders in such a way that the hardening is completed to such an extent immediately after casting, at the latest after 24 hours, preferably at the latest after 8 hours, that no further change in the sensitometry caused by the crosslinking reaction and the swelling of the layer structure occurs . Swelling is understood to mean the difference between the wet film thickness and the dry film thickness during the aqueous processing of the film (Photogr. Sci. Eng. 8 (1964), 275; Photogr. Sci. Eng. (1972), 449).

These hardening agents that react very quickly with gelatin are e.g. to carbamoylpyridinium salts, which are able to react with free carboxyl groups of the gelatin, so that the latter react with free amino groups of the gelatin to form peptide bonds and crosslink the gelatin.

worin
R₁ Alkyl, Aryl oder Aralkyl bedeutet,
R₂ die gleiche Bedeutung wie R₁ hat oder Alkylen, Arylen, Aralkylen oder Alkaralkylen bedeutet, wobei die zweite Bindung mit einer Gruppe der Formel

verknüpft ist, oder
R₁ und R₂ zusammen die zur Vervollständigung eines gegebenenfalls substituierten heterocyclischen Ringes, beispielsweise eines Piperidin-, Pipe­razin- oder Morpholinringes erforderlichen Atome bedeuten, wobei der Ring z.B. durch C₁-­C₃-Alkyl oder Halogen substituiert sein kann,
R₃ für Wasserstoff, Alkyl, Aryl, Alkoxy, -NR₄-COR₅, -(CH₂)_m-NR₈R₉, -(CH₂)_n-CONR₁₃R₁₄ oder

oder ein Brückenglied oder eine direkte Bindung an eine Polymerkette steht, wobei
R₄, R₆, R₇, R₉, R₁₄, R₁₅, R₁₇, R₁₈, und R₁₉ Wasserstoff oder C₁-C₄-Alkyl,
R₅ Wasserstoff, C₁-C₄-Alkyl oder NR₆R₇,
R₈ -COR₁₀
R₁₀ NR₁₁R₁₂
R₁₁ C₁-C₄-Alkyl oder Aryl, insbesondere Phenyl,
R₁₂ Wasserstoff, C₁-C₄-Alkyl oder Aryl, insbeson­dere Phenyl,
R₁₃ Wasserstoff, C₁-C₄-Alkyl oder Aryl, insbeson­dere Phenyl,
R₁₆ Wasserstoff, C₁-C₄-Alkyl, COR₁₈ oder CONHR₁₉,
m eine Zahl 1 bis 3
n eine Zahl 0 bis 3
p eine Zahl 2 bis 3 und
Y O oder NR₁₇ bedeuten oder
R₁₃ und R₁₄ gemeinsam die zur Vervollständigung eines gegebenenfalls substituierten hetero­cyclischen Ringes, beispielsweise eines Piperidin-, Piperazin- oder Morpholinringes erforderlichen Atome darstellen, wobei der Ring z.B. durch C₁-C₃-Alkyl oder Halogen substituiert sein kann,
Z die zur Vervollständigung eines 5- oder 6-­gliedrigen aromatischen heterocyclischen Ringes, gegebenenfalls mit anelliertem Ben­zolring, erforderlichen C-Atome und
X^⊖ ein Anion bedeuten, das entfällt, wenn bereits eine anionische Gruppe mit dem übrigen Molekül verknüpft ist;

worin
R₁, R₂, R₃ und X^⊖ die für Formel (a) angegebene Bedeutung besitzen.Suitable examples of instant hardeners are, for example, compounds of the general formulas

wherein
R₁ denotes alkyl, aryl or aralkyl,
R₂ has the same meaning as R₁ or means alkylene, arylene, aralkylene or alkaralkylene, the second bond having a group of the formula

