DE19500441A1 - Colour photographic material contains immobile photostable UV absorber - Google Patents

Abstract

Colour photographic material has a base coated with red-,green- and blue-sensitive Ag halide (AgX) emulsion layer(s) associated with cyan, magenta and yellow couplers respectively and opt. other layers. The novelty is that at least one layer contains a polymeric UV absorber (I), obtd. by polymerising ethylenically unsatd. 2-phenyl-4-(2-hydroxyphenyl)-1,3,5- triazine monomer(s) of formula (II), R<1>, R<3> = 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 a gp. of formula (III), R<5> = H, alkyl or aryl,m R<6> = H, alkyl, aryl, acyl, alkoxycarbonyl, carbamoyl or sulphamoyl, m, n, o = 1, 2, 3 or 4, at least one of R<1>-4 contains an ethylenically unsatd. polymerisable gp.

Description

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

It is known to produce colored photographic images by chromogenic development put, d. H. in that image-wise exposed silver halide emulsions layers in the presence of suitable color couplers by means of suitable color-forming Developer substances - so-called color developer - developed, the in Conformity with the silver image resulting oxidation product of the development Lersubstanzen reacts with the color coupler to form a dye image. As color developers are usually aromatic, primary amino groups ent holding compounds, especially those of the p-phenylenediamine type used.

It is also known that the image color produced by chromogenic development to varying degrees under the influence of environmental conditions to undergo certain changes. This is particularly noticeable what the exposure of light and in particular short-wave UV light.

From US-A 4,009,039 it is known, 2- (2'-hydroxyphenyl) benzotriazole UV absorber as dye stabilizers in a red-sensitive silver halide emulsion layer to bring. Emulsifiable 2-hydroxyphenyltriazines as UV absorbers and their use in certain light-insensitive layers or in red sensitive silver halide emulsion layers are described, for example in EP-A-0 520 938, EP-A-0 530 135, EP-A-0 531 258 and DE-A 43 40 725. Poly  mere 2- (2'-hydroxyphenyl) -benzotriazole UV absorbers are described in EP-A 0 577 122 and other references cited therein.

The use of polymeric UV absorbers is advantageous because they are without Oil former or with only small amounts of oil former embedded in the layers can be. As a result, thinner layers can be produced, resulting in has a favorable effect on the sharpness. You can compare with only a small amount of binder produce thin UV protective coatings without compromising their stability term. In particular, when using low molecular weight UV absorber frequently observed exudation of organic substances can be avoided. The polymeric 2- (2'-hydroxyphenyl) benzotriazole UV absorbers also comply visibly of their absorption spectrum, the requirements directed to them. all However, their extinction coefficient is still too low and achievable with them Light stability leaves much to be desired.

The invention is based on the object, a color photographic recording provide material with UV absorber, which can be used without oil or with only disperse small amounts of oil (<50 wt .-%) and not from sweat, as well as excellent light stability and high extinction coefficients respectively.

The UV absorbers according to the invention are polymeric UV Absorber obtained by polymerization of monomers of the formula (I) wherein the resulting polymer has the UV absorber residue as sides group is wearing.

wherein
R¹ and R³ are halogen, hydroxy, mercapto, alkyl, aryl, alkoxy, aryloxy, acyloxy, alkylthio, arylthio, -NR⁵-R⁶, alkoxycarbonyl, carbamoyl or sulfamoyl;
R² is H, hydroxy, halo or alkyl;
R⁴ is alkyl, alkoxy, alkylthio, aryloxy, arylthio or a radical of the formula

R⁵ is H, alkyl or aryl;
R⁶ is H, alkyl, aryl, acyl, alkoxycarbonyl, carbamoyl, sulfamoyl or sulfonyl,
m, n and o are 1, 2, 3 or 4,
wherein a plurality of R¹, R² and R³ are the same or different and wherein at least one of R¹ to R⁴ contains an ethylenically unsaturated polymerizable group.

The alkyl and aryl groups may be further substituted.

The ethylenically unsaturated, polymerizable group of UV absorber monomers corresponds to one of the formulas

wherein
Ra H, halogen, in particular chlorine, -COOH or alkyl, preferably having 1 to 4 carbon atoms.

The ethylenically unsaturated group may be directly or indirectly via a link L be bound to one of the directly bound to the triazine phenyl radicals. Such a link -L- may have a composite structure and For example, as shown below:

- (L⁰) _k - (L¹) _l - (L²) _m - (L³) _n - (L⁴) _o - (L⁵) _p - (L⁶) _q - (L⁷) _r -

wherein L⁰ is the phenyl radical and L⁷ that of the ethylenically unsaturated group denote initially located part of the link and in which mean (equal or different):

L⁰, L², L⁴, L⁶ -O-, -NR-, -NRCO-, -CONR-, -NRSO₂-, -SO₂NR-, -COO-, -O-CO-, -NR-CO-NR-, - O-CO-NR-, -NR-COO- (with R = H or alkyl);
L¹, L³, L⁵, L⁷ alkylene, aralkylene, arylene;
k, l, m, n, o, p, q, r are each 0 or 1, where 1 - m + n - o + p - q = 0.

