EP0437818A2 - Colour photographic recording material - Google Patents

Abstract

A colour-photographic recording material having at least one light-sensitive silver halide emulsion layer and, associated therewith, a diffusion-resistant yellow coupler of the formula <IMAGE> in which Y is an aliphatic or cycloaliphatic radical, X is a hydrogen atom or a group which can be eliminated on colour coupling, R<1> is an alkyl radical having 1 to 20 C atoms and R<2> is an alkyl radical having 1 to 20 C atoms, the alkyl radicals R<1> and R<2> together having at least 12 C atoms, the yellow coupler being dissolved in a liquid compound containing ester groups and having a molecular weight of at least 350, gives a yellow dyestuff which has a high colour density, is particularly light-fast, resistant to dark fading and stable under tropical conditions and produces less casting faults, even in a high-speed process (development in less than 60 seconds).

Description

The invention relates to a color photographic recording material having at least one silver halide emulsion layer and a diffusion-resistant α-acylacetanilide yellow coupler, the anilide group of which is substituted by an N-acylsulfamoyl group which is dissolved in a specific organic solvent.

It is known to produce colored photographic images by chromogenic development, that is to say by developing imagewise exposed silver halide emulsion layers in the presence of suitable color couplers by means of suitable color-forming developer substances - so-called color developers - the oxidation product of the developer substances with the color coupler which is formed in accordance with the silver image being formed of a dye image reacts. Aromatic compounds containing primary amino groups, in particular those of the p-phenylenediamine type, are usually used as color developers.

In practice, a number of requirements are placed on the color couplers and on the dyes obtained therefrom by chromogenic development. For example, the coupling speed of the color couplers with the oxidation product of the color developer should be as high as possible and the highest possible color density should be achieved. The color couplers and the dyes obtained from them must be sufficiently stable to light, elevated temperature and moisture. This applies to both fresh material and processed material. For example, the remaining coupler still present in the image whites of the processed material must not turn yellow. In addition, the dyes should be sufficiently resistant to gaseous reducing or oxidizing agents. They must also be firmly anchored in the image layer and should separate as fine a grain as possible during the chromogenic development. Finally, the dyes resulting from the color couplers in the chromogenic development must have a favorable absorption curve with a maximum that corresponds to the color of the desired partial image and the lowest possible secondary absorptions.

The above-mentioned requirements apply to yellow couplers in particular, because they are often arranged in color photographic recording materials in the uppermost color-generating layer and are therefore not only particularly exposed to environmental influences, but also influence the layers below, particularly with regard to their sharpness. There are Therefore, all measures are advantageous by means of which the layer load, particularly of the layer containing yellow coupler, can be reduced. For this reason, the use of 2-equivalent yellow couplers is particularly advantageous.

worin

Y

einen aliphatischen oder cycloaliphatischen Rest,

X

ein Wasserstoffatom oder eine bei Farbkupplung abspaltbare Gruppe,

R¹

einen Alkylrest mit 1 bis 20 C-Atomen,

R²

einen Alkylrest mit 1 bis 20 C-Atomen,

bedeuten, wobei die Alkylreste R¹ und R² zusammen wenigstens 12 C-Atome aufweisen, vorteilhaft, weil sie große Empfindlichkeit, dark-fading-Stabilität und Tropenstabilität zeigen und in benzylalkoholfreier Entwicklung eine steile Gradation neben großer Farbdichte erzeugen.Known yellow couplers include, in particular, compounds of the formula (I)

wherein

Y

an aliphatic or cycloaliphatic radical,

X

a hydrogen atom or a group which can be split off on color coupling,

R¹

an alkyl radical with 1 to 20 carbon atoms,

R²

an alkyl radical with 1 to 20 carbon atoms,

mean, wherein the alkyl radicals R¹ and R² together have at least 12 carbon atoms, advantageous because they show great sensitivity, dark fading stability and tropical stability and produce a steep gradation in addition to high color density in benzyl alcohol-free development.

An aliphatic radical represented by Y is preferably a tert-alkyl radical, in particular tert-butyl. A cycloaliphatic radical represented by Y is, for example, a cyclohexyl, norbornyl or adamantyl radical.

