EP0330948A2 - Process for producing colour images - Google Patents

Abstract

High-speed processing with development within less than 1.5 minutes, the developer containing less than 30 mg/l of bromide, of a photographic silver halide material with at least one emulsion layer sensitive to blue light and associated with at least one yellow coupler, at least one emulsion layer sensitive to red light and associated with a cyan coupler and at least one emulsion layer sensitive to green light and associated with at least one magenta coupler, wherein the silver halide emulsions consist of 95 to 100 mol% of silver chloride, 0 to 5 mol% of silver bromide and 0 to 1 mol% of silver iodide, is possible without colour distortions, if the photographic material contains acutance dyes of the formula <IMAGE> wherein R1 and R2 are a carboxyl group or a carboxamide group.

Description

The invention relates to a method for producing color images from light-sensitive silver halide materials containing chloride-rich emulsions and special filter dyes by imagewise exposure, development, bleaching, fixing, washing and stabilizing or water-free stabilizing and drying.

The addition of dyes to photographic layers to absorb unwanted radiation is known. If these dyes are added directly to a light-sensitive layer, they are also called sharpness dyes because they absorb the radiation scattered between the emulsion layers and thereby improve the sharpness. At the same time, such dyes can be used to control the sensitivity because they absorb part of the incident light.

• 1. Der Farbstoff muß Licht des gewünschten Spektral­bereiches in möglichst hohem Maße absorbieren. Dabei ist es, vor allem bei Colormaterialien, nötig, daß der Farbstoff in benachbarten Spektral­bereichen möglichst wenig absorbiert.
• 2. Der Farbstoff soll möglichst wasserlöslich sein, damit er leicht in das Material eingebracht werden kann.
• 3. Der Farbstoff darf nach der Verarbeitung des Mate­rials keinerlei Anfärbung hinterlassen, er darf auch die Verarbeitungsbäder, z.B. den Entwickler, nicht anfärben oder durch Schlammbildung verun­reinigen.
• 4. Der Farbstoff muß fotografisch inert sein. Selbst­verständlich darf der Farbstoff keine Schleierbil­dung verursachen oder die Sensitometrie des Mate­rials beeinflussen. Insbesondere darf er weder die Emulsion selbst desensibilisieren, noch durch Ver­drängung von Sensibilisatoren eine Desensibilisie­rung hervorrufen.

The choice of dyes depends on many factors. A usable dye must meet various requirements:

• 1. The dye must absorb light of the desired spectral range as much as possible. It is necessary, especially with color materials, that the dye absorbs as little as possible in neighboring spectral ranges.
• 2. The dye should be as water soluble as possible so that it can be easily introduced into the material.
• 3. The dye must not leave any staining after processing the material, it must also not stain the processing baths, eg the developer, or contaminate them with sludge formation.
• 4. The dye must be photographically inert. Of course, the dye must not cause fog or affect the sensitometry of the material. In particular, it must neither desensitize the emulsion itself nor cause desensitization by displacing sensitizers.

Dyes from the series of oxonols are of particular interest as sharpness dyes, oxonol dyes of the pyrazolone series in particular being used.

Suitable sharpening dyes are known, for example, from DE-A-2 453 217, 2 259 746 and EP-A-246 553.

Color photographic silver halide materials are also known which contain only chloride-rich emulsions and are processed in so-called short processes in which the development time is less than 90 seconds. The development baths required for this usually contain at most small amounts of bromide; they are preferably free of bromide or contain only as much bromide as is released from the photographic material, the emulsions of which contain only low amounts of bromide.

This measure creates a large developer activity. In order to achieve a high color yield, the sulfite content of the developer is advantageously kept as low as possible, or attempts are made to avoid sulfite entirely. The selection of a suitable antioxidant must be done carefully from the point of view of high color yield and good developer stability at higher temperatures. An N, N-dialkylhydroxylamine is usually used. In the manner described, e.g. built up the color developer, which belongs to the rapid processing process known as RA 4. This developer does not contain benzyl alcohol.