An alkylene group represented by L¹, L³, L⁵, L⁷ may be straight chain or be branched and have up to 20 carbon atoms and optionally substituted his.

An aralkylene group represented by L¹, L³, L⁵ is, for example, one of following groups:

An arylene group represented by L¹, L³, L⁵, L⁷ is preferably one Phenylene group which may be substituted, e.g. With alkyl, alkoxy, halogen, Acylamino.

Examples of suitable UV absorber monomers (M-) are as follows specified.

The UV absorber polymers according to the invention are formed by polymerization the compounds of formula I, wherein further polymerizable Comono mers can be present. The polymers contain at least 20 wt .-% of polymerized units of the formula (I), preferably 30 to 70 wt .-%.

The UV absorber polymers according to the invention can therefore in addition to the Recurring units of UV absorber monomer additionally recurring Contain units of at least one other copolymerized monomer. Examples of such monomers include esters and amides of acrylic acid and their derivatives, z. Example of acrylic acid, α-chloroacrylic acid, methacrylic acid (For example, acrylamide, methyl methacrylate, ethyl acrylate, ethyl methacrylate, n- Propyl acrylate, n-butyl acrylate, 2-ethylhexyl acrylate, octyl methacrylate, lauryl methacrylate and methylenebisacrylamide), vinyl esters (for example vinyl acetate, Vinyl propionate and vinyl laurate), acrylonitrile, methacrylonitrile, aromatic Vinyl compounds (for example, styrene, vinyltoluene, divinylbenzene, vinylaceto  phenone, styrenesulfonic acid), itaconic acid, citraconic acid, crotonic acid, methacrylic acid acid, vinylidene chloride, vinyl alkyl ethers (for example, vinyl ethyl ether), esters of maleic acid, N-vinyl-2-pyrrolidone, N-vinyl, 2-vinyl and 4-vinylpyridine. The proportion of monomer C in the polymeric UV absorber can be 0 to 80% by weight, preferably 30 to 70 wt .-% amount.

It is particularly preferred, as comonomer, an ester of acrylic acid or Methacrylic acid and / or to use an aromatic vinyl compound. Two or more of the above-described comonomers may optionally be used to be used simultaneously. For example, it is possible a combination of n-butyl acrylate and divinylbenzene, styrene and methyl methacrylate, Methyl acrylate and butyl methacrylate to use. The comonomer can do this be selected that it is favorable to the physical properties and / or chemical properties of the copolymer to be produced, for example, the solubility, compatibility with a binder such as gelatin or other photographic additives such as coloring compounds, others UV absorbers, antioxidants and on the flexibility of the layer compositions or color photographic recording materials effect. Although the comonomers generally do not contain groups that it is possible to develop a photographic effect, even such To use compounds other than the ethylenically unsaturated polymerizable group, a photographically active group, for. Legs Coupling group, included. Such coupling groups can For example, color coupler, white coupler or mask coupler properties or in coupling a photographically active radical, eg. B. an inhibitor or release development accelerators.

The molecular weights (weight average) of the polymers of the invention are preferably greater than 5000, in particular greater than 20 000. The upper limit is not critical and can, especially when comonomers bi- or poly functional monomers can be used, reaching values of over 10 million.

The UV absorber polymers of the invention are the color photographic Recording materials usually in the form of polymer dispersions, eg. B. added as a polymer latex.  

The polymerization of the compound of formula I or of the monomer mixture can be carried out according to one of the usual polymerization, z. B. by emulsion polymerization or by polymerization in an organic Solvent.

The polymerization of the ethylenically unsaturated monomers is generally initiated by free radicals, which are formed by thermal decomposition a chemical initiator, by the action of a reducing agent on a oxidizing compound (redox initiator) or by physical action, such as irradiation with UV rays or other high-energy radiation, high frequencies, etc.

Examples of chemical initiators include a persulfate (for example, Ammo niumpersulfat or potassium persulfate, etc.), a peroxide (for example, hydrogen peroxide, benzoyl peroxide or tert-butyl peroctoate), an azonitrile compound (in For example, 4,4'-azo-bis-4-cyanovaleric acid or azobisisobutyronitrile) and an azoester (for example, 2,2'-azobis (methyl isobutyrate)).

Examples of conventional redox initiators include hydrogen peroxide-iron (II) salt, potassium persulfate, sodium metabisulfite and cerium IV salt alcohol.

Examples of the initiators and their functions are described by F.A. Bovey, in Emulsion Polymerization, Interscience Publishers Inc., New York, 1955, Pages 59 to 93.

As an emulsifier which can be used in the emulsion polymerization is used a compound with surface active action. Preferred examples these include soaps, sulfonates, sulfates, cationic compounds, amphoteric Compounds and high molecular weight protective colloids. Special examples of the Emulsifiers and their functions are described in Belgian Chemical Industrie, Vol. 28, pages 16 to 20, 1963.

An in the preparation of the polymer or in dispersing the polymer in an organic solution optionally used in an aqueous gelatin solution medium can be removed from the casting solution before casting.  

Suitable solvents are, for example, those which have a certain Have a degree of water solubility, so that they easily by washing with Water in a Gelatinenudelzustand can be removed, and those that can be removed by spray drying, vacuum or steam rinsing.