A group represented by X on color coupling is preferably a cyclic group linked via an oxygen atom or via a nitrogen atom, in particular a ring nitrogen atom, e.g. an optionally substituted 5- or 6-membered heterocyclic ring linked via a ring nitrogen atom. Such cleavable groups, also referred to as escape groups, usually give the coupler the behavior of a 2-equivalent coupler, i.e. the coupler only requires half as much developable silver halide for color coupling as the corresponding 4-equivalent coupler, in which X denotes a hydrogen atom. The refugee groups also include those that are photographically effective and, for example, inhibit or accelerate development.

The couplers are known from US-A-4 617 256.

worin

R³

C₁₁-C₂₀-Alkyl,

R⁴

C₁-C₄-Alkyl und

R⁵

ein gegebenenfalls durch Halogen oder C₁-C₄-Alkyl substituiertes Phenyl bedeuten.

Preferred couplers correspond to the formula

wherein

R³

C₁₁-C₂₀ alkyl,

R⁴

C₁-C₄ alkyl and

R⁵

is a phenyl optionally substituted by halogen or C₁-C₄-alkyl.

Die Kuppler der Formel (I) zeigen den Nachteil, daß die mit den üblichen Farbentwicklern der p-Phenylendiaminreihe aus ihnen erzeugten Farbstoffe unbefriedigende Lichtechtheiten aufweisen. Außerdem sind diese Kuppler in gebräuchlichen Lösungsmitteln wie Trikresylphosphat schwerlöslich, was zu kristallinen Ausscheidungen und somit zu Gießfehlern (sogenannte Punktfehler) führt.The following compounds are mentioned as examples of these yellow couplers:

The couplers of the formula (I) have the disadvantage that the dyes produced from them with the customary color developers of the p-phenylenediamine series have unsatisfactory lightfastness. In addition, these couplers are sparingly soluble in common solvents such as tricresyl phosphate, which leads to crystalline precipitations and thus to casting errors (so-called point errors).

The object of the invention was therefore to remedy these disadvantages without the positive properties of this coupler class being lost.

It has now surprisingly been found that this object can be achieved by choosing a particular coupler solvent ("oil former").

The invention therefore relates to a color photographic recording material having at least one silver halide emulsion layer and a diffusion-resistant coupler of the formula (I), characterized in that liquid ester-containing compounds which have a molecular weight of at least 350 are used as oil formers for the color couplers of the formula (I).

The oil formers are preferably mono- or diesters of aliphatic or aromatic dicarboxylic acids and aliphatic or araliphatic alcohols or polyesters of aliphatic or aromatic dicarboxylic acids and aliphatic diols.

There is no upper limit on the molecular weight as long as the compounds containing ester groups are liquid. The molecular weight preferably does not exceed 1200.

Suitable oil formers are, for example, dinonyl adipate, dinonyl phthalate, octadecylene succinic acid monobenzyl ester and polymers of adipic acid or phthalic acid and diols, for example butanediol and / or pentanediol. Up to 30% by weight of the oil binder can be replaced by other oil formers, for example tricresyl phosphate or polyalkylene glycols. Preferably the yellow couplers are only released in the oil former according to the invention.

In the production of the light-sensitive color photographic recording material, the diffusion-resistant yellow couplers of the present invention are incorporated into the casting solution of the silver halide emulsion layers or other colloid layers in the oil formers according to the invention, if appropriate in the presence of a wetting or dispersing agent. The hydrophilic casting solution can of course contain other conventional additives in addition to the binder. The color coupler solution does not need to be directly dispersed in the casting solution for the silver halide emulsion layer or other water permeable layer; Rather, it can also be advantageously first dispersed in an aqueous non-photosensitive solution of a hydrophilic colloid, whereupon the mixture obtained is mixed with the coating solution for the photosensitive silver halide emulsion layer or another water-permeable layer before application.

Suitable light-sensitive silver halide emulsions are emulsions of silver chloride, silver bromide or mixtures thereof, possibly with a low silver iodide content of up to 10 mol% in one of the commonly used hydrophilic binders. Gelatin is preferably used as the binder for the photographic layers used. However, this can be replaced in whole or in part by other natural or synthetic binders.

The advantages according to the invention become particularly clear when the color material according to the invention contains only silver halide emulsion with at least 95 mol% silver chloride in the light-sensitive layers.

