EP0520938B1 - UV-absorber containing photographic material - Google Patents

UV-absorber containing photographic material Download PDF

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Publication number
EP0520938B1
EP0520938B1 EP92810397A EP92810397A EP0520938B1 EP 0520938 B1 EP0520938 B1 EP 0520938B1 EP 92810397 A EP92810397 A EP 92810397A EP 92810397 A EP92810397 A EP 92810397A EP 0520938 B1 EP0520938 B1 EP 0520938B1
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Prior art keywords
alkyl
formula
group
independently
phenyl
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EP92810397A
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German (de)
French (fr)
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EP0520938A1 (en
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David G. Dr. Leppard
Kurt Dr. Burdeska
Mario Dr. Slongo
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BASF Schweiz AG
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Ciba Geigy AG
Ciba Spezialitaetenchemie Holding AG
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    • GPHYSICS
    • G03PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03CPHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C1/00Photosensitive materials
    • G03C1/76Photosensitive materials characterised by the base or auxiliary layers
    • G03C1/815Photosensitive materials characterised by the base or auxiliary layers characterised by means for filtering or absorbing ultraviolet light, e.g. optical bleaching
    • G03C1/8155Organic compounds therefor
    • GPHYSICS
    • G03PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03CPHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C7/00Multicolour photographic processes or agents therefor; Regeneration of such processing agents; Photosensitive materials for multicolour processes
    • G03C7/30Colour processes using colour-coupling substances; Materials therefor; Preparing or processing such materials
    • G03C7/392Additives
    • G03C7/39208Organic compounds
    • G03C7/3924Heterocyclic
    • G03C7/39244Heterocyclic the nucleus containing only nitrogen as hetero atoms
    • G03C7/39256Heterocyclic the nucleus containing only nitrogen as hetero atoms three nitrogen atoms
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10STECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S430/00Radiation imagery chemistry: process, composition, or product thereof
    • Y10S430/132Anti-ultraviolet fading

Definitions

  • the present invention relates to new photographic material which contains UV absorbers, in particular of the bis-2-hydroxyphenyltriazinyl type.
  • a group of triazine UV absorbers has now been found which, surprisingly, has proven to be largely free from such disadvantages. They show improved stability to natural light and have the property of better protecting image dyes and color couplers against exposure to light than was possible with the hydroxyphenylbenztriazoles and triazines conventionally used in photographic materials.
  • this group of triazines is suitable for increasing the stability of the magenta and cyan layers of photographic materials, e.g. in layers, which are applied over the magenta or cyan layer, or directly embedded in the cyan layer.
  • the UV absorbers according to the invention can be used for all types of photosensitive material.
  • they can be used for color paper, color reversal paper, direct positive color material, color negative film, color positive film, color reversal film and others.
  • they are preferably used for photosensitive color material which contains a reversal substrate or which forms positives.
  • these triazines can advantageously be combined with UV absorbers of the hydroxyphenylbenztriazole type, in particular representatives thereof which are liquid at room temperature (cf. for example US Pat. Nos. 4,853,471, 4,973,702, 4,921,966 and 4,973,701).
  • UV absorbers of the hydroxyphenylbenztriazole type in particular representatives thereof which are liquid at room temperature (cf. for example US Pat. Nos. 4,853,471, 4,973,702, 4,921,966 and 4,973,701).
  • Such combinations allow considerable Reduction in the amount of oil required to incorporate the UV absorbers into the photographic layer in question. This results in a small layer thickness or, if the layer thickness is kept constant, a higher concentration of UV absorber.
  • Combinations of the triazines with other types of UV absorbers such as benzophenones, oxanilides, cyanoacrylates, salicylic acid esters, acrylonitriles or thiazolines are also suitable for use in photographic materials.
  • substituents in the compounds of the formula (I) are alkyl having 1 to 18 carbon atoms, radicals such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tetradecyl, hexadecyl and Octadecyl and corresponding branched isomers in question.
  • alkyl radicals having 3 to 24 carbon atoms which are interrupted by oxygen are or
  • the material according to the invention preferably contains intermediate gelatin layers between the silver halide emulsion layers.