Examples of such solvents include esters (eg, ethyl acetate), ethers, Ketones, halogenated hydrocarbons (e.g., methylene chloride, tri chloroethylene), alcohols (for example, methanol, ethanol, butanol) and Kombina tions of it.

To improve the dispersion stability and the flexibility of the aufich To improve emulsion, a small amount (preferably not more as 50% by weight, based on the UV absorber polymer according to the invention) of a permanent solvent, especially one that is immiscible with water high-boiling organic solvent, for example dibutyl phthalate and / or tricresyl phosphate. The concentration of the permanent Solvent should be sufficient to plasticize the polymer while it is kept in a state of a solid particle. On the other hand, the Concentration of the permanent solvent in the interest of a low Layer thickness and layer load to be as low as possible.

Hereinafter, some representative synthesis examples of the invention described according to UV absorber polymers.

UV absorber polymer P-I (Copolymer of monomer M-2 and ethyl acrylate)

Under nitrogen, a solution of 2.1 g Oleylmethyltaurid in 409 g Water heated to 80 ° C. While stirring, 4.05 g of ethyl was added to this solution acrylate and 0.94 g of a 4.3% methanolic azobiscyanevaleric acid solution added and stirred at 80 ° C for 1 hour. Subsequently, during 1 hour a heated solution of 22.95 g of ethyl acrylate and 18 g of monomer M-2 in 204.4 ml of methanol and 9.5 g of a 4.3% methanolic Azobiscyan valeric acid solution is added dropwise. After stirring for a further 2 hours at 80 ° C was  The methanol evaporated from the reaction mixture and the resulting latex filtered. A finely divided 10.6% solids UV absorber latex was obtained.

UV absorber polymer P-2 (Copolymer of monomer M-7 and butyl acrylate)

Under nitrogen, a solution of 0.63 g Oleylmethyltaurid in 121 g Water heated to 80 ° C. To this was added 1.4 g of butyl acrylate and 0.33 g of a 4.3% methanolic solution of azobiscyanvaleric acid solution and Stirred for 1 hour at 80 ° C. Subsequently, a mixture of 8 g of butyl acrylate, 36.3 ml of methanol and 23.2 g of a 17.3% methanolic solution of M-7 and 2.8 g of a 4.3% methanolic Azobiscyanvaleriansäurelösung added to the reaction solution. It was stirred for 2 hours at 80 ° C and then the methanol is separated by distillation. It was a finely divided Obtained UV absorber latex. Solid: 12.0%.

UV absorber polymer P-3 (Copolymer of monomer M-2 and butyl acrylate)

The preparation was carried out as described for the UV absorber polymer P-1, but Instead of ethyl acrylate butyl acrylate was used and instead of methanoli Azobiscyanvaleriansäure was an aqueous potassium peroxide sulfate solution used. It was a finely divided UV absorber latex with a solids content of 12.6%.

UV absorber polymers P-4 to P-15

Using the UV absorber monomers described above the UV absorber monomers described in Table 1 below same manner as described for the copolymers in the preceding examples manufactured.

The following abbreviations are used for the comonomers:
BA: butyl acrylate
EA: ethyl acrylate
EHA: ethylhexyl acrylate
MA: methyl acrylate
BM: butyl methacrylate
PPA: i-Propylacrylamide
AMPS: 2-acrylamido-2-methylpropanesulfonic acid

Table 1

The color photographic recording material according to the invention contains at least a photosensitive silver halide emulsion layer and preferably an Ab follow several such photosensitive silver halide emulsion layers and optionally further auxiliary layers such as in particular protective layers and zwi the photosensitive layers arranged non-photosensitive Bin  demittelschichten, wherein according to the present invention, at least one of the existing those photosensitive silver halide emulsion layers or not photosensitive layer contains a UV absorber polymer according to the invention.

The total amount of inventive UV absorber polymer in the or Layers of the color photographic recording material is generally 50 to 3000 mg / m², preferably 100 to 1500 mg / m². The invention UV absorber polymer is preferably used in one or more layers, which is above the green-sensitive silver halide emulsion layer or above the green-sensitive and the blue-sensitive silver halide emulsion layer with the respectively assigned color couplers are located. The addition to the respective Schichtgießzusammensetzungen appropriate manner in the form of UV absorber polymer latices, optionally with concomitant use of oil formers in an amount of up to 50% by weight, based on the amount UV absorber polymer (solid substance).

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 dye bleach process.

Suitable carriers for the production of color photographic materials are, for. B. movies and films of semi-synthetic and synthetic polymers, such as cellulose nitrate, cellulose acetate, cellulose butyrate, polystyrene, polyvinyl chloride, polyethylene terephthalate and polycarbonate and with a baryta or α-olefin polymer layer (eg polyethylene) laminated paper. These carriers can contain dyes and pigments, for example, titanium dioxide. You can also go to Purpose of shielding from light to be colored black. The surface of the The carrier is generally subjected to a treatment to prevent the adhesion of the photographic emulsion layer to improve, for example, a corona Ent charge with subsequent application of a substrate layer.