The emulsions can be chemically and spectrally sensitized in the usual way.

The light-sensitive layer to which the yellow coupler according to the invention is assigned is in particular blue-sensitized.

The color photographic material, which preferably contains a reflective support, also contains at least one green-sensitive layer to which a magenta coupler is assigned and at least one red-sensitive layer to which a cyan coupler is assigned, and optionally intermediate and protective layers.

Research Disclosure 17643/1978 in Department IV contains an overview of the polymethine dyes suitable as spectral sensitizers, their suitable combinations and combinations with a super-sensitizing effect.

• 1. als Rotsensibilisatoren
  9-Ethylcarbocyanine mit Benzthiazol, Benzselenazol oder Naphthothiazol als basische Endgruppen, die in 5- und/oder 6-Stellung durch Halogen, Methyl, Methoxy, Carbalkoxy, Aryl substituiert sein können sowie 9-Ethyl-naphthoxathia- bzw. -selencarbocyanine und 9-Ethyl-naphthothiaoxa- bzw. -benzimidazocarbocyanine, vorausgesetzt, daß die Farbstoffe mindestens eine Sulfoalkylgruppe am heterocyclischen Stickstoff tragen.
• 2. als Grünsensibilisatoren
  9-Ethylcarbocyanine mit Benzoxazol, Naphthoxazol oder einem Benzoxazol und einem Benzthiazol als basische Endgruppen sowie Benzimidazocarbocyanine, die ebenfalls weiter substituiert sein können und ebenfalls mindestens eine Sulfoalkylgruppe am heterocyclischen Stickstoff enthalten müssen.
• 3. als Blausensibilisatoren
  symmetrische oder asymmetrische Benzimidazo-, Oxa-, Thia- oder Selenacyanine mit mindestens einer Sulfoalkylgruppe am heterocyclischen Stickstoff und gegebenenfalls weiteren Substituenten am aromatischen Kern, sowie Apomerocyanine mit einer Rhodaningruppe.

The following dyes, sorted by spectral range, are particularly suitable:

• 1. as red sensitizers
  9-ethyl carbocyanines with benzthiazole, benzselenazole or naphthothiazole as basic end groups, which can be substituted in the 5- and / or 6-position by halogen, methyl, methoxy, carbalkoxy, aryl, and 9-ethyl-naphthoxathia or -selencarbocyanines and 9- Ethyl-naphthothiaoxa- or -benzimidazocarbocyanine, provided that the dyes carry at least one sulfoalkyl group on the heterocyclic nitrogen.
• 2. as green sensitizers
  9-ethyl carbocyanines with benzoxazole, naphthoxazole or a benzoxazole and a benzthiazole as basic end groups, and also benzimidazocarbocyanines, which may also be further substituted and must likewise contain at least one sulfoalkyl group on the heterocyclic nitrogen.
• 3. as blue sensitizers
  symmetrical or asymmetrical benzimidazo, oxa, thia or selenacyanines with at least one sulfoalkyl group on the heterocyclic nitrogen and optionally further substituents on the aromatic nucleus, and apomerocyanines with a rhodanine group.

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), and the white couplers that react with color developer oxidation products yield essentially colorless products. The 2-equivalent couplers also include those couplers that contain a cleavable residue in the coupling site, 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.

Color couplers for producing the blue-green partial color image are usually couplers of the phenol or α-naphthol type.

Color coupler for generating the purple partial color image are generally couplers of the 5-pyrazolone, indazolone or pyrazoloazole type.

The blue-green and purple couplers can be incorporated in the same way and with the same oil formers as the yellow couplers.

Suitable oil formers for magenta and cyan couplers are in addition other alkyl phthalates, phosphonic esters, phosphoric acid esters, citric acid esters, benzoic acid esters, amides, fatty acid esters, trimesic acid esters, alcohols, phenols, aniline derivatives and hydrocarbons.