However, rapid processing processes that contain benzyl alcohol in the color developer must also be taken into account. The regeneration rate of the developer can be chosen so that the developer overflow is 0 to 200 ml / m².

The benzyl alcohol content of the developer is preferably less than 8 g / l, in particular 0 to 0.5 g / l.

It has now been shown that the processing of such chloride-rich materials achieves flawless results with only a few of the known sharpness dyes.

From the point of view of rapid processing and the developer composition mentioned, increased demands are made on sharpness dyes in a color paper, e.g. with regard to rapid decolorization and good solubility, so that the color paper whites do not show any residual staining, and with regard to the interactions in the layer and on the silver halide grain, so that there are no undesirable secondary densities and, as a result, color distortions.

enthält, worin
R₁ und R₂ eine Carboxylgruppe, die auch in Form eines Salzes vorliegen kann, oder eine Gruppe CONR₃R₄,
R₃ und R₄ Wasserstoff, Alkyl oder Aryl oder zusammen die restlichen Glieder eines heterocyclischen Ringes und
n 3 oder 5 bedeuten.The invention therefore relates to a method for producing color images, in particular on a reflective base, by exposure and processing of a photographic silver halide material with at least one emulsion layer sensitive to blue light, the at least one yellow coupler, with at least one emulsion layer sensitive to red light, the at least one Teal couplers and at least one emulsion layer sensitive to green light, which is assigned at least one magenta coupler, the silver halide emulsions of 95 to 100 mol% of silver chloride, 0 to 5 mol% of silver bromide and 0 to 1 mol% of silver iodide exist, the development being carried out in less than 1.5 minutes and the developer containing less than 30 mg / l bromide, characterized in that the photographic material has sharpness dyes of the formula

contains what
R₁ and R₂ are a carboxyl group, which may also be in the form of a salt, or a group CONR₃R₄,
R₃ and R₄ are hydrogen, alkyl or aryl or together the remaining members of a heterocyclic ring and
n is 3 or 5.

Alkyl R₃ and R₄ is in particular optionally substituted C₁-C₆ alkyl, the substituents being e.g. Hydroxy, cyano or phenyl come into question. Aryl R₃ and R₄ is in particular optionally substituted by C₁-C₄-alkyl, chlorine or C₁-C₄-alkoxy phenyl or naphthyl.

Rings which R₃ and R₄ can form together are, for example, pyrrolidine, piperidine, cyclohexamethyleneimine, indoline, Tetrahydroquinoline, morpholine, thiomorpholine, piperazine, N-methylpiperazine.

The sharpness dyes of the present invention are preferably added to the silver halide color photographic material in an amount of 0.0005 to 0.05 mmol / m².

Suitable sharpness dyes are listed below:

The silver halide can be predominantly compact crystals, e.g. are regular cubic or octahedral or can have transitional forms. However, platelet-shaped crystals can preferably also be present, the average ratio of diameter to thickness of which is preferably at least 5: 1, the diameter of a grain being defined as the diameter of a circle with a circle content corresponding to the projected area of the grain. However, the layers can also have tabular silver halide crystals in which the ratio of diameter to thickness is greater than 5: 1, e.g. 12: 1 to 30: 1.

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 doping the one individual grain areas are different. The average grain size of the emulsions is preferably between 0.2 μm and 2.0 μm, the grain size distribution can be both homo- and heterodisperse. In addition to the silver halide, the emulsions can also contain organic silver salts, for example 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. Be 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, a fine-grained, so-called Lippmann emulsion preferably being mixed with a less soluble emulsion and being 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, for example 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 usually 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 preparation of such gelatins is described, for example, in The Science and Technology of Gelatine, published by AG 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. The gelatin can be partially or completely oxidized.

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 connection are such. 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.) Benzotriazoles or benzothiazolium salts can also be used as antifoggants. Heterocycles containing mercapto groups, e.g. B. mercaptobenzthiazoles, mercaptobenzimidazo le, 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 silver halide emulsions are usually chemically ripened, for example by the action of gold compounds or compounds of divalent sulfur.