Essential constituents of the photographic emulsion layers are binders, Silver halide grains and color couplers.  

The binder used is preferably gelatin. However, this can be quite or partly by other synthetic, semi-synthetic or even natural upcoming polymers are replaced. Synthetic gelatin substitutes are included For example, polyvinyl alcohol, poly-N-vinylpyrrolidone, polyacrylamides, polyacrylic acid and its derivatives, in particular their copolymers. Of course, before For example, future gelatin substitutes are other proteins such as albumin or casein, cellulose, sugar, starch or alginates. Semi-synthetic gelatin Substances are usually modified natural products. Cellulose derivatives such as Hydroxyalkylcellulose, carboxymethylcellulose and phthalylcellulose and Gela tinederivate obtained by reaction with alkylating or acylating agents or obtained by grafting polymerizable monomers are Examples of this.

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

The gelatin preferably used may be acidic or alkaline Be received digestion. Oxidized gelatin can also be used. The Preparation of such gelatins is described, for example, in The Science and Technology of Gelatine, edited by A.G. Ward and A. Courts, Academic Press 1977, Page 295 ff. The gelatine used should be as possible low content of photographically active impurities (inert gelatin). Gelatins with high viscosity and low swelling are particularly advantageous.

The photosensitive component contained in the photographic material Silver halide may be chloride, bromide or iodide or mixtures as halide included. For example, the halide content of at least one layer to 0 to 15 mol% of iodide, to 0 to 100 mol% of chloride and 0 to 100 mol% consist of bromide. In the case of color negative and color reversal films are usually Silberbromidiodidemulsionen, in the case of color negative and Color reversal paper usually high silver chloride bromide emulsions Chloride content used to pure silver chloride emulsions. It can be around  predominantly compact crystals act, the z. Regular cubic or octahedral or may have transitional forms. It can also be platelike Crystals are present whose average diameter to thickness ratio preferably at least 5: 1, wherein the diameter of a grain is defined as the diameter of a circle with a circle content corresponding to the projected one Area of the grain. Preferably, AgBrCl emulsions with at least 80 mol% AgCl, in particular at least 95 mol% AgCl used.

The silver halide grains may also have a multi-layered grain structure have, in the simplest case with an inner and an outer grain area (core / shell), wherein the halide composition and / or other modifizie ments, such as B. doping of the individual grain areas are different. The average grain size of the emulsions is preferably between 0.2 microns and 2.0 μm, the particle size distribution can be both homo- and heterodisperse. Homodisperse particle size distribution means that 95% of the grains do not exceed + 30% deviate from the mean grain size. The emulsions can be next to the silver halide also contain organic silver salts, for. B. Silberbenzotriazo lat or silver behenate.

Two or more types of silver halide emulsions can be separated be prepared, used as a mixture.

The photographic emulsions can be prepared by various methods (eg P.I. Glafkides, Chimie et Physique Photographique, Paul Montel, Paris (1967), G.F. Duffin, Photographic Emulsion Chemistry, The Focal Press, London (1966), V.L. Zelikman et al., Making and Coating Photographic Emulsion, The Focal Press. London (1966) made from soluble silver salts and soluble halides become.

After crystallization has been completed or already at an earlier time point the soluble salts are removed from the emulsion, z. B. by pasta and washing, by flocculation and washing, by ultrafiltration or by ions exchangers.  

The silver halide emulsion generally becomes a chemical sensitiser under defined conditions - pH, pAg, temperature, gelatin, silver halide and sensitizer concentration - until reaching the Sensitive subjected to keits- and Schleieroptimums. The procedure is z. B. at H. Frieser "The Fundamentals of Photographic Processes with Silver Halides" Pages 675-734, Akademische Verlagsgesellschaft (1968).

In this case, the chemical sensitization with the addition of compounds of Sulfur, selenium, tellurium and / or compounds of the metals of VIII. Subgroup of the periodic table (eg gold, platinum, palladium, iridium), furthermore For example, thiocyanate compounds, surface-active compounds such as thioethers, heterocyclic nitrogen compounds (eg imidazoles, azaindenes) or also spectral sensitizers (described, for example, in F. Hamer "The Cyanine Dyes and Related Compounds ", 1964, or Ullmann's Encyclopedia of Industrial Chemistry, 4th Edition, Vol. 18, p. 431 ff. And Research Disclosure 17643 (Dec., 1978), chapter III) are added. Alternatively or additionally, a Reduktionsensibili with the addition of reducing agents (stannous salts, amines, hydrazine derivatives, aminoboranes, silanes, formamidinesulfinic acid) by hydrogen, by low pAg (eg, less than 5) and / or high pH (eg, above 8) become.

The photographic emulsions may be compounds for preventing the Fogging or to stabilize the photographic function during the Production, storage or photographic processing.