Examples of suitable oil formers are dibutyl phthalate, dicyclohexyl phthalate, di-2-ethylhexyl phthalate, decyl phthalate, triphenyl phosphate, tricresyl phosphate, 2-ethylhexyl diphenyl phosphate, tricyclohexyl phosphate, tri-2-ethylhexyl phosphate, tridecoxy phosphate, 2-ethylhexyl phosphate, tridecoxy phosphate, 2-ethylhexyl phylate, , 2-ethylhexyl p-hydroxybenzoate, diethyldodecanamide, N-tetradecylpyrrolidone, isostearyl alcohol, 2,4-di-tert-amylphenol, dioctyl acylate, glycerol tributyrate, isostearyl lactate, trioctyl citrate, N, N-doxy-5-butyl-2-. -octylaniline, paraffin, dodecylbenzene and diisopropylnaphthalene.

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 prevent from one photosensitive to another photosensitive layer with different spectral sensitization.

Suitable agents, which are also called scavengers or EOP-catchers, are described in Research Disclosure 17 643 (Dec. 1978), Chapter VII, 17 842/1979, pages 94-97 and 18.716 / 1979, page 650 and in EP-A- 69,070, 98,072, 124,877, 125,522 and in US-A-463,226.

The silver halide present as a light-sensitive component in the photographic material can be predominantly compact crystals, which are 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 substantially 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 of the individual grain areas, being different. The middle The 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. Homodisperse grain size distribution means that 95% of the grains do not deviate from the mean grain size by more than ± 30%. 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.

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.

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 silver halide emulsion is generally subjected to chemical sensitization under defined conditions - pH, pAg, temperature, gelatin, silver halide and sensitizer concentration - until the optimum sensitivity and fog have been reached. The procedure is e.g. described by H. Frieser "The basics of photographic processes with silver halides" page 675-734, Akademische Verlagsgesellschaft (1968).

Chemical sensitization can be carried out with the addition of compounds of sulfur, selenium, tellurium and / or compounds of the metals of subgroup VIII of the periodic table (for example gold, platinum, palladium, iridium). Thiocyanate compounds, surface-active compounds such as thioethers, heterocyclic compounds can also be used Nitrogen compounds (e.g. imidazoles, azaindenes) or spectral sensitizers (described, for example, by F. Hamer "The Cyanine Dyes and Related Compounds", 1964, or Ullmanns Encyclopedia of Industrial Chemistry, 4th edition, vol. 18, pp. 431 ff. and Research Disclosure No. 17643, Section III). As an alternative or in addition, reduction sensitization with the addition of reducing agents (tin-II salts, Amines, hydrazine derivatives, aminoboranes, silanes, formamidinesulfinic acid) can be carried out by hydrogen, by low pAg (for example less than 5) and / or high pH (for example above 8).

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 for example from 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, optionally substituted benzotriazoles or benzothiazolium salts can also be used as antifoggants. Heterocycles containing mercapto groups, for example mercaptobenzthiazoles, mercaptobenzimidazoles, mercaptotetrazoles, mercaptothiadiazoles, mercaptopyrimidines, are particularly suitable, these mercaptoazoles also being able to contain 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.). In addition to natural surface-active compounds, for example saponin, synthetic surface-active compounds (surfactants) are mainly used: non-ionic surfactants, for example alkylene oxide compounds, glycerol compounds or glycidol compounds, cationic surfactants, for example higher alkylamines, quaternary ammonium salts, pyridine compounds and other heterocyclic compounds, sulfonium compounds or phosphonium compounds, anionic surfactants containing an acid group, for example carboxylic acid, sulfonic acid, a phosphoric acid, sulfuric acid ester or phosphoric acid ester group, ampholytic surfactants, for example amino acid and aminosulfonic acid compounds and sulfur or phosphoric acid esters of an amino alcohol.

The photographic material can also contain UV light-absorbing compounds, whiteners, spacers, filter dyes, formalin scavengers, light stabilizers, antioxidants, D _min dyes, additives to improve dye, coupler and white stabilization and to reduce the color fog, plasticizers (latices), Contain biocides 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).