is linked, or
R₁ and R₂ together represent the atoms required to complete an optionally substituted heterocyclic ring, for example a piperidine, piperazine or morpholine ring, which ring can be substituted, for example, by C₁-C₃alkyl or halogen,
R₃ for hydrogen, alkyl, aryl, alkoxy, -NR₄-COR₅, - (CH₂) _m -NR₈R₉, - (CH₂) _n -CONR₁₃R₁₄ or

or a bridge link or a direct bond to a polymer chain, wherein
R₄, R₆, R₇, R₉, R₁₄, R₁₅, R₁₇, R₁₈, and R₁₉ are hydrogen or C₁-C₄-alkyl,
R₅ is hydrogen, C₁-C₄-alkyl or NR₆R₇,
R₈ -COR₁₀
R₁₀ NR₁₁R₁₂
R₁₁ C₁-C₄ alkyl or aryl, especially phenyl,
R₁₂ is hydrogen, C₁-C₄ alkyl or aryl, especially phenyl,
R₁₃ is hydrogen, C₁-C₄ alkyl or aryl, especially phenyl,
R₁₆ is hydrogen, C₁-C₄-alkyl, COR₁₈ or CONHR₁₉,
m is a number 1 to 3
n is a number 0 to 3
p is a number 2 to 3 and
YO or NR₁₇ mean or
R₁₃ and R₁₄ together represent the atoms required to complete an optionally substituted heterocyclic ring, for example a piperidine, piperazine or morpholine ring, which ring can be substituted, for example, by C₁-C₃alkyl or halogen,
Z the C atoms and required to complete a 5- or 6-membered aromatic heterocyclic ring, optionally with a fused benzene ring
X ^{⊖ is} an anion which is omitted if an anionic group is already linked to the rest of the molecule;

wherein
R₁, R₂, R₃ and X ^{⊖ have} the meaning given for formula (a).

example 1

Color paper, e.g. Agfacolor Type 8, is exposed imagewise and processed in the following process: Develop: 3.5 minutes at 33 ° C, regeneration rate 325 ml / m² Bleach fixation: 1.5 minutes at 30 ° C, regeneration rate 100 ml / m² Stabilize: 3-stage countercurrent cascade, 1 minute at 30 ° C in each stage, regeneration rate 250 ml / m², regeneration in the 3rd stage. Dry. Composition of the bathrooms Developer , 1 liter Benzyl alcohol 13 ml Hydroxylammonium sulfate 3 g Sodium sulfite 2 g 4-amino-N-ethyl-N (β-methanesulfonamido-ethyl) -m-toluidine-sesquisulfate (monohydrate) 4.5 g Potassium carbonate 36 g Potassium bromide 1.4 g Diethylene triamino pentaacetic acid, pentasodium salt 2 g Diethylene glycol 12 ml pH = 10.4

Bleach-fix bath , 1 liter

In line with the used condition, it also contains silver and developer substance: Ammonium iron salt of ethylenediaminetetraacetic acid 45 g Sodium sulfite 5 g Ethylenediaminetetraacetic acid 5 g Ammonium thiosulfate 100 g 4-amino-N-ethyl-N (β-methanesulfonamidoethyl) -m-toluidine sesquisulfate (monohydrate) 2 g Silver (13.5 g silver chloride dissolved in the bathroom) 10 g pH = 8.0 (adjusted with potassium carbonate)

Stabilizing bath 1

1 l of water contains:
Ammonium salt of hydroxyethane diphosphonic acid: 2 g
Ammonium salt of ethylenediaminetetraacetic acid: 0.5 g
Ammonium bisulfite: 1.7 g
5-chloro-3-methylisothiazolone: 0.03 g
pH: 7.5

• 1. Stufe: 800 ml Stabilisierbad + 200 ml gebrauchtes Bleichfixierbad
• 2. Stufe: 960 ml Stabilisierbad + 40 ml gebrauchtes Bleichfixierbad
• 3. Stufe: 992 ml Stabilisierbad + 8 ml gebrauchtes Bleichfixierbad.