  • the material according to the invention contains a further layer with a UV absorber of the formula (I), which is arranged between the green and red-sensitive silver halide emulsion layer.
  • UV absorber of the formula (I) is additionally contained in the red-sensitive silver halide emulsion layer.
  • benzotriazole compounds can advantageously be used instead of the UV absorbers of the formula (I).
  • HBT benzotriazole compounds
  • T 1 , T 2 and T 3 are independently hydrogen, halogen, alkyl, alkyl substituted with a carboxylic acid ester group, alkoxy, aryloxy, hydroxyl or acyloxy, and T 4 is hydrogen, alkoxy, aryloxy or acyloxy.
  • the present invention also relates to photographic material containing, on a support, a blue-sensitive, a green-sensitive and / or a red-sensitive silver halide emulsion layer and a protection layer, a layer with a UV absorber being arranged between the uppermost silver halide emulsion layer and the protection layer that (a) the UV absorber of the formula where T 1 , T 2 and T 3 are independently hydrogen, halogen, alkyl, alkyl substituted with a carboxylic acid ester group, alkoxy, aryloxy, hydroxyl or acyloxy and T 4 is hydrogen, alkoxy, aryloxy or acyloxy, and (b) that Material has at least one further layer which contains a UV absorber of the formula (I).
  • the further layer is preferably arranged between the green and red-sensitive silver halide emulsion layer.
  • the photographic material additionally contains a UV absorber of the formula (I) in the red-sensitive layer. It can also be advantageous if the UV absorber of the formula (I) is replaced by one of the formula (III) in the further layer or in the red-sensitive layer; but at least one layer should contain a UV absorber of the formula (I).
  • Preferred photographic materials contain intermediate gelatin layers between the silver halide emulsion layers.
  • the photographic material contains at least 2 silver halide emulsion layers with a layer between these layers with a UV absorber, characterized in that the UV absorber corresponds to the formula (I).
  • the two silver halide emulsion layers are preferably a green-sensitive and a red-sensitive silver halide emulsion layer.
  • a corresponding material is preferred, in which the red-sensitive silver halide emulsion layer additionally contains a UV absorber of the formula (I) or (III).
  • Another embodiment of the present invention relates to photographic material having a red sensitive silver halide emulsion layer on a support and optionally also contains a blue-sensitive and / or green-sensitive silver halide emulsion layer, characterized in that the red-sensitive silver halide emulsion layer contains a UV absorber of the formula (I). It preferably contains a layer with a UV absorber of the formula (III) between the red-sensitive silver halide emulsion layer and the support.
  • Preferred photographic materials are those which contain silver chloride bromide, which consists of at least 90 mol% silver chloride, as silver halide in the blue-sensitive, green-sensitive and / or red-sensitive layer.
  • photographic materials which contain the silver halide emulsion layers in the order of blue-sensitive, green-sensitive and red-sensitive silver halide emulsion layers.
  • the photographic materials according to the invention offer the advantage over materials with benzotriazole UV absorbers that the UV absorbers of the formula (I) are required in a comparatively small amount in order to ensure adequate protection against UV radiation.
  • the use of a comparable amount of UV absorber will result in even better protection.
  • Yellow couplers which can be used in the material according to the invention are preferably compounds of the formula A. wherein R 1 is alkyl or aryl, R 2 is aryl and Q is hydrogen or a group that can be cleaved by reaction with the oxidized developer.
  • a group of yellow couplers are those compounds of the formula A in which R 1 is t-butyl and R 2 is a group of the formula is where R 3 is hydrogen, halogen, alkyl or alkoxy and R 4 , R 5 and R 6 are hydrogen, halogen, alkyl, alkenyl, alkoxy, aryl, carboxy, alkoxycarbonyl, a carbamoyl group, a sulfone or sulfamoyl group, an alkylsulfonamino group, Acylamino group, ureido group or amino group.
  • R 3 is preferably chlorine, R 4 and R 5 are hydrogen and R 6 is an acylamino group. This also includes the compounds of the formula wherein x is 0-4, R 7 is hydrogen or alkyl and R 8 and R 9 are alkyl.