Certain binder layers, in particular the layer furthest away from the carrier, but also occasionally intermediate layers, especially if they represent the layer furthest away from the carrier during production, can contain photographically inert particles of an inorganic or organic nature, e.g. as matting agents or as spacers ( DE-A-33 31 542, DE-A-34 24 893, Research Disclosure 17 643, (Dec. 1978), 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 layers of the photographic material can be hardened with the usual hardening agents. Suitable curing agents are, for example, formaldehyde, glutaraldehyde and similar aldehyde compounds, diacetyl, cyclopentadione and similar ketone compounds, bis (2-chloroethyl urea), 2-hydroxy-4,6-dichloro-1,3,5-triazine and other compounds, the reactive halogen included (US-A-3 288 775, US-A-2 732 303, GB-A-974 723 and GB-A-1 167 207) divinyl sulfone compounds, 5-acetyl-1,3-diacryloylhexahydro-1,3,5 triazine and other compounds containing a reactive olefin bond (US-A-3 635 718, US-A-3 232 763 and GB-A-994 869); N-hydroxymethylphthalimide and other N-methylol compounds (US-A-2 732 316 and US-A-2 586 168); Isocyanates (US-A-3 103 437); Aziridine compounds (US-A-3 017 280 and US-A-2 983 611); Acid derivatives (US-A-2 725 294 and US-A-2 725 295); Carbodiimide type compounds (US-A-3 100 704); Carbamoylpyridinium salts (DE-A-22 25 230 and DE-A-24 39 551); Carbamoyloxypyridinium compounds (DE-A-24 08 814); Compounds with a phosphorus-halogen bond (JP-A-113 929/83); N-carbonyloximide compounds (JP-A-43353/81); N-sulfonyloximido compounds (US-A-4 111 926), dihydroquinoline compounds (US-A-4 013 468), 2-sulfonyloxypyridinium salts (JP-A-110 762/81), formamidinium salts (EP-A-0 162 308), compounds with two or more N-acyloximino groups (US-A- 4,052,373), epoxy compounds (US-A-3 091 537), isoxazole-type compounds (US-A-3 321 313 and US-A-3 543 292); Halocarboxyaldehydes such as mucochloric acid; Dioxane derivatives such as dihydroxydioxane and di-chlorodioxane; and inorganic hardeners such as chrome alum and zirconium sulfate.

The hardening can be effected in a known manner by adding the hardening agent to the casting solution for the layer to be hardened or by overlaying the layer to be hardened with a layer which contains a diffusible hardening agent.

There are slow-acting and fast-acting hardeners and so-called instant hardeners, which are particularly advantageous, in the classes listed. 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.

Color photographic negative materials are usually processed by developing, bleaching, fixing and washing or by developing, bleaching, fixing and stabilizing without subsequent washing, whereby bleaching and fixing can be combined into one processing step. All developer compounds which have the ability to react in the form of their oxidation product with color couplers to form azomethine or indophenol dyes can be used as the color developer compound. Suitable color developer compounds are aromatic compounds of the p-phenylenediamine type containing at least one primary amino group, for example N, N-dialkyl-p-phenylenediamines such as N, N-diethyl-p-phenylenediamine, 1- (N-ethyl-N-methanesulfonamidoethyl) -3 -methyl-p-phenylenediamine, 1- (N-ethyl-N-hydroxyethyl) -3-methyl-p-phenylenediamine and 1- (N-ethyl-N-methoxyethyl) -3-methyl-p-phenylenediamine. Further useful color developers are described, for example, in J. Amer. Chem. Soc. 73 , 3106 (1951) and G. Haist, Modern Photographic Processing, 1979, John Wiley and Sons, New York, page 545 ff.

After the color development, an acidic stop bath or watering can follow.

Usually the material is bleached and fixed immediately after color development. As bleaching agents e.g. Fe (III) salts and Fe (III) complex salts such as ferricyanides, dichromates, water-soluble cobalt complexes can be used. Iron (III) complexes of aminopolycarboxylic acids are particularly preferred, especially e.g. of ethylenediaminetetraacetic acid, propylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, nitrilotriacetic acid, iminodiacetic acid, N-hydroxyethylethylenediaminetriacetic acid, alkyliminodicarboxylic acids and corresponding phosphonic acids. Persulphates and peroxides, e.g. Hydrogen peroxide.

The bleach-fixing bath or fixing bath is usually followed by washing, which is designed as countercurrent washing or consists of several tanks with their own water supply.

Favorable results can be obtained using a subsequent final bath which contains little or no formaldehyde.

