EP0379893A2 - Colour-photographic recording material containing an emulsified compound providing colour - Google Patents

Abstract

Polypropylene oxides having an OH content of 1 - 3% by weight are suitable as oil formers for non-diffusing colour-donating compounds, for example colour couplers. In the case of comparatively hydrophilic compounds, especially yellow couplers with an -SO2-NH- grouping or a phenolic hydroxyl group, they reduce the tendency to crystallise and the undesired diffusion into adjacent layers. This allows a reduction of the gelatine content. The light stability is improved.

Description

The invention relates to a color photographic recording material which, in association with at least one light-sensitive silver halide emulsion layer, contains an emulsified, comparatively hydrophilic coloring compound.

Hydrophilic color couplers and other coloring compounds are generally added to the photographic coating solutions in the form of an aqueous or aqueous-alcoholic solution. The required amounts of alkali are used in the preparation of the solutions, provided that the coupler is not already present in water-soluble form as the alkali salt. Hydrophilic color couplers are often characterized by particularly high coupling speeds and are therefore very desirable in the production of highly sensitive color photographic recording materials. However, when incorporating Hydrophilic compounds from aqueous-alkaline solution in photographic layers have serious disadvantages, insofar as the high salt content in the emulsion caused by the neutralization of the alkaline solutions causes poor flatness and high brittleness of the materials. Furthermore, the casting solutions generally have to be diluted heavily with water in order to compensate for the increase in viscosity caused by the reaction of the sulfo groups or carboxyl groups with the amino groups of the gelatin. This results in a relatively high wet application of the layers during casting, which in turn requires a great deal of effort in drying the layers. In addition, this method makes it difficult to produce layers with a desired high packing density on color couplers or other coloring compounds.

The difficulties described are avoided if hydrophobic coloring compounds are used and these are incorporated in an emulsified form into the photographic coating solutions in a known manner using high-boiling organic solvents, so-called oil formers. The method is described for example in US-A-2 322 027. Preferred oil formers are phthalic acid esters, such as dibutyl phthalate or di-n-nonyl phthalate, and phosphoric acid esters, such as tricresyl phosphate; the oil formers mentioned are comparatively hydrophobic and therefore mostly very well suited for incorporating hydrophobic substances. The suitability of an oil producer is expressed in that the coloring compound in the relevant oil former has the highest possible solubility and a low tendency to crystallize. Coloring compounds are occasionally used due to their special properties, which in the aforementioned hydrophobic oil formers still have a certain, in many cases still sufficient, but nevertheless reduced solubility and have a clearly hydrophilic character. Such coloring compounds are referred to below as "comparatively hydrophilic".

The reduced solubility in the hydrophobic oil formers manifests itself in an increased tendency to crystallize and affects the technical production of the O / W emulsion (oil in water) of the coloring compounds on the one hand, and on the other hand their use in low-binder layers, for example in layers with no more than 40% by weight gelatin, particularly noticeable. If the O / W emulsions are produced on an industrial scale and a co-solvent used is removed rapidly, for example at a rate of more than 30 g / s, crystallization often occurs. In addition, the comparatively hydrophilic coloring compounds mentioned are obviously not sufficiently diffusion-resistant in many cases when using the conventional hydrophobic oil formers, and this disadvantage is particularly evident when used in low-binder layers.

The invention has for its object to provide new oil formers for coloring compounds, especially for comparatively hydrophilic coloring compounds. It has now been found that polypropylene oxides with an OH group content of between 1 and 3% by weight are suitable for this.

The present invention relates to a color photographic recording material with at least one silver halide emulsion layer, which is associated with a coloring compound incorporated with the aid of an oil former, characterized in that the oil former contains at least 30% by weight of a polypropylene oxide with an OH content of 1-3 % By weight.

The polypropylene oxide used according to the invention as an oil former can be produced by reacting water or monohydric or polyhydric alcohols with propylene oxide (PO), water with about 20-50 times the amount by weight of PO and the alcohol in question, depending on the molecular weight and value, with about 10 - 100 times the molar amount of PO are reacted to set an OH content of 1-3% by weight. As a rule, a statistical distribution over the entirety of the molecules is obtained with regard to the molecular weight of the polypropylene oxide.

Examples of monohydric or polyhydric alcohols to be used are ethanol, propanol, isopropanol, n-butanol, isobutanol, ethylene glycol, 1,2- and 1,3-propylene glycol, glycerol, tetramethylolethane, pentaerythritol, trimethylolpropane.