The following is used to establish the state of use:

• 1st stage: 800 ml stabilizing bath + 200 ml used bleach-fixing bath
• 2nd stage: 960 ml stabilizing bath + 40 ml used bleach-fixing bath
• 3rd stage: 992 ml stabilizing bath + 8 ml used bleach-fixing bath.

The processed color paper is stored at 60 ° C and 90% relative humidity for 7 days.

The results are shown in the table below.

Example 2

The processing and developer and bleach-fix bath composition correspond to Example 1.

Stabilizing bath 2

1 l contains:
Ammonium salt of hydroxyethane diphosphonic acid: 8 g
Ammonium salt of ethylenediaminetetraacetic acid: 0.5 g
Ammonium hydrogen sulfide: 1.7 g
Ammonium chloride: 2 g
5-chloro-3-methylisothiazolone: 0.03 g
pH: 7.5

The use condition of the stabilizing bath was produced and the processed images were stored as in Example 1.

Example 3

The processing process and developer and bleach-fix bath composition corresponded to Example 1.

Stabilizing bath 3

1 l contains:
Ammonium salt of hydroxyethane diphosphonic acid: 8 g
Ammonium salt of ethylenediaminetetraacetic acid: 0.5 g
Ammonium hydrogen sulfide: 1.7 g
Ammonium chloride: 2 g
Pyrazole compound 1: 1 g
5-chloro-3-methylisothiazolone: 0.03 g
pH: 7.5

Production of the condition of use of the stabilizing bath and storage of the processed images corresponded to example 1.

Example 4

This example corresponds to Example 3, except that pyrazole compound 1 was replaced by pyrazole compound 12 in the same amount.

Example 5

This example corresponds to Example 1, except that the stabilizing bath used in the three-stage countercurrent cascade was replaced by a 3-minute soak at 30 ° C with 5 l / m².

The storage of the processed images corresponded to example 1.

Examples 3 and 4 are examples according to the invention, which are compared with Examples 1 and 2 not according to the invention, which likewise relate to a stabilizing bath free of washing water, and with Example 5, in which washing is carried out conventionally. A material before storage at 60 ° C and 90% relative humidity was also included in the comparison. The minimum densities of the three different image colors were determined. Table of minimum densities before storage After 7 days of storage at 60 ° C and 90% relative humidity Ex. 1 Ex. 2 Ex. 3 Ex. 4 Ex. 5 yellow 0.10 0.20 0.18 0.15 0.16 0.16 purple 0.10 0.13 0.12 0.12 0.12 0.12 blue green 0.09 0.10 0.10 0.09 0.09 0.09

The table shows that the processing method according to the invention, which is essentially based on the stabilizing bath according to the invention, exceeds previously known washing water-free stabilizing methods and gives the same or even better results as are achieved in the conventional method with one washing step.

Example 6

The processing and developer and bleach-fix bath composition correspond to Example 1.

Stabilizing bath 5

1 l contains:
Sodium salt of hydroxyethane diphosphonic acid: 6 g
Sodium salt of ethylenediaminetetraacetic acid: 0.4 g
Sodium sulfite: 2.2 g
5-chloro-3-methylisothiazolone: 0.03 g
pH: 5.0 (adjust with hydroxyethane diphosphonic acid)

The use condition of the stabilizing bath was produced as in Example 1.

Example 7

The processing process and developer and bleach-fix bath composition corresponded to Example 1.

Stabilizing bath 6

1 l contains:
Sodium salt of hydroxyethane diphosphonic acid: 6 g
Sodium salt of ethylenediaminetetraacetic acid: 0.4 g
Sodium sulfite: 2.2 g
Pyrazole compound 1: 1 g
5-chloro-3-methylisothiazolone: 0.03 g
pH: 5.0 (adjust with hydroxyethane diphosphonic acid)

The preparation of the state of use of the stabilizing bath corresponded to Example 1.