However, the washing can be completely replaced by a stabilizing bath, which is usually carried out in countercurrent. When formaldehyde is added, this stabilizing bath also functions as a final bath.

example 1

In each case 8 mmol of the couplers listed below were dissolved in 15 ml of ethyl acetate, 5 ml of the oil former specified below and 5 ml of a 10% by weight aqueous solution of the sodium salt of a C₁₂-alkylnaphthylsulfonic acid and at 60 ° C in 150 ml of 7.5% .-% emulsified aqueous gelatin solution. The finished emulsate was added 126 ml of a silver bromide chloride emulsion (99 mol% AgCl), with a silver content corresponding to 6.8 g AgNO₃. This casting solution was poured onto a polyethylene-coated paper at 40 ° C. with an order of 1.5 g AgNO₃ per m².

aufgetragen und die Proben getrocknet.A protective layer of 0.9 g / m² of gelatin and 0.3 g / m² of the hardening agent of the formula was applied to this layer

applied and the samples dried.

The samples were exposed behind a grayscale wedge, developed in the color developer specified below, then fixed to bleach, washed and dried.

DBP =

Dibutylphthalat

TKP =

Trikresylphosphat

DLA =

Diethylauramid

A =

Diisononylphthalsäureester

B =

Polyester aus Adipinsäure und einer Mischung aus 1,3-, 1,4-Butandiol und 2-Ethylpropandiol-1,3

C =

Polyester aus Phthalsäure und einer Mischung aus Hexandiol-1,6 und Isodecylalkohol

D =

Polyester aus Adipinsäure und einer Mischung aus 1,3-Butylenglykol und 1,6-Hexandiol

E =

1:1-Mischung aus den Ölformen A und B

F =

3:1-Mischung aus Ölformer B und dem Polypropylenglykol der Formel

The results of the sensitometric tests are given in Table 1.

DBP =

Dibutyl phthalate

CPM =

Tricresyl phosphate

DLA =

Diethylauramide

A =

Diisononylphthalic acid ester

B =

Polyester from adipic acid and a mixture of 1,3-, 1,4-butanediol and 2-ethylpropanediol-1,3

C =

Polyester from phthalic acid and a mixture of 1,6-hexanediol and isodecyl alcohol

D =

Polyester made from adipic acid and a mixture of 1,3-butylene glycol and 1,6-hexanediol

E =

1: 1 mixture of oil forms A and B.

F =

3: 1 mixture of oil former B and the polypropylene glycol of the formula

Es zeigt sich, daß bei Verwendung von DBP die Lichtechtheit des gebildeten Farbstoffs schlechter ist als mit erfindungsgemäßen Ölformern, daß bei Verwendung von DLA-Nachteile in der Tropenstabilität auftreten und daß der Vergleichskuppler V1 sogar in erfindungsgemäßen Lösungsmitteln niedrige Empfindlichkeit, schlechte Darkfadingstabilität und schlechte Tropenstabilität zeigt. TKP ist hinsichtlich der sensitometrischen Eigenschaften den erfindungsgemäßen Ölbildner vergleichbar, zeigt aber eine gegenüber den erfindungsgemäßen Proben erhöhte Anzahl von Gießfehlern, was in Beispiel 2 gezeigt wird.D _min = veil; E₀ _, ₆ = sensitivity at density 0.6; G1 = threshold gradation; G2 = shoulder gradation, D _max = maximum density; Xe = determination of the light fastness in the Xenotest with 15.10⁶ lux.h; Df = Darkfading test 3 weeks at 80 ° C and 40% rel. Air humidity; Tr = tropical storage for 14 days at 60 ° C and 90% relative humidity; ΔD (1.0) = density change at density 1.0 in%;
Coupler V1 has the formula:

It turns out that when DBP is used the lightfastness of the dye formed is worse than with oil formers according to the invention, that when using DLA disadvantages in tropical stability occur and that the comparative coupler V1 shows low sensitivity, poor dark fading stability and poor tropical stability even in solvents according to the invention . TKP is comparable to the oil formers according to the invention with regard to the sensitometric properties, but shows an increased number of pouring errors compared to the samples according to the invention, which is shown in Example 2.

Samples 4 to 11 are according to the invention.