Examples of compounds according to the invention (polypropylene oxides) are given below. The molar amount of PO which has been reacted with 1 mol of water or mono- or polyhydric alcohol is given.

A detailed description of the use of polyethylene oxide adducts in photography with many references can be found in Nikolaus Schönfeldt, interfacially active ethylene oxide adducts, Wissenschaftliche Verlagsgesellschaft mbH Stuttgart, 1976, pages 826-829.

Using the polypropylene oxides according to the invention as oil formers, emulsions of coloring compounds can be prepared in a manner known per se. These are generally O / W emulsions (oil-in-water emulsions) in which the oily phase contains the coloring compound to be emulsified, at least one polypropylene oxide (oil former) according to the invention, optionally an auxiliary solvent and further optionally an emulsifying aid, and the aqueous phase usually contains a suitable binder, for example gelatin. The auxiliary solvent is normally removed again in the course of the preparation of the emulsate. The oil former according to the invention can also be used in the form of a mixture. Conventional oil formers, such as tricresyl phthalate (TKP) or dibutyl phthalate (DBP) and similar, also more hydrophilic oil formers such as, for example, long-chain aliphatic substituted succinic acid esters of the like, as described for example in DE-A 1 772 192, can also be used. However, the proportion of polypropylene oxides according to the invention in the total amount of oil former should not be less than 30% by weight.

With the help of the oil formers according to the invention, coloring compounds of all kinds can be incorporated into photographic layers. As a rule, these are non-diffusing compounds, which can be colored or colorless. Under the conditions of photographic development, a dye is formed from such compounds, either by releasing an optionally pre-formed colored residue as a diffusing dye or by chromogenic coupling with the oxidation product of a color developer. In the latter case, there are color couplers, e.g. Yellow coupler, magenta coupler or cyan coupler.

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

Color couplers for producing the purple partial color image are generally couplers of the 5-pyrazolone, indazolone or pyrazoloazole type; suitable examples are

Color couplers for producing the yellow partial color image are generally 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 of the formulas

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 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 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 in the DIR, DAR or FAR couplers the effectiveness of the residue released during the 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-15 47 640).

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).

The oil formers according to the invention are used with particular advantage for the incorporation of those compounds which — as explained at the beginning — are referred to as “comparatively hydrophilic”. These are in particular compounds which contain one or more -SO₂-NH groups and / or phenolic hydroxyl groups in their molecule. Examples of such compounds are couplers C-26, M-2, M-8, M-19, M-20, M-21, Y-3, Y-7 and Y-13. By virtue of such groupings, the coloring compounds have an increased solubility in the alkaline processing baths usually used, so that undesired diffusion into adjacent layers cannot normally be completely prevented during processing. The less binder the individual layers contain, the more this undesirable effect occurs.

In addition, because of the -SO₂-NH groups or phenolic hydroxyl groups, the comparatively hydrophilic coloring compounds are obviously less soluble in the commonly used hydrophobic oil formers, which manifests itself in an increased tendency to crystallize. If, on the other hand, the comparatively hydrophilic coloring compounds are incorporated with the help of the oil formers according to the invention, then not only the tendency to crystallize, but also the tendency to diffuse is significantly reduced. When using the oil formers according to the invention it is therefore possible to reduce the weight fraction of the binder in an at least one coloring compound and optionally silver halide layer to 40% or less.

Particularly preferred examples of comparatively hydrophilic coloring compounds are 2-equivalent yellow couplers, for example the following:

Examples of color photographic materials are color negative films, color reversal films, color positive films, color photographic paper, color reversal photographic paper, color sensitive materials for the color diffusion transfer process or the silver color bleaching process.

Suitable supports for the production of color photographic materials are e.g. Films and sheets of semi-synthetic and synthetic polymers such as cellulose nitrate, cellulose acetate, cellulose butyrate, polystyrene, polyvinyl chloride, polyethylene terephthalate and polycarbonate and paper laminated with a baryta layer or α-olefin polymer layer (e.g. polyethylene). These supports can be colored with dyes and pigments, for example titanium dioxide. They can also be colored black for the purpose of shielding light. The surface of the support is generally subjected to a treatment in order to improve the adhesion of the photographic emulsion layer, for example a corona discharge with subsequent application of a substrate layer. Layers with a light reflecting surface are preferred.

The color photographic materials usually contain at least one red-sensitive, green-sensitive and blue-sensitive silver halide emulsion layer and, if appropriate, intermediate layers and protective layers.