Particularly suitable are azaindenes, preferably tetra- and penta-azaindenes, in particular those which are substituted by hydroxyl or amino groups. the like connections are z. B. von Birr, Z. Wiss. Phot. 47 (1952), pp. 2-58 be been written. Further, as antifogging agents, salts of metals such as Mercury or cadmium, aromatic sulfonic or sulfinic acids such as Benzolsul finsäure, or nitrogen-containing heterocycles such as nitrobenzimidazole, nitroindazole, optionally substituted benzotriazoles or Benzthiazoliumsalze used who the. Particularly suitable are mercapto-containing heterocycles, for. B. Mercaptobenzothiazoles, mercaptobenzimidazoles, mercaptotetrazoles, mercaptothia diazoles, mercaptopyrimidines, these mercaptoazoles also being a water-soluble  making group, z. As a carboxyl group or sulfo group may contain. Other suitable compounds are described in Research Disclosure 17643 (Dec., 1978), Chapter VI, published.

The stabilizers may be added to the silver halide emulsions before, during or after their maturation are added. Of course you can do the connections also other photographic layers associated with a silver halide layer are, enforce.

It is also possible to use mixtures of two or more of the compounds mentioned be used.

The photographic emulsion layers or other hydrophilic colloid layers of the photosensitive material produced according to the present invention may be surface active agents for various purposes, such as coating aids, for Prevention of electric charge, to improve gliding to emulsify the dispersion, to prevent adhesion and to Improvement of photographic characteristics (eg development acceleration high contrast, sensitization, etc.). In addition to natural surface active Compounds, e.g. As saponin, find mainly synthetic surface-active Compounds (surfactants) Use: non-ionic surfactants, eg. B. alkylene oxide compounds, glycerol compounds or glycidol compounds, cationic Surfactants, e.g. B. higher alkylamines, quaternary ammonium salts, pyridine compounds and other heterocyclic compounds, sulfonium compounds or phosphines phonium compounds, anionic surfactants containing an acid group, e.g. B. Carboxylic acid, sulfonic acid, a phosphoric acid, or Sulfosäureester- Phos phosphoric ester group, ampholytic surfactants, eg. B. amino acid and aminosulfone acid compounds and sulfuric or phosphoric acid esters of an aminoalcohol.

The photographic emulsions can be prepared using methine dyes or other dyes spectrally sensitized. Particularly suitable color cyanine dyes, merocyanine dyes and complex merocyanine dyes substances.  

An overview of the suitable as Spektralsensibilisatoren Polymethinfarb substances, their suitable combinations and supersensitizing Kom contains Research Disclosure 17643 (Dec., 1978), Chapter IV.

In particular, the following dyes - ordered by spectral regions - suitable:

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

Sensitisers can be omitted if for a specific spectral Area the intrinsic sensitivity of the silver halide is sufficient, for example show the blue sensitivity of silver bromides.

The differently sensitized emulsion layers will not diffuse associated monomeric or polymeric color couplers that are in the same  Layer or in a layer adjacent thereto. Usually the red-sensitive layers become cyan couplers, the green-sensitive ones Layers of magenta coupler and the blue-sensitive layers yellow coupler assigned.

Color couplers for producing the cyan partial color image are usually Phenolic or α-naphthol type couplers. Color coupler for the production of purple partial color image are usually couplers of the 5-pyrazolone type, of indazolone or pyrazoloazole. Color coupler for the production of yellow Part color images are usually couplers with an open-chain keto methylene moiety, especially couplers of the α-acylacetamide type For example, α-Pivaloylacetanilidkuppler, Cycloalkylcarbonylacetanilidkuppler and Carbamoylacetanilidkuppler.

The color couplers can be 4-equivalent couplers, but also to Act 2-equivalent couplers. The latter are derived from the 4-equivalent couplers characterized in that they contain a substituent in the coupling site at the clutch is split off. Among the 2-equivalent couplers are those too which are colorless, as well as those which have an intense inherent color, which disappears in the color coupling or by the color of the generated Image dye is replaced (mask coupler), and the white couplers, at Reak tion with color developer oxidation products essentially colorless products result. In addition to the 2-equivalent couplers such couplers are to be expected, the in the coupling point contain a cleavable radical which reacts with Color developer oxidation products is set free and either directly or after one or more of the primary cleavage residues Groups have been split off (eg DE-A 27 03 145, DE-A 28 55 697, DE-A 31 05 026, DE-A 33 19 428), a certain desired photographic Effectiveness unfolded, z. As a development inhibitor or accelerator. Examples for such 2-equivalent couplers, the known DIR couplers as well as DAR or FAR coupler.

DIR couplers, the azole type of development inhibitors, e.g. Triazoles and benzo triazoles are disclosed in DE-A 24 14 006, 26 10 546, 26 59 417, 27 54 281, 28 42 063, 36 26 219, 36 30 564, 36 36 824, 36 44 416 described. Further  Advantages for color rendering, d. H. Color separation and color purity, and for the Detail reproduction, d. H. Sharpness and graininess are with such DIR couplers too achieve that z. B. the development inhibitor not directly as a result of Kupp split off with an oxidized color developer, but only after a further subsequent reaction, which is achieved for example with a timing group. Examples thereof are described in DE-A 28 55 697, 32 99 671, 38 18 231, 35 18 797, in EP-A-0 157 146 and 0 204 175, in US Pat. Nos. 4,146,396 and 4,438,393 and in US Pat GB-A-2 072 363.

