EP0762197A1 - Photographic recording material - Google Patents

Abstract

- In colour photographic material with a base and red-, green- and blue-sensitive Ag halide (AgX) emulsion layers and opt. light-insensitive layers, at least one of the layers contains a combination of 2-phenyl-4-(2-hydroxyphenyl)-1,3,5-triazine(s) of formula (I) as UV absorber and low-mol. or polymeric oil former(s) (II) contg. acid gps.; in which R<1>, R<3> = H, halogen, OH, SH, alkyl, aryl, alkoxy, aryloxy, acyloxy, alkylthio, arylthio, -NR<5>R<6>, alkoxycarbonyl, carbamoyl or sulphamoyl; R<2> = H, OH, halogen or alkyl; R<4> = alkyl, alkoxy, alkylthio, aryloxy, arylthio or an opt. substd. phenyl gp. of the formula; R<5> = H, alkyl or aryl; R<6> = H, alkyl, aryl, acyl, alkoxycarbonyl, carbamoyl, sulphamoyl or sulphonyl; m, n, o = 1, 2, 3 or 4.

Description

The invention relates to a photographic recording material which contains a UV absorber and an oil former in a light-sensitive silver halide emulsion layer and / or a non-light-sensitive layer.

It is known to produce color photographic images by chromogenic development, i.e. in that imagewise exposed silver halide emulsion layers are developed 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 resulting in accordance with the silver image reacting with the color coupler to form a dye image. Aromatic compounds containing primary amino groups, especially those of the p-phenylenediamine type, are usually used as color developers.

It is also known that the image dyes produced by chromogenic development undergo certain changes to varying degrees under the influence of environmental conditions. This is particularly noticeable when it comes to the effects of light and especially UV light.

From EP-A 0 520 938, EP-A 0 530 135 and EP-A 0 531 258 it is known to disperse hydroxyphenyltriazine UV absorbers in gelatin layers using high-boiling solvents.

Hydroxylphenyltriazine UV absorbers are characterized by high light stability and a high specific extinction coefficient in dilute solution from which is significantly higher than that of the commonly used hydroxyphenylbenztriazole UV absorbers. However, dispersion in gelatin layers with the aid of the usual high-boiling solvents leads to a significant reduction in the specific extinction coefficients.

The object of the invention is to provide oil formers which improve the absorption properties of hydroxyphenyltriazine UV absorbers.

It has been found that the absorption properties of hydroxyphenyltriazine UV absorbers emulsified with high-boiling solvents improve can be used if compounds with at least one acid group are used as high-boiling solvents (oil formers).

worin bedeuten

R¹ und R³

H, Halogen, Hydroxy, Mercapto, Alkyl, Aryl, Alkoxy, Aryloxy, Acyloxy, Alkylthio, Arylthio, -NR⁵-R⁶, Alkoxycarbonyl, Carbamoyl oder Sulfamoyl;

R²

H, Hydroxy, Halogen oder Alkyl;

R⁴

Alkyl, Alkoxy, Alkylthio, Aryloxy, Arylthio oder einen Rest der Formel

R⁵

H, Alkyl oder Aryl;

R⁶

H, Alkyl, Aryl, Acyl, Alkoxycarbonyl, Carbamoyl, Sulfamoyl oder Sulfonyl;

m, n und o

(gleich oder verschieden) 1, 2, 3 oder 4,

und worin mehrere Reste R¹, R² und R³ gleich oder verschieden sind.The invention relates to a color photographic recording material with a layer support and arranged thereon at least one red-sensitive silver halide emulsion layer, at least one green-sensitive silver halide emulsion layer, at least one blue-sensitive silver halide emulsion layer and optionally further non-light-sensitive layers which contains a UV absorber in at least one of its layers, characterized in that that it contains in at least one of its light-sensitive or non-light-sensitive layers a combination of at least one UV absorber of the following general formula I and at least one low molecular weight or polymeric oil group containing acid groups:

in what mean

R ¹ and R ³

H, halogen, hydroxy, mercapto, alkyl, aryl, alkoxy, aryloxy, acyloxy, alkylthio, arylthio, -NR ⁵ -R ⁶ , alkoxycarbonyl, carbamoyl or sulfamoyl;

R ²

H, hydroxy, halogen or alkyl;

R ⁴

Alkyl, alkoxy, alkylthio, aryloxy, arylthio or a radical of the formula

R ⁵

H, alkyl or aryl;

R ⁶

H, alkyl, aryl, acyl, alkoxycarbonyl, carbamoyl, sulfamoyl or sulfonyl;

m, n and o

(same or different) 1, 2, 3 or 4,

and wherein a plurality of R ¹ , R ² and R ^{3 are the} same or different.