Essential components of the photographic emulsion layers are binders, light-sensitive silver halide and coloring compounds, for example color couplers.

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-vinylpyrrolidone, 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. Oxidized gelatin can also be used. The production such gelatins are described, for example, in The Science and Technology of Gelatine, edited 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 silver halide present as a light-sensitive component in the photographic material can contain chloride, bromide or iodide or mixtures thereof as the halide. For example, the halide content of at least one layer can consist of 0 to 15 mol% of iodide, 0 to 100 mol% of chloride and 0 to 100 mol% of bromide. In the case of color negative and color reversal films, silver bromide iodide emulsions are usually used; in the case of color negative and color reversal paper, silver chloride bromide emulsions with a high chloride content are used up to pure silver chloride emulsions. The crystals can be predominantly compact, which are, for example, regularly cubic or octahedral or can have transitional forms. However, platelet-shaped crystals may 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, for example 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 e.g. Doping of the 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. Homodisperse grain size distribution means that 95% of the grains do not deviate from the mean grain size by more than ± 30%.

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

The photographic emulsions may contain compounds to prevent fogging or to stabilize the photographic function during production, storage or photographic processing.

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.

Research Disclosure 17643 (Dec. 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.

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 bromides.

The differently sensitized 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, the red sensitive layers are cyan couplers, the green sensitive layers are magenta couplers and the blue sensitive layers are yellow couplers.

The couplers or other compounds can be incorporated into silver halide emulsion layers and other layers in such a way that a solution, a dispersion or an emulsion is first prepared from the compound in question and then added 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.

Hydrophobic compounds can 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.

Examples of suitable oil formers which can be used in addition to the polypropylene oxides according to the invention are dibutyl phthalate, dicyclohexyl phthalate, di-2-ethylhexyl phthalate, decyl phthalate, triphenyl phosphate, tricresyl phosphate, 2-ethylhexyl diphenyl phosphate, tricyclohexyl phosphate, tri-2-ethylhexyl tri-ethylhexyl tri-ethyl-tri-ethyl-tri-ethyl-tri-ethyl-tri-ethyl-trihydrate, -2-ethylhexylphenylphosphate, 2-ethylhexylbenzoate, dodecylbenzoate, 2-ethylhexyl p-hydroxybenzoate, diethyldodecanamide, N-tetradecylpyrrolidone, isostearyl alcohol, 2,4-di-t-amylphenol, dioctylacelate, tri-trearyl-nylate, n-trityl-n-tritylate, n-triteryl-n-tritylate, n-triteryl-n-tritylate, n-triteryl-tri-nylate -2-butoxy-5-t-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 from one light-sensitive layer into another light-sensitive layer with different spectral sensitization.

Suitable agents, which are also called scavengers or EOP-catchers, are described in Research Disclosure 17 643 (Dec. 1978), chapters VII, 17 842 (Feb. 1979) and 18 716 (Nov. 1979), page 650 and in EP A-0 069 070, 0 098 072, 0 124 877 and 0 125 522.

The photographic recording material can furthermore contain UV light-absorbing compounds, whiteners, spacers, filter dyes, formalin scavengers, light stabilizers, antioxidants, D _min dyes, additives for improving the stabilization of dyes, couplers and whites and for reducing the color fog, plasticizers (latices), Contain biocides.

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, styryl dyes, merocyanine dyes, cyanine dyes and azo dyes. Of these dyes, oxonol dyes, hemioxonol dyes and merocyanine dyes are used particularly advantageously.

Suitable white toners are e.g. in Research Disclosure 17,643 (Dec. 1978), Chapter V, in US-A-2,632,701, 3,269,840 and in GB-A-852,075 and 1,319,763.

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-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.

Additives to improve dye, coupler and whiteness stability and to reduce the color fog (Research Disclosure 17 643 (Dec. 1978), Chapter VII) can belong to the following chemical substance classes: hydroquinones, 6-hydroxychromanes, 5-hydroxycoumarans, spirochromanes, spiroindanes , p-alkoxyphenols, sterically hindered phenols, gallic acid derivatives, methylenedioxybenzenes, aminophenols, sterically hindered amines, derivatives with esterified or etherified phenolic hydroxyl groups, metal complexes.