DIR couplers that release a development inhibitor that in the developer to is decomposed essentially photographic ineffective products are, for example in DE-A 32 09 486 and in EP-A-0 167 168 and 0 219 713. With This measure is a trouble-free development and processing consistency reached.

When using DIR couplers, especially those that diffuse well split off dierbaren development inhibitor, can be by appropriate measure Improved color rendering in optical sensitization, z. B. achieve a more sophisticated color reproduction, such as in EP-A-0 115 304, 0 167 173, GB-A-2 165 058, DE-A 37 00 419 and US-A-4,707,436.

The DIR couplers can be used in a multilayer photographic material be added to various layers, for. B. also insensitive to light or intermediate layers. Preferably, however, they become the photosensitive Added silver halide emulsion layers, wherein the characteristic Eigen the silver halide emulsion, e.g. B. their iodide content, the structure of Silver halide grains or their particle size distribution of influence on he are targeted photographic properties. The influence of the released inhibitors For example, by incorporating an inhibitor scavenger layer according to DE-A 24 31 223 limited. For reasons of reactivity or stability it may be advantageous to use a DIR coupler which is in the respective Layer in which it is introduced, one of the in this layer to be produced Color deviating color forms at the coupling.  

To increase the sensitivity, the contrast and the maximum density In particular, DAR or FAR couplers can be used which have a development release accelerator or a veiling agent. Compounds of this type are for example in DE-A 25 34 466, 32 09 110, 33 33 355, 34 10 616, 34 29 545, 34 41 823, in EP-A-0 089 834, 0 110 511, 0 118 087, 0 147 765 and in US-A-4,618,572 and 4,656,123.

As an example of the use of BAR coupler (Bleach Accelerator Releasing Coupler), reference is made to EP-A-0 193 389.

It may be advantageous to the effect of a cleaved from a coupler photo graphically effective group by modifying an intermolecular Re according to their release with another group according to DE-A 35 06 805 occurs.

Since the DIR, DAR and FAR couplers mainly the effectiveness of the in the clutch released residue is desired and less on the color-forming properties of these couplers are important, are also such DIR-, DAR or FAR coupler suitable which in the coupling substantially colorless Products result (DE-A 15 47 640).

The cleavable residue may also be a ballast residue, so that in the reaction with Color developer oxidation products are obtained coupling products that diffuse or at least weak or limited mobility (US-A-4,420,556).

The material may further contain compounds other than couplers, for example, a development inhibitor, a development accelerator, a bleach accelerator, a developer, a silver halide solvent Veiling agent or an antifoggant can be set free, for example so-called DIR-hydroquinones and other compounds, such as in US-A-4 636 546, 4 345 024, 4 684 604 and in DE-A 31 45 640, 25 15 213, 24 47 079 and in EP-A-0 198 438 are described. Meet these connections the same function as the DIR, DAR or FAR couplers, except that they have no Form coupling products.  

High molecular color couplers are described, for example, in DE-C 12 97 417, DE-A 24 07 569, DE-A 31 48 125, DE-A 32 17 200, DE-A 33 20 079, DE-A 33 24 932, DE-A 33 31 743, DE-A 33 40 376, EP-A-27 284, US-A-4 080 211. The high molecular color couplers are used in the Rule by polymerization of ethylenically unsaturated monomer Farbkupp produced. But you can also by polyaddition or polycondensation to be obtained.

The incorporation of the couplers or other compounds in silver halide emuls layers can be carried out in such a way that first of all the Ver Made a solution, a dispersion or an emulsion and then the Casting solution for the relevant layer is added. The selection of the appropriate Solvent or dispersant depends on the particular solubility of the verbin from.

Methods for introducing substantially insoluble in water Verbin Applications by grinding processes are described for example in DE-A 26 09 741 and DE-A 26 09 742 described.

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

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

The compounds may also be in the form of loaded latices in the casting solution be introduced. Reference is made, for example, to DE-A 25 41 230, DE-A 25 41 274, DE-A 28 35 856, EP-A-0 014 921, EP-A-0 069 671, EP-A-0 130 115, US-A-4 291 113.

The diffusion-resistant incorporation of anionic water-soluble compounds (eg. of dyes) can also be made with the help of cationic polymers, so-called Beizenpolymeren done.  

Suitable oil formers are z. Phthalic acid alkyl ester, phosphonic acid ester, Phosphoric acid esters, citric acid esters, benzoic acid esters, amides, fatty acid esters, Trimesic acid esters, alcohols, phenols, aniline derivatives and hydrocarbons.

Each of the differently sensitized photosensitive layers may be made consist of a single layer or two or more Silberhalogenidemul partial spreading layers comprise (DE-C 11 21 470). These are red-sensitive silver halide emulsion layers often closer to the substrate than green sensitive silver halide emulsion layers and these in turn closer than blue sensitive, which is generally between green sensitive Layers and blue-sensitive layers a non-photosensitive yellow Filter layer is located.

With suitably low intrinsic sensitivity of the green or red sensitive Layers can be waived by dispensing with the yellow filter layer other Schichtanord choose where the carrier has B. the blue-sensitive, then the red sensitive and finally the green sensitive layers follow.

The usually between layers of different spectral sensitivity arranged non-photosensitive intermediate layers may contain agents, the unwanted diffusion of developer oxidation products from a light sensitive in another photosensitive layer with different spek prevent trol sensitization.