The alkyl and aryl groups can be further substituted.

X²¹

T

H oder ein Segment eines Polymergerüstes;

Q¹ und Q²

-O- oder -NR²²-;

R²¹

Alkylen oder Arylen;

R²²

H, Alkyl oder Aryl;

p, q, und r

(gleich oder verschieden) 0 oder 1.

The low molecular weight or polymeric acid group-containing oil formers are in particular compounds of the formula II

T- [R ²¹ - (Q ¹ ) _p ] _q -X ²¹ -OH (II),

in which mean:

X ²¹

T

H or a segment of a polymer backbone;

Q ¹ and Q ²

-O- or -NR ²² -;

R ²¹

Alkylene or arylene;

R ²²

H, alkyl or aryl;

p, q, and r

(same or different) 0 or 1.

The alkylene and arylene radicals represented by R ²¹ and the alkyl and aryl radicals represented by R ²² contain up to 20 C atoms and in turn can carry further substituents. Examples of such substituents are halogen atoms, hydroxyl groups, alkoxy groups, acyloxy groups, alkoxycarbonyl groups, Acylamino groups, carbamoyl groups, urea groups, further acid groups and alkyl side chains. In particular, alkyl and alkylene groups can be interrupted by oxygen atoms.

In a preferred embodiment of the invention, T (in formula II) is H and q is 1. In this case, it is a low-molecular acid group-containing oil former with at least 10 carbon atoms. Examples of such low molecular weight oil formers are given below (compounds II-1 to II-19).

In another preferred embodiment of the invention, T (in formula II) represents a segment of a polymer backbone. The acid group-containing oil former used according to the invention is then a polymer with recurring structural units (segments), which has at least one group of the formula

- [R ²¹ - (Q ¹ ) _p ] _q -X ²¹ -OH

included, where q is preferably 0. Suitable polymers are copolymers or polycondensation or polyaddition products with an acid number of 10 to 200, preferably 40 to 150. Examples of suitable monomers with acidic groups in copolymers are: acrylic acid, methacrylic acid, itaconic acid, methacylamide undecanoic acid, maleic acid, fumaric acid, vinylphosphonic acid, vinylsulfonic acid, 2 -Acrylamido-2-methylpropanesulfonic acid, sulfoethyl methacrylate, vinylbenzoic acid, methacrylamidopropyl phosphate, styrene sulfonic acid, acrylamidohexane carboxylic acid, succinic acid semiesters of hydroxyalkyl acrylates or methacrylates, phthalic acid half esters of hydroxyalkyl acrylates or methacrylates.