Example 8

This example corresponds to Example 1, except that the stabilizing bath used in the three-stage countercurrent cascade was replaced by a 3-minute soak at 30 ° C with 5 l / m².

The images processed according to Examples 6, 7 and 8 were stored for 7 days at 60 ° C. and 90% relative humidity and for 14 days at 80 ° C. and 40% relative humidity.

Example 7 is an example according to the invention which is compared with example 6 not according to the invention, which likewise relates to a stabilizing bath free of washing water, and with example 8, in which washing is carried out conventionally. A material before storage was also included in the comparison. The minimum densities of the three different image colors were determined. Minimum density tables before storage After 7 days of storage at 60 ° C and 90% relative humidity Ex. 6 Ex. 7 Ex. 8 yellow 0.09 0.23 0.20 0.19 purple 0.09 0.14 0.14 0.14 blue green 0.09 0.09 0.09 0.09 before storage After 14 days of storage at 80 ° C and 40% relative humidity Ex. 6 Ex. 7 Ex. 8 yellow 0.09 0.20 0.17 0.16 purple 0.09 0.12 0.12 0.11 blue green 0.09 0.09 0.09 0.09

The tables show that the processing method according to the invention, which is essentially based on the stabilizing bath according to the invention, exceeds known washing water-free stabilizing methods and gives practically the same results as are achieved in the conventional method with one washing step.

Example 9

Color paper, eg Ektacolor 2001, is exposed imagewise and processed in the following process: Develop: 45 s at 35 ° C, regeneration rate 160 ml / m² Bleach fixation: 45 s at 30 ° C, regeneration rate 100 ml / m² Stabilize: 4-stage countercurrent cascade, 22.5 s at 30 ° C in each stage, regeneration rate 250 ml / m², regeneration in the 4th stage. Dry. Composition of the bathrooms Developer , 1 liter Triethanolamine 9 ml N, N-diethylhydroxylamine 4.4 g 4-amino-N-ethyl-N (β-methanesulfonamido-ethyl) -m-toluidine-sesquisulfate (monohydrate) 5 g Potassium carbonate 20 g Potassium chloride 1.6 g Ethylene diamino tetraacetic acid, tetrasodium salt 2 g 1,2-Dihydroxybenzene-3,4,6-trisulfonic acid trisodium salt 0.5 g pH = 10.05

Bleach-fix bath , 1 liter

In line with the used condition, it also contains silver and developer substance: Ammonium iron salt of ethylenediaminetetraacetic acid 57 g Sodium sulfite 16 g Ethylenediaminetetraacetic acid 5 g Ammonium thiosulfate 100 g 4-amino-N-ethyl-N (β-methanesulfonamido-ethyl) -m-toluidine sesquisulfate (monohydrate) 2 g Silver (13.5 g silver chloride dissolved in the bathroom) 10 g pH = 5.5 (adjusted with acetic acid)

Stabilizing bath 7

1 l of water contains:
Sodium salt of ethylenediaminetetraacetic acid: 0.4 g
Sodium sulfite: 2.2 g
5-chloro-3-methylisothiazolone: 0.03 g
pH: 6.0

• 1. Stufe: 800 ml Stabilisierbad + 200 ml gebrauchtes Bleichfixierbad
• 2. Stufe: 960 ml Stabilisierbad + 40 ml gebrauchtes Bleichfixierbad
• 3. Stufe: 992 ml Stabilisierbad + 8 ml gebrauchtes Bleichfixierbad.
• 4. Stufe: 998,4 ml Stabilisator + 1,6 ml gebrauchtes Stabilisierbad.

The following is used to establish the state of use:

• 1st stage: 800 ml stabilizing bath + 200 ml used bleach-fixing bath
• 2nd stage: 960 ml stabilizing bath + 40 ml used bleach-fixing bath
• 3rd stage: 992 ml stabilizing bath + 8 ml used bleach-fixing bath.
• 4th stage: 998.4 ml stabilizer + 1.6 ml used stabilizing bath.