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

If several partial layers of the same spectral sensitization are present, then these in terms of their composition, especially what kind and quantity the silver halide grains are different. In general, the Particle layer with higher sensitivity of the carrier can be arranged more remote than the sub-layer with lower sensitivity. Sublayers of the same spectral Sensitization may be adjacent to each other or through other layers, e.g. B.  separated by layers of other spectral sensitization. So z. B. all highly sensitive and all low-sensitive layers in each case to one Layer pack be summarized (DE-A 19 58 709, DE-A 25 30 645, DE-A 26 22 922).

The photographic material may further UV-absorbing compounds, whiteners, spacers, filter dyes, formalin scavenger, light stabilizers, antioxidants, D _Min dyes, additives to improve the dye, Kupp ler- and whitening stabilization and to reduce color fog, plasticizer (latices ), Biocide and others.

UV-absorbing compounds should on the one hand the image dyes before the To prevent fading by UV-rich daylight and on the other hand as a filter color substances absorb the UV light in daylight during the exposure and thus the color improve the playback of a movie. Usually, for the two tasks Compounds of different structure used. To protect the image dyes the UV absorber polymers according to the invention are used. additionally Further UV absorbers can be used. Examples are aryl-substituted Benzotriazole compounds (US Pat. No. 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 compound (US Pat. No. 4,045,229) or benzoxazole compounds (US Pat. No. 3,700,455).

Certain binder layers, in particular those of the carrier farthest ent distant layer, but also occasionally intermediate layers, especially if they during manufacture, represent the layer furthest away from the wearer, can photographically inert particles of inorganic or organic nature enthal th, z. B. 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 of 0.2 to 10 microns. The spacers are water insoluble and can alkali-insoluble or alkali-soluble, the alkali-soluble in general in alkaline development bath are removed from the photographic material. Examples of suitable polymers are polymethyl methacrylate, copolymers of  Acrylic acid and methyl methacrylate, as well as hydroxypropylmethyl cellulose hexa hydrophthalat.

Additives to improve the dye, coupler and whitening stability and to Color Veil Reduction (Research Disclosure 307105 (Nov. 1989), Chapter VII, EP-A-0 246 766, 0 273 712, 0 304 067, 0 471 341, 0 524 540, 0 544 316, 0 544 317 and 0 545 305 as well as DE-A 42 09 346, 43 20 444 and 43 23 477) may belong to the following chemical classes o-, m- and p-dihy hydroxybenzenes, hydroxychromans, 5-hydroxycoumarans, spirochromans, spiroin dane, p-alkoxyphenols, sterically hindered phenols, gallic acid derivatives, methyl lendioxybenzenes, aminophenols, aminoanilines, hindered amines, Derivatives with esterified or etherified phenolic hydroxyl groups or Derivatives with acylated or alkylated aromatic amine groups, metal complex.

In many cases, the use of certain combinations of color image Stabilizers proved to be particularly effective. Such combinations are z. As described in US-A-5,104,782 and 5,139,931, EP-A-0 298 321, 0 355 660, 0 457 543, 0 477 870 and JP-A-0 305 1846, as well as in DE-A 43 14 669, 43 23 512 and 43 26 647.  

Example 1

A color photographic recording suitable for a fast-processing process material was prepared by applying to a support made of both sides Polyethylene coated paper the following layers in the specified Order were applied. The quantities refer to each 1 m². For the Silberhalogenidauftrag the appropriate amounts of AgNO₃ specified.

Layer structure Sample 1

Layer 1: (substrate layer)
0.2 g of gelatin

Layer 2: (blue-sensitive layer)
blue-sensitive silver halide emulsion (99.5 mol% chloride, 0.5 mol% bromide, mean grain diameter 0.8 μm)
0.63 g of AgNO₃ with
1.11 g of gelatin
0.60 g yellow coupler XY-1
0.15 g white coupler XW-1
0.12 g of dye stabilizer XST-1
0.24 g of oil former XOF-1

Layer 3: (protective layer)
1.1 g of gelatin
0.04 g of 2,5-di-tert-octylhydroquinone
0.04 g of compound XSC-1
0.04 g tricresyl phosphate (TKP)

Layer 4: (green-sensitive layer)
green-sensitized silver halide emulsion (99.5 mole% chloride, 0.5 mole% bromide, average grain diameter 0.6 μm)
0.25 g of AgNO₃ with
0.95 g gelatin
0.20 g magenta coupler XM-1
0.20 g of dye stabilizer XST-2
0.10 g of dye stabilizer XST-3
0.18 g of oil former XOF-2
0.12 g of oil former XOF-3

Layer 5: (UV protection layer)
0.75 g of gelatin
0.2 g UV absorber XUV-1
0.1 g UV absorber XUV-2
0.025 g of 2,5-di-tert-octylhydroquinone
0.02 g of compound XSC-1
0.1 g of oil former XOF-4
0.04 g TKP

Layer 6: (red-sensitive layer)
red sensitized silver halide emulsion (99.5 mole% chloride, 0.5 mole% bromide, average grain diameter 0.5 μm)
0.30 g of AgNO₃ with
0.75 g of gelatin
0.36 g of cyan coupler XC-1
0.36 g TKP

Layer 7: (UV protection layer)
0.85 g of gelatin
0.36 g UV absorber XUV-1
0.18 g UV absorber XUV-2
0.18 g of oil former XOF-4

Layer 8: (protective layer)
0.9 g of gelatin
0.3 g of hardener XH-1

In the samples of Example 1 the following compounds were used:

Samples 2 to 12

Samples 2 to 12 are prepared as sample 1 with the difference that in the layers 5 and 7, the UV absorbers XUV-1 and XUV-2 and the oil former XOF-4 was replaced by the compounds shown in Table 1 and the Gelatin quantity in layers 7 and 8 was varied.  