Examples of comonomers without acidic groups are glycidyl methacrylate, N ( m -hydroxyphenyl) methacrylamide, 2-hydroxyethyl acrylate, 2-phenyl-1-vinylimidazole, 2-hydroxypropyl acrylate, N-isopropylacrylamide, N- (1,1-dimethyl-3-dimethylaminopropyl) acrylamide, 2-methyl-1-vinylimidazole, 1-vinylimidazole, N-vinyl-ε-caprolactam, p -Methansultonamidostyrol, N-methyl methacrylamide, methacrylamide, N- (3-oxo-n butyl) maleimide, maleimide, N- ( 2-aminoethyl) methacrylamide hydrochloride, 2-hydroxyethyl methacrylate, methacryloyl urea, N- (3-aminopropyl) methacrylamide hydrochloride, N- (2-amino-2-methylpropyl) methacrylamide, acrylonitrile, α-chloroacrylonitrile, methacrylonitrile, N- (2-hydroxypropyl) methacrylamide , N-acryloylpiperidine, N-vinylsuccinimide, N-vinylphthalimide, 2-hydroxypropyl methacrylate, 2- (5-ethyl-2-pyridyl) ethyl acrylate, N- (3-methacryloyloxypropyl) thiourea, N-vinyl-2-pyrrolidone, p- aminostyrene , 2- (N, N-dibutylamino) ethyl acrylate, N- (4-vinylphenyl) thiourea, 3-acrylamido-2-oxotetrahydrothiophene, N- (4-methacryloyloxyphenyl) methanesulfonamide, 1,1-dicyan-4- [N- (t-butyl) -N- (2-methacryloyloxyethylamino) -1,3-butadiene, N- ( p -sulfamoylphenyl) maleimide, N-methacryloyl- p -toluenesulfonamide, N- (4-vinylphenyl) -N'-methylthiourea, 2-acrylamido-2-hydroxymethyl-1,3-propanediol , N, N-dimethyl methacrylamide, N-methyl acrylamide, 2-ureidoethyl vinyl ether, N-methacryloyl-N'-ureidoacetylhydrazine, N-vinyl-N '- (2-hydroxyethyl) succinamide, 2-methyl-5-vinylpyridine, N-vinyl- N '- (2-amino-2-methylpropyl) succinamide, N-vinylcarbazole, 2-vinylpyridine, 4-vinylpyridine, N-isopropylmethacrylamide, N, N-dimethylacrylamide, 2- (2-chloro-4,6-dimethylphenyl) - 5-acrylamidopyrazolin-3-one, 2- (diethylamino) ethyl acrylate, 3,6-dimethyl-3,6-diazoheptylacrylate, 2- (dimethylamino) ethyl acrylate, 2- (dimethylamino) ethyl methacrylate, 2- (diethylamino) ethyl methacrylate, 3- [3- (dimethylamino) propyl] acrylamide, acrylamide, N- (3-methyl-5-oxo-3-heptyl) acrylamide, N- (2-methyl-4-oxo-2-p entyl) acrylamide, N-methyl-2-aminoethyl methacrylate hydrochloride, allyl alcohol, N-acryloyl methionine methyl ester, N-methylolacrylamide, N- (3- or -5-hydroxymethyl-2-methyl-4-oxo-2-pentyl) acrylamide, bis (1 -Dimethylaminoethyl) methyl methacrylate, N- (isobutoxymethyl) acrylamide, N- (isobutoxymethyl) methacrylamide, N- (m- and p-vinylbenzyl) -N, N-dimethylamine, m- and p-vinylbenzyl alcohol, 2-poly (ethyleneoxy) ethyl acrylate , Ethyl acrylamido acetate, methacryloyloxypolyglycerol, 2- ( t- butylamino) ethyl methacrylate, 3- [2- (dimethylamino) ethyl] acrylamide, 3- [2- (dimethylamino) ethyl] methacrylamide, 3- (diethylamino) propyl acrylate, 4- (diethylamino) -1-methylbutyl acrylate, 4- [N- (2-acryloyloxyethyl) -N-ethylamino] -1,1-dicyan-1,3-butadiene, 1,1-dicyan-4- [N- (1,1-dimethylethyl ) -N- (2-methacryloyloxyethyl) amino] -1,3-butadiene, 1,1-dicyano-4 - ([N- (1-dimethylethyl) -N- (2-methacryloyloxyethylcarbamoylethyl) amino] -1,3- butadiene, N, N-diethyl-5- (m -and p -vinylphenyl) -3-keto-pentanoylamid, t -Pentylacrylat, n -Pentylacrylat, 3-pentyl, n- butyl acrylate, benzyl acrylate, t- butyl methacrylate, 5-methyl-1,3,6-heptatriene, 1,1-dihydroperfluorobutyl acrylate, di- n- butyl-α-methylene glutarate, benzyl methacrylate, 3-oxo-n-butyl acrylate, t - butyl acrylate, cyclohexyl acrylate, cyclopentyl acrylate, cetyl acrylate, cyclohexyl methacrylate, cyclopentadiene, butadiene, 2-Norbornylmethylacrylat, 2- (p-toluenesulfonyloxy) ethyl acrylate, trans-1,2-dichloroethylene, 2-norbornylmethyl, Diethylmethacryloylmalonat, dimethyl-α-methylenglutarat, ethyl methacrylate, ethylene , p -chlorostyrene, vinylthio (methylthio) methane, 1-vinylthio-4-methylthiobutane, isobutyl acrylate, ethyl-N-acryloylglycine, ethyl 5- ( m - and p -vinylphenyl) -3-ketopentanoate, methyl 5- ( m - and p- vinylphenyl) -3-ketopentanoate, N- (3,6-dithiaheptyl) acrylamide, 2-ethylhexyl acrylate, bis (cyclohexylmethyl) -α-methylene glutarate, n- hexyl methacrylate, 3-ethyl-1-methylbutyl acrylate, N- (3,6-dithiaoctyl) acrylate, 2-ethylhexyl methacrylate, 2-isobornyl methacrylate, 6- ( m - and p- vinylphenyl) -2,4-hexanedione, diisobutyl-α-methylene glutarate, chloroprene, bis- (2- thiabutyl) methyl acrylate, n-butyl methacrylate, isobutyl methacrylate, 3-oxo-n-butyl methacrylate, isopropyl methacrylate, t-butyl-5- (m - and p -vinylphenyl) -3-ketopentanoat, lauryl acrylate, lauryl methacrylate, methyl acrylate, methyl α-chloroacrylate , Methyl methacrylate, methyl vinyl ketone, 3-methyl-2-nitropropyl acrylate, 2- (3-nortricyclylmercapto) ethyl methacrylate, 1-vinylthio-3-methylthiopropan, 5-norbornen-2-yl-methyl methacrylate, N- (1,1-dimethyl-3 -methylthiopropyl) acrylamide, 2-methyl-2-nitropropyl methacrylate, 5- (or 6-) methylmercapto-2-norbornylmethyl methacrylate, 3,7-dithio-1-octene, 3-methyl-2-norbornylmethyl methacrylate, 4-methyl-2- propylpentylacrylat, n -Octylacrylat, n -Octadecylacrylat, n -Octadecylmethacrylat, 2-ethoxyethyl, 2-ethoxyethyl, n -Octylmethacrylat, 2-methoxyethyl methacrylate, 2-Methoxyethylacr ylate, 2-methoxymethoxyethyl acrylate, 1,3,6-octanes, ethyl acrylate, propyl acrylate, 2-cyanoethyl acrylate, dicyclopentenyl acrylate, 2,2,2-trifluoroethyl acrylate, phenyl acrylate, isopropyl acrylate, n-propyl methacrylate, N- (1,1-dimethyl-3 -ethylthiopropyl) acrylamide, N- (3-thiabutyl) acrylamide, N- (3-thiaheptyl) acrylamide, 2,5-dichlorosryrol, N- [2- (4-t-butylphenylthio) ethyl] acrylamide, N- (2- Phenylthioethyl) acrylamide, N- [2- ( p- tolylthio) ethyl] acrylamide, n -hexyl acrylate, N- (1,1-dimethyl-2-methylthioethyl) acrylamide, 2-methacryloyloxyethyl tosylate, N- (3-thiabutyl) methacrylamide, Styrene, N- [2,2-bis (ethylthio) ethyl] acrylamide, sec-butyl acrylate, p- bromosryrol, o -chlorosryrol, p -fluorosryrol m -chlorostyrene, p - t -butylstyrene, m - and p - (2nd -Thiapropyl) styrene, 2- (methylsulfinyl) ethyl acrylate, 2- (ethylsulfinyl) ethyl acrylate, trichlorethylene, 2,2-dimethylbutyl acrylate, neohexyl acrylate, 3-thiapentryl acrylate, N- (3-thiapentyl) methacrylamide, 3-thiapentyl methacrylate -Thiapentyl) acrylamide, N- t -Butylacrylamide, Vinylace tat, vinyl bromide, butyl vinyl ether, vinylidene bromide, vinyl chloride, vinyl ethyl thioacetate, vinyl isobutyrate, vinyl chloroacetate, vinyl 2-ethylhexanoate, m - and p -vinyltoluene, 1-bromo-1-chloroethylene, vinyl neodecanoate, 3,4-dichlorostyrene, dimethyl-2-methyl 1,3-butadienyl phosphate, dimethyl-1-propen-2-yl-phosphate, α-methylstyrene, methacryloyloxyethyl trifluoroacetate, N-phenylmaleimide, N- ( p- chlorophenyl) maleimide, methyl vinyl ether, 2- (methoxymethoxy) ethyl acrylate, vinylbenzyl acetate.