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 spectrally sensitized using methine dyes or other dyes. Particularly suitable dyes are cyanine dyes, merocyanine dyes and complex merocyanine dyes.

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 ketomethylene group, 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 usually couplers of the 5-pyrazolone type Indazolone or pyrazoloazole; 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 which contain a cleavable residue at 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 ( e.g. DE-A-27 03-145, DE-A-28 55 697, DE-A-31 05 026, DE-A-33 19 428), a certain desired photographic effectiveness unfolds, e.g. 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 the DIR, DAR and FAR couplers mainly the effectiveness of the residue released during the coupling is desired and it is less due to the color the forming properties of these couplers, DIR, DAR or FAR couplers are also suitable which, when coupled, result in essentially colorless products (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. The selection of the suitable solvent or dispersing agent depends 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 (e.g. dyes) can also be carried out with the help of cationic polymers, so-called pickling polymers.

Suitable oil formers for other couplers and other compounds are, for example, alkyl phthalates, phosphoric esters, citric acid esters, benzoic acid esters, alkylamides, fatty acid esters and trimesic acid esters.

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.

If the green or red sensitive layers have a suitably low intrinsic sensitivity, one can choose other layer arrangements without the yellow filter layer, in which e.g. the blue-sensitive, then the red-sensitive and finally the green-sensitive layers follow.

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. Generally I think the sublayer with higher sensitivity will be arranged further away from the support than the sublayer with lower sensitivity. Partial layers of the same spectral sensitization can be adjacent to one another or separated by other layers, for example by layers of different 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 UV light absorbing compounds, whites, spacers, 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 Pat. No. 3,533,794), 4-thiazolidone compounds (US Pat. Nos. 3,314,794 and 3,352,681), benzophenone compounds (JP-A 2784/71), cinnamic acid ester compounds (US Pat. Nos. 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.

Suitable white toners are e.g. in Research Disclosure December 1978, page 22 ff, presentation, 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 ethyleneimine 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 containers are understood to mean compounds which crosslink suitable binders in such a way that the hardening is completed immediately after casting, at the latest after 24 hours, preferably after 8 hours at the latest, so 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 which react very quickly with gelatin are, for example, 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 with the formation of peptide bonds and crosslinking of the gelatin.

• (a)
  
  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 -(CH₂)_p-
  
  Y-R₁₆
  
  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-C₁₄-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;
• (b)
  
  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

• (a)
  
  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 - (CH₂) _p -
  
  Y-R₁₆
  
  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-C₁₄ 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;
• (b)
  
  wherein
  R₁, R₂, R₃ and X ^{⊖ have} the meaning given for formula (a).

example

A color photographic recording material which is suitable for a rapid processing process was produced by applying the following layers in the order given to a support on paper coated on both sides with polyethylene. The quantities given relate to 1 m². For the silver halide application, the corresponding amounts of AgNO₃ are given.

Layer structure 1:

• 1st layer (substrate layer):
  0.2 g gelatin
• 2nd layer (blue-sensitive layer):
  blue-sensitive silver halide emulsion (99.5 mol% chloride, 0.5 mol% bromide, average grain diameter 0.8 µm) from 0.63 g AgNO₃ with
  1.38 g gelatin
  0.95 g yellow coupler
  0.2 g white coupler
  0.29 g tricresyl phosphate (CPM)
• 3rd layer (protective layer)
  1.1 g gelatin
  0.06 g 2,5-dioctylhydroquinone
  0.06 g dibutyl phthalate (DBP)
• 4th layer (green-sensitive layer)
  green-sensitized silver halide emulsion (99.5 mol% chloride, 0.5 mol% bromide, average grain diameter 0.6 µm) from 0.45 g AgNO₃ with
  1.08 g gelatin
  0.41 g purple coupler
  0.16 g of ethyl α- (3-t-butyl-4-hydroxyphenoxy) myristic acid
  0.08 g 2,5-dioctyl hydroquinone
  0.34 g DBP
  0.04 g CPM
• 5th layer (UV protective layer)
  1.15 g gelatin
  0.6 g UV absorber of the formula
  