Compounds which have both a hindered amine partial structure and a hindered phenol partial structure in one molecule (US-A-4,268,593) are particularly effective in preventing the deterioration of yellow color images as a result of the development of heat, moisture and light. In order to prevent the deterioration of purple color images, in particular as a result of exposure to light, spiroindanes (JP-A-159 644/81) and chromanes which are substituted by hydroquinone diethers or monoethers (JP-A-89 835/80 ) particularly effective.

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 having 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.

The last-mentioned 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.

example 1

Coupler emulsions are produced according to the following general emulsification instructions. Aqueous phase Desalinated water 7.9 l gelatin 0.55 kg Phenol (80%) 0.033 kg Temperature: 55 ° C Oil phase Ethyl acetate 2.4 kg Color coupler 1 kg White coupler 0.02 kg Oil producer 0.55 kg Docecylbenzenesulfonate 0.017 kg Temperature: 55 ° C

The oil phase is emulsified into the aqueous phase using a mixed siren. After the addition has ended, the mixture is post-homogenized at 50 bar using a high-pressure homogenizer.

The auxiliary solvent (ethyl acetate) is removed on a solvent evaporator, evaporating between 30 and 50 g of ethyl acetate per second.

The behavior of the emulsions produced in this way during digestion (40 ° C.) or cold storage (3 weeks, 4-6 ° C.) is shown in Table 1 below. It is indicated which oil formers and which color couplers were used (columns 1 and 2). Furthermore, the time after complete crystallization had occurred (column 3), the results after three weeks of cold storage and subsequent digestion, and the time after which crystallization had occurred (column 5).

The following connection W-1 was used as the white coupler

Example 2

A color photographic recording material was produced by applying the following layers in the order given to a support made of 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 Layer 1 (substrate layer )

Schicht 6 (rotempfindliche Schicht) rotsensibilisierte Silberhalogenidemulsion (99,5 mol-% Chlorid, 0,5 mol-% Bromid, mittlerer Korndurchmesser 0,5 µm) aus 0,3 g AgNO₃, mit 0,75 g Gelatine 0,36 g Cyankuppler C-24 0,36 g TKP Schicht 7 (UV-Schutzschicht) 0,35 g Gelatine 0,15 g UV-Absorber wie in Schicht 5 0,2 g TKP Schicht 8 (Schutzschicht) 0,9 g Gelatine 0,3 g Härtungsmittel Carbamoylpyridinium-Verbindung CAS Reg.-No. 65411-60-1 0.2 g gelatin Layer 2 (blue sensitive layer) blue-sensitive silver halide emulsion (99.5 mol% chloride, 0.5 mol% bromide, average grain diameter 0.8 µm) from 0.58 g AgNO₃ with 0.685 g total gelatin 0.685 g Total gelatin (from silver halide emulsion and coupler emulsate) 0.70 g Yellow coupler as indicated in Tables 2 and 3 0.15 g White couplers as indicated in Tables 2 and 3 0.32 g Oil formers as indicated in Tables 2 and 3 Layer 3 (intermediate layer ) 1.1 g gelatin 0.06 g 2,5-dioctyl hydroquinone 0.06 g DBP Layer 4 (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 Magenta M-3 0.08 g 2,5-dioctyl hydroquinone 0.5 g DBP 0.04 g CPM

Layer 6 (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 AgNO₃, with 0.75 g gelatin 0.36 g C-24 cyan coupler 0.36 g CPM Layer 7 (UV protective layer) 0.35 g gelatin 0.15 g UV absorber as in layer 5 0.2 g CPM Layer 8 (protective layer) 0.9 g gelatin 0.3 g Hardening agent Carbamoylpyridinium Compound CAS Reg.-No. 65411-60-1

The oil formers and yellow couplers used in the blue-sensitive layer are given in Tables 2 and 3.

und einem Grünfilter bzw. Blau­ filter belichtet und dann in folgender Weise entwickelt: Farbentwickler 33°C 3,5 min Bleichfixierbad 33°C 1,5 min Wässerung 33°C 3 min The materials so produced were behind a wedge of gradation

and a green filter or blue filter exposed and then developed in the following manner: Color developer 33 ° C 3.5 min Bleach-fixer 33 ° C 1.5 min Watering 33 ° C 3 min

The processing baths were produced according to the following recipes: developer 900 ml water 15 ml Benzyl alcohol 15 ml Ethylene glycol 3 g Hydroxylamine sulfate 4.5 g 3-methyl-4-amino-N-ethyl-N- (β-methanesulfonamidoethyl) aniline sulfate 32 g Potassium carbonate sicc. 2 g Potassium sulfite sicc. 0.6 g Potassium bromide 1 g Disodium salt of 1-hydroxyethane-1,1-diphosphonic acid Make up to 1 liter with water and adjust to pH 10.2. Bleach-fixer 700 ml water 35 ml Ammonia solution (28%) 30 g Ethylenediamine-N, N, N ′, N′-tetraacetic acid 15 g Sodium sulfite sicc. 100 g Ammonium thiosulfate sicc. 60 g Sodium (ethylenediaminetetraacetate) iron (III) complex Make up to 1 l with water and adjust to pH 7.