Examples of polymeric acid group-containing oil formers according to the invention are given below (P-1 to P-10).

Further suitable polymeric compounds of the formula II containing acid groups are polyester carboxylic acids which are constructed in block form, each hydrophobic polyester block being followed by a hydrophilic block with two free carboxyl groups. Such polyester carboxylic acids are described, for example, in DE-A-38 30 522. For example, the polyester carboxylic acids I-1 to I-13 described there are suitable.

worin bedeuten

R³¹

H, Alkyl, Aryl oder Acyl;

R³², R³⁵ und R³⁸

Halogen, Alkyl, Aryl, Alkoxy, Aryloxy, Acyloxy, Alkylthio, Arylthio oder Acylamino;

R³³, R³⁴, R³⁶ und R³⁷

(gleich oder verschieden) H, -OH oder einen Rest wie R³²;

s, t und u

0, 1 oder 2.

In a preferred embodiment of the invention, the hydroxyphenyl UV absorbers correspond to formula III

in what mean

R ³¹

H, alkyl, aryl or acyl;

R ³² , R ³⁵ and R ³⁸

Halogen, alkyl, aryl, alkoxy, aryloxy, acyloxy, alkylthio, arylthio or acylamino;

R ³³ , R ³⁴ , R ³⁶ and R ³⁷

(identical or different) H, -OH or a radical such as R ³² ;

s, t and u

0, 1 or 2.

An alkyl radical represented by R ³¹ to R ³⁸ or contained therein can be straight-chain, branched or cyclic and contain 1-36, preferably 1-20 C atoms. An alkyl or aryl radical represented by R ³¹ to R ³⁸ or contained therein can in turn be substituted; possible substituents are the groups given for R ³² . An acyl radical represented by R ³¹ to R ³⁸ or contained therein can be derived from an aliphatic or aromatic carboxylic or sulfonic acid, a carbonic acid semi-ester, a carbamic or sulfamic acid, a phosphoric or phosphonic acid. Several radicals R ³² , R ³⁵ and R ³⁸ can be the same or different; these radicals are preferably alkyl, aryl, acylamino, acyloxy, halogen and / or alkoxy.