  • R 10 is hydrogen, halogen or alkoxy
  • R 11 , R 12 and R 13 are hydrogen, halogen, alkyl, alkenyl, alkoxy, aryl, carboxyl, alkoxycarbonyl, a carbamoyl group, a sulfone group, sulfamoyl group, sulfonamido group, acylamino group, ureido group or amino group and R 1 and Q have the meaning given above .
  • R 1 is t-butyl
  • R 10 is chlorine
  • R 11 and R 13 are hydrogen
  • R 12 is alkoxycarbonyl
  • the leaving group Q can be hydrogen or it is a heterocyclic group wherein R 14 is an organic divalent group that complements the ring to a 4-7 membered ring, or Q is a group -OR 15 , wherein R 15 is alkyl, aryl, acyl or a heterocyclic radical.
  • Typical examples of common yellow couplers are the compounds of the following formulas:
  • the yellow couplers are usually used in an amount of 0.05-2 mol and preferably 0.1-1 mol per mol of silver halide.
  • Typical and preferred yellow couplers correspond to the formulas:
  • Magenta couplers can e.g. simple 1-aryl-5-pyrazolones or pyrazole derivatives condensed with 5-membered hetero rings, e.g. Imidazopyrazole, pyrazolopyrazole, pyrazolotriazole or pyrazolotetrazole.
  • a group of magenta couplers are 5-pyrazolones of the formula C, as described in British Patent 2,003,473.
  • R 16 is hydrogen, alkyl, aryl, alkenyl or a heterocyclic group.
  • R 17 is hydrogen, alkyl aryl, a heterocyclic group, an ester group, alkoxy group, alkylthio group, carboxyl group, arylamino group, acylamino group, (thio) urea group, (thio) carbamoyl group, guanidino group or sulfonamido group.
  • R 17 is preferably a group wherein R 18 is imino, acylamino or ureido, R 19 is hydrogen, halogen, alkyl or alkoxy, R 20 is hydrogen, alkyl, acylamino, carbamoyl, sulfamoyl, sulfonamido, alkoxycarbonyl, acyloxy or a urethane group.
  • magenta coupler is tetra-equivalent to that Silver halide.
  • Typical examples of this type of magenta coupler are compounds of the formula wherein R 20 has the meanings given above, and Q ', as described above, is a leaving group. These compounds are preferably present in the material according to the invention.
  • Q 'in formula C is not hydrogen but a group that is eliminated in the reaction with the oxidized developer, then it is a equivalent magenta coupler.
  • Q can e.g. Halogen or a group bonded to the pyrazole ring via O, S or N.
  • Such equivalent couplers result in a higher color density and are more reactive towards the oxidized developer than the corresponding tetra-equivalent magenta couplers.
  • Typical and preferred magenta couplers correspond to the formulas
  • Two pyrazolone rings can be linked via a divalent Q 'and so-called bis couplers are then obtained.
  • Such are e.g. described in US-A-2,632,702, US-A-2,618,864, GB-A-968,461, GB-A-786,859, JP-A-76/37646, 59/4086, 69/16110, 69/26589, 74/37854 and 74/29638.
  • Y is preferably an O-alkoxyarylthio group.
  • pyrazoles - so-called pyrazoloazoles - condensed with 5-membered heterocycles can also be used as magenta couplers.
  • Their advantages over simple pyrazoles is that they have colors with greater formalin resistance and purer absorption spectra.
  • Pyrazoloazole type magenta couplers which are also preferred, can be represented by the formulas in which R 1 is hydrogen or a substituent, Z represents the non-metallic atoms necessary to complete a 5-membered ring with 2 or 3 nitrogen atoms, which ring may be substituted, and Q is hydrogen or a leaving group.