Table 1

(V: comparison, E: according to the invention)

The order of UV absorber was chosen so that at λ _max an optical density of D is about 3 achieved.

The samples were exposed behind a graduated gray wedge and then processed as follows:

a) Color developer - 45 s - 35 ° C Tetraethylene glycol | 20.0 g N, N-diethyl 4.0 g N-ethyl-N- (2-methanesulfonamidoethyl) -4-amino-3-methyl benzene sulphate 5.0 g potassium 0.2 g   potassium carbonate 30.0 g polymaleic 2.5 g hydroxyethane 0.2 g Whitening agent (4,4'-diaminstilbene sulfonic acid derivative) 2.0 g potassium 0.02 g make up to 1000 ml with water; Adjust pH to pH 10.2 with KOH or H₂SO₄.

b) Bleach-fix bath - 45 s - 35 ° C Ammonium thiosulphate | 75.0 g sodium bisulfite 13.5 g Ethylenediaminetetraacetic acid (ferric ammonium salt) 45.0 g make up to 1000 ml with water; Adjust pH to pH 6.0 with ammonia (25%) or acetic acid.

c) watering - 2 min - 33 ° C

The samples became the light of a normalized xenon lamp exposed and irradiated with 15 × 10⁶ lux / h or 25 × 10⁶ lux × h; after that the percentage density decrease measured (Table 2).

The samples were also at 60 ° C and 90% rel. Moisture stored; after that was the appearance of oily compounds caused by sweating on the Sample surface visually assessed (Table 2).  

Table 2

(V: comparison E: according to the invention)

As can be seen from Table 2, with the monomeric UV absorbers XUV-1, XUV-2, XUV-3 and XUV-6 necessary, a protective layer with larger gelatin Apply quantity above the UV protection layer (layer 7) to an off to prevent perspiration from UV absorbers or oil-formers. This means one greater layer thickness and larger amount of curing agent. A comparison the inventive polymeric triazine UV absorbers with the polymeric Comparative compounds (benzotriazole UV absorber) XUV-4 according to EP-A 577 122 and XUV-5 according to EP-A 2 128 005 gives an improvement of the protection against UV radiation in the case of the compounds according to the invention. The improvement increases significantly with longer exposure times, which in the much higher Light resistance of the triazine UV absorbers compared to the benzotriazole Types justified, d. H. at longer irradiation times are the Benz Triazole UV absorber has already been destroyed to a significant percentage.

Claims (5)

A color photographic recording material having a support and having thereon at least one red-sensitive silver halide emulsion layer associated with a cyan coupler, at least one green-sensitive silver halide emulsion layer having a magenta coupler associated therewith, at least one blue-sensitive silver halide emulsion layer having associated therewith a yellow coupler and optionally further layers , characterized in that it contains in at least one of its photosensitive or non-photosensitive layers a polymeric UV absorber obtained by polymerisation of at least one monomer of formula I. wherein
R¹ and R³ are halogen, hydroxy, mercapto, alkyl, aryl, alkoxy, aryloxy, acyloxy, alkylthio, arylthio, -NR⁵-R⁶, alkoxycarbonyl, carbamoyl or sulfamoyl;
R² is H, hydroxy, halo or alkyl;
R⁴ is alkyl, alkoxy, alkylthio, aryloxy, arylthio or a radical of the formula R⁵ is H, alkyl or aryl;
R⁶ is H, alkyl, aryl, acyl, alkoxycarbonyl, carbamoyl, sulfamoyl or
m, n and o are 1, 2, 3 or 4,
wherein a plurality of R¹, R² and R³ are the same or different and wherein at least one of R¹ to R⁴ contains an ethylenically unsaturated polymerizable group. 2. Recording material according to claim 1, characterized in that in Formula I at least one of R² is a hydroxy group. 3. Recording material according to one of claims 1 and 2, characterized characterized in that the polymeric UV absorber in at least one Layer is included, which is above the greenish silver halide emulsion layer is located with the associated Magentakuppler. 4. Recording material according to one of claims 1 and 2, characterized characterized in that the polymeric UV absorber in at least one Layer is included, which is above the greenish silver halide emulsion layer with the associated magenta coupler and above the blue-sensitive silver halide emulsion layer with the associated yellow coupler is located. 5. Recording material according to one of claims 1 to 4, characterized characterized in that the polymeric UV absorber in the recording contained in a total amount of 100-1500 mg / m².