Examples of preferred compounds of formula I according to the invention are as follows

According to the invention, the low molecular weight or polymeric acid group-containing oil formers are used as oil formers for the hydroxylphenyltriazine UV absorbers of the formula I, ie acid group-containing oil formers and the UV absorber of the formula I are advantageously dispersed in the casting solution for the layer in question in the form of a common emulsifier. The amounts used for all layers together are 50 to 1,500 mg / m ² , preferably 200 to 700 mg / m ² for the UV absorber and 50 to 1,500 mg / m ² , preferably 100 to 500 mg / m ² for the oil group containing acid groups. The combination of hydroxylphenyltriazine UV absorber of the formula I and acid group-containing oil former is preferably used above or in the light-sensitive silver halide emulsion layer which is the most distant from the support.

The recording material according to the invention has significantly improved absorption properties in the UV light range. The hydroxylphenyltriazine UV absorbers dispersed with the aid of the oil formers according to the invention have a significantly higher absorption compared to the dispersion with conventional oil formers. This makes it possible to use smaller amounts with the same effect and thereby reduce the layer thickness.

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.

The photographic materials consist of a support on which at least one light-sensitive silver halide emulsion layer is applied. Thin films and foils are particularly suitable as supports. An overview of carrier materials and auxiliary layers applied to the front and back are shown in Research Disclosure 37254, Part 1 (1995), p. 285.

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.

Depending on the type of photographic material, these layers can be arranged differently. This is shown for the most important products:

Color photographic films such as color negative films and color reversal films have 2 or 3 red-sensitive, cyan-coupling silver halide emulsion layers, 2 or 3 green-sensitive, purple-coupling silver halide emulsion layers and 2 or 3 blue-sensitive, yellow-coupling silver halide emulsion layers on the support in the order given below. The layers of the same spectral sensitivity differ in their photographic sensitivity, the less sensitive sub-layers generally being arranged closer to the support than the more sensitive sub-layers.

A yellow filter layer is usually applied between the green-sensitive and blue-sensitive layers, which prevents blue light from reaching the layers below.

Color photographic paper, which is generally much less sensitive to light than a color photographic film, usually has a blue-sensitive, yellow-coupling silver halide emulsion layer, a green-sensitive, purple-coupling silver halide emulsion layer and a red-sensitive, cyan-coupling silver halide emulsion layer on the support in the order given below; the yellow filter layer can be omitted.

Deviations in the number and arrangement of the photosensitive layers can be carried out in order to achieve certain results. For example, all highly sensitive layers can be combined in one layer package and all low-sensitivity layers can be combined in another layer package in a photographic film in order to increase the sensitivity (DE 25 30 645).

The possibilities of the different layer arrangements and their effects on the photographic properties are described in J. Int. Rec. Mats., 1994, Vol. 22, pages 183-193.

Binding agents, silver halide grains and color couplers are essential components of the photographic emulsion layers.

Information on suitable binders can be found in Research Disclosure 37254, Part 2 (1995), p. 286.

Information on suitable silver halide emulsions, their preparation, maturation, stabilization and spectral sensitization, including suitable spectral sensitizers, can be found in Research Disclosure 37254, Part 3 (1995), p. 286 and in Research Disclosure 37038, Part XV (1995), p. 89.

Photographic materials with camera sensitivity usually contain silver bromoiodide emulsions, which may also contain small amounts of silver chloride. Photographic copying materials contain either silver chloride bromide emulsions with up to 80 mol% AgBr or silver chloride bromide emulsions with over 95 mol% AgCl.

Information on the color couplers can be found in Research Disclosure 37254, Part 4 (1995), p. 288 and in Research Disclosure 37038, Part II (1995), p. 80. The maximum absorption of the dyes formed from the couplers and the color developer oxidation product is preferably in the following ranges: yellow couplers 430 to 460 nm, purple couplers 540 to 560 nm, cyan couplers 630 to 700 nm.

In color photographic films, compounds are often used to improve sensitivity, graininess, sharpness and color separation, which, when reacted with the developer oxidation product, release compounds which are photographically active, e.g. DIR couplers that release a development inhibitor.

Information on such compounds, in particular couplers, can be found in Research Disclosure 37254, Part 5 (1995), p. 290 and in Research Disclosure 37038, Part XIV (1995), p. 86.