Example 2

• 1. Schicht (Substratschicht):
  0,2 g Gelatine
• 2. Schicht (blauempfindliche Schicht):
  blauempfindliche Silberhalogenidemulsion (99,5 Mol-% Chlorid, 0,5 Mol-% Bromid, mittlerer Korndurchmesser 0,8 µm) aus 0,63 g AgNO₃ mit
  1,38 g Gelatine
  0,95 g Gelbkuppler 15
  0,2 g Weißkuppler W-1
  0,55 g Ölbildner gemäß Tabelle 2
• 3. Schicht (Schutzschicht)
  1,1 g Gelatine
  0,06 g 2,5-Dioctylhydrochinon
  0,06 g Dibutylphthalat (DBP)
• 4. Schicht (grünempfindliche Schicht)
  grünsensibilisierte Silberhalogenidemulsion (99,5 Mol-% Chlorid, 0,5 Mol-% Bromid, mittlerer Korndurchmesser 0,6 µm) aus 0,45 g AgNO₃ mit
  1,08 g Gelatine
  0,41 g Purpurkuppler M-1
  0,08 G 2,5-Dioctylhydrochinon
  0,34 g DBP
  0,20 g TKP
• 5. Schicht (UV-Schutzschicht)
  1,15 g Gelatine
  0,06 g UV-Absorber der Formel
  
  0,045 g 2,5-Dioctylhydrochinon
  0,04 g TKP
• 6. Schicht (rotempfindliche Schicht)
  rotsensibilisierte Silberhalogenidemulsion (99,5 Mol-% Chlorid, 0,5 Mol-% Bromid, mittlerer Korndurchmesser 0,5 µm) aus 0,3 g AgNO 3 mit
  0,75 g Gelatine
  0,36 g Blaugrünkuppler C-1
  0,36 TKP
• 7. Schicht (UV-Schicht)
  0,35 g Gelatine
  0,15 g UV-Absorber wie Schicht 5
  0,2 g TKP
• 8. Schicht (Schutzschicht)
  0,9 g Gelatine
  0,3 g Härtungsmittel der Formel

The following layers were applied in the order given to a support made of paper coated on both sides with polyethylene. The quantities each refer to 1 m². For the silver halide application, the corresponding amounts of AgNO₃ are given.

• 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 15
  0.2 g white coupler W-1
  0.55 g of oil generator according to Table 2
• 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 M-1
  0.08 G 2,5-dioctyl hydroquinone
  0.34 g DBP
  0.20 g CPM
• 5th layer (UV protective layer)
  1.15 g gelatin
  0.06 g UV absorber of the formula
  
  0.045 g 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% bromide, average grain diameter 0.5 µm) from 0.3 g AgNO 3 with
  0.75 g gelatin
  0.36 g of cyan coupler C-1
  0.36 CPM
• 7th layer (UV layer)
  0.35 g gelatin
  0.15 g UV absorber as layer 5
  0.2 g CPM
• 8th layer (protective layer)
  0.9 g gelatin
  0.3 g hardening agent of the formula

The emulsifier stability was checked by counting punctiform yellow coupler deposits / m² on the cast material, with a freshly prepared coupler solution ("fresh") and a coupler solution stored at 40 ° C for 24 hours (" stored ") were used. The results are shown in Table 2.

Claims (3)

Color photographic recording material with at least one light-sensitive silver halide emulsion layer and a diffusion-resistant yellow coupler of the formula assigned to it

wherein Y is an aliphatic or cycloaliphatic radical, X is a hydrogen atom or a group which can be split off on color coupling, R¹ is an alkyl radical with 1 to 20 C atoms, R² is an alkyl radical with 1 to 20 carbon atoms, mean, wherein the alkyl radicals R¹ and R² together have at least 12 carbon atoms, characterized in that liquid, ester group-containing compounds having a molecular weight of at least 350 are used as oil formers for the color couplers of the formula (I). The color photographic material of claim 1, wherein the photosensitive layers comprise silver halide emulsions with at least 95 mol% of silver chloride. The color photographic material of claim 1, wherein the yellow coupler is of the formula

corresponds to what R³ C₁₁-C₂₀ alkyl, R⁴ C₁-C₄ alkyl and R⁵ is a phenyl optionally substituted by halogen or C₁-C₄-alkyl.