  0.045g 2,5-dioctyl hydroquinone
  0.04 g CPM
• 6th layer (red-sensitive layer)
  red-sensitized silver halide emulsion (99.5 mol% chloride, 0.5 mol-5 bromide, average grain diameter 0.5 µm) from 0.3 g of AgNO₃ with
  0.75 g gelatin
  0.36 g cyan coupler
  0.36 g CPM
• 7th layer (UV protective layer)
  0.35 g gelatin
  0.15 g UV absorber as in 5, layer
  0.2 g CPM
• 8th layer (protective layer)
  0.9 g gelatin
  0.3 g hardening agent of the formula
  

The following connections were used as color couplers:

The following sharpness dyes according to the invention were added to the layer structure 1:

The 4th, green-sensitive layer 4 mg / m² of dye 2 and the 6th, red-sensitive layer 15 mg / m² of dye 12.

For comparison, 3 further layer structures were created by adding the following sharpness dyes to the 6th, red-sensitive layer: 15 mg / m²:

All 4 layer structures were exposed behind a gray wedge with light in the green spectral range and subjected to the subsequent rapid processing. The purple densities were then measured in the purple color extracts and the associated secondary yellow densities were determined: Layer construction no. Prime purple density Yellow secondary density 1 1.00 0.49 2nd 1.00 1.26 3rd 1.00 1.20 4th 1.00 1.29

Only in the case of the layer structure 1 according to the invention only a low secondary yellow density occurs, while in the comparative structures 2, 3 and 4 there are considerable secondary yellow densities which result in severe color falsifications.

The processing was carried out in the following way: Developer: 45 Seconds, 35 ° C Bleach-fix bath: 45 Seconds, 305 ° C Water: 90 Seconds, 30 ° C Dry. Composition of the bathrooms Developer: Triethanolamine 11.0 ml N, N-diethylhydroxylamine 5.1 G 4-Amino-N-ethyl-N- (β-methanesulfonamidoethyl) -m-toluidene sequisulfate monohydrate 5.0 G Potassium chloride 2.3 G Ethylenediaminetetraacetic acid 3.0 G 3,4-dihydroxy-1,2,5-benzenetrisulfonic acid, trisodium salt 0.6 G Potassium carbonate 25.0 G additional usual surface-active agents and optical brighteners Make up to 1 liter with water pH = 10.04 Bleach-fix bath: Sodium disulfite 15 G Ammonium thiosulfate 100 G Ammonium-iron-ethylenediaminetetraacetic acid 50 G Ethylenediaminetetraacetic acid 5 G Make up to 1 liter pH = 6.0

Claims (4)

1. A method for producing color images by exposure and processing of a photographic silver halide material with at least one emulsion layer sensitive to blue light, the at least one yellow coupler, with at least one emulsion layer sensitive to red light, the at least one cyan coupler and at least one emulsion layer sensitive to green light, associated with at least one magenta coupler whose silver halide emulsions consist of 95 to 100 mol% of silver chloride, 0 to 5 mol% of silver bromide and 0 to 1 mol% of silver iodide, the development in less than 1.5 minutes is carried out and the developer contains less than 30 mg / l bromide, characterized in that the photographic material has sharpness dyes of the formula

contains what
R₁ and R₂ are a carboxyl group, which may also be in the form of a salt, or a group CONR₃R₄,
R₃ and R₄ are hydrogen, alkyl or aryl or together the remaining members of a heterocyclic ring and
n is 3 or 5. 2. The method according to claim 1, characterized in that the color images have a reflective base. 3. The method according to claim 1, characterized in that the regeneration rate of the developer is chosen so that the developer overflow is 0 to 200 ml / m². 4. The method according to claim 1, characterized in that the benzyl alcohol content of the developer is less than 8 g / l.