The mostly hydrophobic color couplers, but also other hydrophobic components of the layers, are usually dissolved or dispersed in high-boiling organic solvents. These solutions or dispersions are then emulsified in an aqueous binder solution (usually gelatin solution) and, after the layers have dried, are present as fine droplets (0.05 to 0.8 μm in diameter) in the layers.

Suitable high-boiling organic solvents, methods for incorporation into the layers of a photographic material and other methods for introducing chemical compounds into photographic layers can be found in Research Disclosure 37254, Part 6 (1995), p. 292.

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 compounds (white couplers, scavengers or EOP scavengers) can be found in Research Disclosure 37254, Part 7 (1995), p. 292 and in Research Disclosure 37038, Part III (1995), p. 84.

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 the stability of dyes, couplers and whites as well as to reduce the color fog, plasticizers (latices), Contain biocides and others.

Suitable compounds can be found in Research Disclosure 37254, Part 8 (1995), p. 292 and in Research Disclosure 37038, Parts IV, V, VI, VII, X, XI and XIII (1995), p. 84 ff.

The layers of color photographic materials are usually hardened, ie the binder used, preferably gelatin, is crosslinked by suitable chemical processes.

Suitable hardener substances can be found in Research Disclosure 37254, Part 9 (1995), p. 294 and in Research Disclosure 37038, Part XII (1995), page 86.

After image-wise exposure, color photographic materials are processed according to their character according to different processes. Details of the procedures and the chemicals required for them are published in Research Disclosure 37254, Part 10 (1995), p. 294 and in Research Disclosure 37038, Parts XVI to XXIII (1995), p. 95 ff. Together with exemplary materials.

Examples example 1 Sample 1

1. Schicht

(Substratschicht)

• 0,10 g Gelatine

2. Schicht

(UV-Schicht)

• 1,00 g Gelatine
• 0,44 g UV-Absorber I-1
• 0,44 g Dibutylphthalat (DBP)

3. Schicht

(Schutzschicht)

• 0,50 g Gelatine
• 0,09 g Härtungsmittel XH-1

The following layers are applied in the order given on a transparent polyester support. The quantities given relate to 1 m ² .

1st layer

(Substrate layer)

• 0.10 g gelatin

2 layer

(UV layer)

• 1.00 g gelatin
• 0.44 g UV absorber I-1
• 0.44 g dibutyl phthalate (DBP)

3 layer

(Protective layer)

• 0.50 g gelatin
• 0.09 g of XH-1 curing agent

The long-wave absorption maximum (λ _max ) and the extinction at λ _max (E (λ _max )) are then determined (Table 1).

Samples 2 to 13

Samples 2 to 13 are produced like sample 1 with the difference that in the third layer the UV absorbers and the oil formers (DBP) are exchanged for the compounds given in table 1.

As Table 1 shows, the absorption of the UV absorbers according to the invention by the oil formers according to the invention is improved by more than 20% compared to the conventional oil formers COF-1 to COF-4.

Example 2

Samples 1 to 13 are irradiated with the light of a xenon lamp standardized for daylight with 40 x 10 ⁶ lux-h. In all samples, the decrease in E (λ _max ) is between 2 and 4%, ie the oil formers according to the invention do not lead to a deterioration in the light stability.

Example 3

Schicht 1

(Substratschicht)

• 0,10 g Gelatine

Schicht 2

(blauempfindliche Schicht):
blauempfindliche Silberhalogenidemulsion (99,5 mol-% Chlorid, 0,5 mol-% Bromid, mittlerer Korndurchmesser 0,9 µm) aus 0,50 g AgNO₃, mit

• 1,25 g Gelatine
• 0,42 g Gelbkuppler XY-1
• 0,18 g Gelbkuppler XY-2
• 0,50 g Trikresylphosphat (TKP)
• 0,10 g Stabilisator XST-1
• 0,70 mg Blausensibilisator XBS-1
• 0,30 mg Stabilisator XST-2

Schicht 3

(Zwischenschicht)

• 1,10 g Gelatine
• 0,06 g Oxformfänger XSC-1
• 0,06 g Oxformfänger XSC-2
• 0,12 g TKP

Schicht 4

(grünempfindliche Schicht)
grünempfindliche Silberhalogenidemulsion (99,5 mol-% Chlorid, 0,5 mol-% Bromid, mittlerer Korndurchmesser 0,47 µm) aus 0,40 g AgNO₃, mit

• 0,77 g Gelatine
• 0,41 g Magentakuppler XM-1
• 0,06 g Stabilisator XST-3
• 0,12 g Oxformfänger XSC-2
• 0,34 g Dibutylphthalat (DBP)
• 0,70 mg Grünsensibilisator XGS-1
• 0,50 mg Stabilisator XST-4

Schicht 5

(UV-Schutzschicht)