After the development, the color wedges obtained were measured.

Table 2 shows the percent yellow secondary density obtained after green exposure, based on a magenta density of 1.0. For comparison, the relevant value is also given in brackets in the first line, which was obtained for CPM and K-4 with a material which differed only in layer 2 by a gelatin content of 50% by weight. It is clear that when the oil formers according to the invention are used, the gelatin content in layer 2 can be reduced to values below 40% by weight without the yellow secondary density being disadvantageously increased by undesirable diffusion of the yellow coupler into the magenta layer.

In an analogous manner in Table 3, the percentage magenta density obtained after blue exposure is given. Here, the value given in brackets in the first line means the magenta secondary density of a corresponding material which has a gelatin content of 50% by weight in layer 2. It is again clear that the reduction in the gelatin content in layer 2 also has a disadvantageous effect on the undesired diffusion of the magenta coupler and that, surprisingly, this disadvantageous effect can be suppressed in the yellow layer when the oil former according to the invention is used. Table 2 Oil producer Coupler Percentage yellow secondary density after green exposure with magenta density 1.0 CPM K-4 32 (17.5) DBP K-4 29 Dinonyl phthalate K-4 30th Connection 10 K-4 17th Connection 6 K-4 18th Connection 18 K-4 17.5 Connection 24 K-4 17th Connection 27 K-4 17th Connection 41 K-4 18.5 Connection 38 K-4 20th Connection 10 K-3 17.5 CPM K-3 29 Connection 10 K-5 18th CPM K-5 32 Connection 10 K-10 18.5 CPM K-10 32.5 Connection 10 K-12 17th CPM K-12 30.5 Oil producer Coupler Percentage magenta density after blue exposure with yellow density 1.0 CPM K-4 42 (36.5) DBP K-4 41 Dinonyl phthalate K-4 41 Connection 8 K-4 36 Connection 11 K-4 37 Connection 13 K-4 36 Connection 18 K-4 38 Connection 21 K-4 36 Connection 24 K-4 36 Connection 32 K-4 37 Connection 40 K-4 37 Connection 10 K-3 38 CPM K-3 42 Connection 10 K-5 36 CPM K-5 41 Connection 10 K-10 37 CPM K-10 42 Connection 10 K-12 35 CPM K-12 40

Example 3

Various of the materials defined in Example 2 in connection with Table 2 with the yellow coupler K-4 were exposed and processed and then exposed to a radiation of 1.5 · 10⁷ lxh in a Xenotest device. The percentage decrease in the yellow density (density of the yellow dye) was determined for different initial densities once in the yellow color separation wedge and once in the neutral wedge and is given in Table 4 (values of the neutral wedge in brackets). Table 4 percentage decrease in yellow density at initial density Oil producer 0.3 0.7 1.1 1.5 DBP 67 51 35 31 (53) (34) (23) (16) Verb 10 50 26 17th 17th (28) (19) (13) (11) Verb. 24 52 27th 19th 20th (30) (21) (15) (12) Verb. 41 49 25th 18th 19th (26) (17) (12) (18)

Claims (6)

1. Color photographic recording material with at least one silver halide emulsion layer, which is associated with a compound incorporated with the aid of an oil former, characterized in that the oil former consists of at least 30% by weight of a polypropylene oxide with an OH content of 1 to 3% by weight . 2. Recording material according to claim 1, characterized in that the polypropylene oxide is a reaction product of water or mono- or polyhydric alcohols with propolyenoxide. 3. Recording material according to claim 1, characterized in that the coloring compound has at least one -SO₂-NH group. 4. Recording material according to claim 3, characterized in that the coloring compound is a color coupler. 5. Recording material according to claim 4, characterized in that the coloring compound is a 2-equivalent yellow coupler. 6. Recording material according to claim 1, characterized in that the proportion by weight of the binder in the layer containing the polypropylene oxide is 40% or less.