The processed color paper is stored at 60 ° C and 90% relative humidity for 7 days and at 80 ° C and 40% relative humidity for 14 days.

The results are shown in the table below.

Example 10

The processing process and developer and bleach-fix bath composition corresponded to Example 9.

Stabilizing bath 8

1 l contains:
Sodium salt of ethylenediaminetetraacetic acid: 0.4 g
Sodium sulfite: 2.2 g
Pyrazole compound 1: 1 g
5-chloro-3-methylisothiazolone: 0.03 g
pH: 6.0

The preparation of the state of use of the stabilizing bath and the storage of the processed images corresponded to Example 9.

Example 11

This example corresponds to Example 9, except that the stabilizing bath used in the four-stage countercurrent cascade was replaced by a 1.5-minute wash at 30 ° C. with 5 l / m².

The storage of the processed images corresponded to example 9.

Example 10 is an example according to the invention, which is compared with example 9 not according to the invention, which likewise relates to a stabilizing bath free of washing water, and with example 11, in which washing is carried out conventionally. A material before storage at 60 ° C. and 90% relative humidity or 80% and 40% relative humidity was also included in the comparison. The minimum densities of the three different image colors were determined. Minimum density tables before storage After 7 days of storage at 60 ° C and 90% relative humidity Ex. 9 Ex. 10 Ex. 11 yellow 0.10 0.24 0.22 0.21 purple 0.11 0.15 0.15 0.15 blue green 0.09 0.10 0.10 0.10 before storage After 14 days of storage at 80 ° C and 40% relative humidity Ex. 9 Ex. 10 Ex. 11 yellow 0.10 0.24 0.23 0.22 purple 0.11 0.17 0.17 0.17 blue green 0.09 0.10 0.10 0.11

The tables show that the processing method according to the invention, which is essentially based on the stabilizing bath according to the invention, surpasses known washing water-free stabilizing methods and gives the same or even better results as are achieved in the conventional method with one washing step.

Claims (9)

1. washing water-free processing method for producing color photographic images with the processing steps developing, bleaching, fixing and stabilizing, the bleaching and fixing steps for the bleach-fixing step being able to be contracted, characterized in that the stabilizing bath used in the stabilizing step contains an effective amount of a pyrazole in a the possible tautomeric formulas of the general formula

corresponds to what
X OH or NH₂,
R₁ alkyl, substituted alkyl, aryl, substituted aryl or carboxyl,
R₂ is hydrogen, alkyl or substituted alkyl,
R₃ is hydrogen, alkyl, substituted alkyl, aryl or substituted aryl. 2. The method according to claim 1, characterized in that the substituents of the substituted alkyl and aryl radicals of the pyrazoles are carboxyl, sulfonyl and sulfonamide groups. 3. The method according to claim 1, characterized in that the pyrazoles contain at least one acidic group. 4. The method according to claim 1, characterized in that the pyrazoles are used in an amount of 0.1 to 10 g / l stabilizing bath. 5. The method according to claim 1, characterized in that the pH of the stabilizing bath is 3.0 to 7.8. 6. The method according to claim 1, characterized in that the stabilizing bath additionally contains at least one sequestering agent. 7. The method according to claim 1, characterized in that the pH of the stabilizing bath is 5.0 to 6.0. 8. stabilizing bath for a washing water-free processing method for producing color photographic images, characterized in that it contains an effective amount of a pyrazole, which is in one of the possible tautomeric forms of the formula

corresponds to what
X OH or NH₂,
R₁ alkyl, substituted alkyl, aryl, substituted aryl or carboxyl,
R₂ is hydrogen, alkyl or substituted alkyl,
R₃ is hydrogen, alkyl, substituted alkyl, aryl or substituted aryl. 9. stabilizing bath according to claim 8, characterized in that it additionally contains at least one sequestering agent and is adjusted to a pH of 3.0 to 7.8.