• 0,95 g Gelatine
• 0,30 g UV-Absorber I-11
• 0,03 g Oxformfänger XSC-1
• 0,03 g Oxformfänger XSC-2
• 0,30 g TKP

Schicht 6

(rotempfindliche Schicht)
rotempfindliche Silberhalogenidemulsion (99,5 mol-% Chlorid, 0,5 mol-% Bromid, mittlerer Korndurchmesser 0,5 µm) aus 0,30 g AgNO₃, mit

• 1,0 g Gelatine
• 0,46 g Cyankuppler XC-1
• 0,46 g TKP
• 0,03 mg Rotsensibilisator XRS-3
• 0,60 mg Stabilisator XST-5

Schicht 7

(UV-Schutzschicht)

• 0,30 g Gelatine
• 0,10 g UV-Absorber I-11
• 0,10 g TKP

Schicht 8

(Schutzschicht)

• 0,90 g Gelatine
• 0,05 g Weißtöner XWT-1
• 0,07 g Beize (PVP)
• 1,20 mg Siliconöl
• 2,50 mg Abstandshalter (Polymethylmethacrylat, mittlere Teilchengröße 0,8 µm)
• 0,30 g Härtungsmittel XH-1

A multilayer color photographic recording material was produced (layer structure A) by applying the following layers in the order given to a layer support made of paper coated on both sides with polyethylene. All amounts refer to 1 m ² , the amount of silver is given as AgNO ₃ :

Layer 1

(Substrate layer)

• 0.10 g gelatin

Layer 2

(blue sensitive layer):
blue-sensitive silver halide emulsion (99.5 mol% chloride, 0.5 mol% bromide, average grain diameter 0.9 µm) from 0.50 g AgNO ₃ , with

• 1.25 g gelatin
• 0.42 g yellow coupler XY-1
• 0.18 g yellow coupler XY-2
• 0.50 g tricresyl phosphate (CPM)
• 0.10 g stabilizer XST-1
• 0.70 mg blue sensitizer XBS-1
• 0.30 mg stabilizer XST-2

Layer 3

(Intermediate layer)

• 1.10 g gelatin
• 0.06 g Oxform catcher XSC-1
• 0.06 g Oxform catcher XSC-2
• 0.12 g CPM

Layer 4

(green sensitive layer)
green-sensitive silver halide emulsion (99.5 mol% chloride, 0.5 mol% bromide, average grain diameter 0.47 µm) from 0.40 g AgNO ₃ , with

• 0.77 g gelatin
• 0.41 g XM-1 magenta coupler
• 0.06 g stabilizer XST-3
• 0.12 g Oxform catcher XSC-2
• 0.34 g dibutyl phthalate (DBP)
• 0.70 mg green sensitizer XGS-1
• 0.50 mg stabilizer XST-4

Layer 5

(UV protective layer)

• 0.95 g gelatin
• 0.30 g UV absorber I-11
• 0.03 g Oxform catcher XSC-1
• 0.03 g Oxform catcher XSC-2
• 0.30 g CPM

Layer 6

(red sensitive layer)
red-sensitive silver halide emulsion (99.5 mol% chloride, 0.5 mol% bromide, average grain diameter 0.5 µm) from 0.30 g AgNO ₃ , with

• 1.0 g gelatin
• 0.46 g cyan coupler XC-1
• 0.46 g CPM
• 0.03 mg red sensitizer XRS-3
• 0.60 mg stabilizer XST-5

Layer 7

(UV protective layer)

• 0.30 g gelatin
• 0.10 g UV absorber I-11
• 0.10 g CPM

Layer 8

(Protective layer)

• 0.90 g gelatin
• 0.05 g XWT-1 white toner
• 0.07 g stain (PVP)
• 1.20 mg silicone oil
• 2.50 mg spacer (polymethyl methacrylate, average particle size 0.8 µm)
• 0.30 g of XH-1 curing agent

Layer structures B to J

Layer structures B to J are produced like layer structure A, with the difference that the UV absorber and the oil generator (CPM) in layers 5 and 7 have been replaced by those given in Table 2. In the layer structures E to J, the yellow couplers XY-1 and XY-2 and the stabilizer XST-1 in the same quantity were replaced by XY-3 or XST-6 in layer 2 and the magenta coupler XM-1 by 0 in layer 4. 20 g XM-2, the Oxform catcher XSC-2 replaced by 0.20 g stabilizer XST-7 and the stabilizer XST-3 by 0.10 g XST-8, as can be seen in Table 2.

Compounds used in Example 3:

The color photographic recording material is exposed through a step wedge. Additional filters are placed in the beam path of the exposure unit so that the wedge appears neutral at an optical density of D = 0.6. The exposed material is processed according to the following scheme: step time temperature Develop 45 s 35 ° C Fix bleach 45 s 35 ° C Water 90 s 33 ° C

Color developer solution (CD)

Tetraethylene glycol 20.0 g N, N-diethylhydroxylamine 4.0 g (N-ethyl-N- (2-methanesulfonamido) ethyl) -4-amino-3-methylbenzenesulfate 5.0 g Potassium sulfite 0.2 g Potassium carbonate 30.0 g Polymaleic anhydride 2.5 g Hydroxyethane diphosphonic acid 0.2 g White toner (4,4'-diaminostilbene type) 2.0 g Potassium bromide 0.02 g make up to 1000 ml with water, adjust the pH to pH = 10.2 with KOH or H ₂ SO ₄ .

Bleach-fix solution (BX)

Ammonium thiosulfate 75.0 g Sodium bisulfite 13.5 g Ethylenediaminetetraacetic acid (iron ammonium salt) 45.0 g make up to 1,000 ml with water, adjust the pH to pH 6.0 with ammonia (25%) or acetic acid.

The samples are then irradiated with the light of a xenon lamp standardized for daylight at 20 × 10 ⁶ lux-h and the percentage decrease is then determined (Table 2). Table 2 (V = comparison, E = according to the invention) Layer structure UV absorber Oil former % Decrease in density at the initial density D = 1.0 gb pp bg A (V) I-11 CPM 43 54 46 B (V) I-16 COF-4 44 53 46 C (E) I-11 TKP / II-10 (1: 1) 39 47 41 D (E) I-16 P-9 39 46 42 E (V) I-3 DBP 35 53 43 F (V) I-4 COF-1 34 53 42 G (E) I-3 II-16 30th 43 36 H (E) I-3 P-10 32 44 38 I (E) I-4 COF-5 / II-1 (1: 1) 31 45 38 J (E) I-4 P-1 32 45 39

As can be seen from Table 2, the decrease in density of the image dyes during irradiation is markedly reduced by using the oil formers according to the invention.

Claims (5)

Color photographic recording material with a layer support and arranged thereon at least one red-sensitive silver halide emulsion layer, at least one green-sensitive silver halide emulsion layer, at least one blue-sensitive silver halide emulsion layer and optionally further non-light-sensitive layers which contains at least one of its layers a UV absorber, characterized in that it is present in at least one its light-sensitive or non-light-sensitive layers contains a combination of at least one UV absorber of the following general formula I and at least one low-molecular or polymeric oil group containing acid groups:

in what mean R ¹ and R ³ H, halogen, hydroxy, mercapto, alkyl, aryl, alkoxy, aryloxy, acyloxy, alkylthio, arylthio, -NR ⁵ -R ⁶ , alkoxycarbonyl, carbamoyl or sulfamoyl; R ^{2 is} H, hydroxy, halogen or alkyl; R ^{4 is} alkyl, alkoxy, alkylthio, aryloxy, arylthio or a radical of the formula

R ^{5 is} H, alkyl or aryl; R ⁶ H, alkyl, aryl, acyl, alkoxycarbonyl, carbamoyl, sulfamoyl or sulfonyl; m, n and o (identical or different) 1, 2, 3 or 4, and wherein a plurality of R ¹ , R ² and R ^{3 are the} same or different. Recording material according to claim 1, characterized in that the low molecular weight or polymeric oil former corresponds to formula II:

T- [R ²¹ - (Q ¹ ) _p ] _q -X ²¹ -OH (II)

in which mean: X ²¹

T H or a segment of a polymer backbone; Q ¹ and Q ² -O- or -NR ²² -; R ²¹ alkylene or arylene; R ^{22 is} H, alkyl or aryl; p, q and r (identical or different) 0 or 1. Recording material according to one of claims 1 and 2, characterized in that the UV absorber corresponds to formula III:

in which mean: R ^{31 is} H, alkyl, aryl or acyl; R ³² , R ³⁵ and R ^{38 are} halogen, alkyl, aryl, alkoxy, aryloxy, acyloxy, alkylthio, arylthio or acylamino; R ³³ , R ³⁴ , R ³⁶ and R ³⁷ (identical or different) are H, -OH or a radical such as R ³² ; s, t and u (same or different) 0, 1 or 2. Recording material according to one of claims 1 to 3, characterized in that the UV absorber of the formula I and the acid group-containing oil former of the formula II are contained in the recording material in a total amount of 50-1,500 mg / m ² each. Recording material according to one of claims 1 to 3, characterized in that the combination of UV absorber of the formula I and acid group-containing oil former of the formula II at least in the light-sensitive silver halide emulsion layer which is furthest away from the support or in a non-light-sensitive layer which is still further away from the support is included.