  • R 11 , R 12 and R 13 independently of one another are, for example, hydrogen, halogen, a group of the formula —CR 3 , in which the radicals R are independently of one another hydrogen or alkyl, aryl, heterocyclyl, cyano, hydroxy, nitro, carboxyl, amino, alkoxy , Aryloxy, acylamino, alkylamino, anilino, ureido, sulfamoylamino, alkylthio, arylthio, alkoxycarbonylamino, sulfonamido, carbamoyl, sulfamoyl, sulfonyl, alkoxycarbonyl, heterocyclyloxy, azo, acyloxy, carbamoyloxy, silylamino, imylyloxy, aryloxy, aryloxy, aryloxy, aryloxy, aryloxy, aryloxy, aryloxy, azo, acy
  • radicals R are independently hydrogen or alkyl, aralkyl, alkenyl, alkynyl, cycloalkyl or cycloalkenyl and particularly preferably methyl, ethyl, propyl, isopropyl, t-butyl , Tridecyl, 2-methanesulfonylethyl, 3- (3-pentadecylphenoxy) propyl, 3- (4- (2- (4- (4-hydroxyphenylsulfonyl) phenoxy) dodecanamido) phenyl) propyl, 2-ethoxytridecyl, trifluoromethyl, cyclopentyl, 3- (2,4-di-t-amylphenoxy) propyl); Aryl (e.g.
  • phenyl 4-t-butylphenyl, 2,4-di-t-amylphenyl, 4-tetradecaneamidophenyl); Heterocyclyl (e.g. 2-furyl, 2-thienyl, 2-pyrimidinyl, 2-benzothiazolyl); Cyano; Hydroxy, nitro; Carboxy; Amino; Alkoxy (e.g. methoxy, ethoxy, 2-methoxyethoxy; 2-dodecylethoxy, 2-methanesulfonylethoxy); Aryloxy (e.g.
  • phenoxy 2-methylphenoxy, 4-t-butylphenoxy, 3-nitrophenoxy, 3-t-butyloxycarbamoylphenoxy, 3-methoxycarbamoyl); Acylamino (e.g. acetoamido, benzamido, tetradecanamido, 2- (2,4-di-t-amylphenoxy) butanamido, 4- (3-t-butyl-4-hydroxyphenoxy) butanamido, 2- (4- (4-hydroxyphenylsulfonyl) phenoxy) decanamido); Methylbutylamino); Anilino (e.g.
  • phenylamino 2-chloroanilino, 2-chloro-5-tetradecanaminoanilino, 2-chloro-5-dodecyloxycarbonylanilino, N-acetylanilino, 2-chloro-5- (alpha- (3-t-butyl-4-hydroxyphenoxy) dodecanamido -anilino); ureido (e.g. phenylureido, methylureido, N, N-dibutylureido); sulfamoylamino (e.g.
  • phenylthio 2-butoxy-5-t-octylphenylthio, 3-pentadecylphenylthio, 2-carboxyphenylthio, 4-tetradecanamidophenylthio); Alkoxycarbonylamino (e.g. methoxycarbonylamino, tetradecyloxycarbonylamino); Sulfonamido (e.g.
  • N-ethylsulfamoyl N, N-dipropylsulfamoyl, N-2 (-dodecyloxyethyl) sulfamoyl, N-ethyl-N-dodecylsulfamoyl, N, N-diethylsulfamoyl); Sulfonyl (e.g. methanesulfonyl, octanesulfonyl, benzenesulfonyl, toluenesulfonyl); Alkoxycarbonyl (e.g.
  • Aryloxycarbonylamino e.g. phenoxycarbonylamino
  • Imido e.g. N-succinimido, N-phthalimido, 3-octadecenylsuccinimido
  • heterocyclic ring thio e.g. 2-benzothiazolylthio, 2,4-diphenyloxy-1,3,5-triazol-6-thio, 2-pyridylthio
  • Sulfinyl e.g.
  • Phosphonyl e.g. phenoxyphosphonyl, octyloxyphosphonyl, phenylphosphonyl
  • Aryloxycarbonyl e.g. phenoxycarbonyl
  • Acyl e.g. acetyl, 3-phenylpropan
  • substituents are optionally further substituted, for example by halogen or by an organic radical bonded via a C, O, N or S atom.
  • the preferred groups R 11 are alkyl, aryl, alkoxy, aryloxy, alkylthio, ureido, urethane and acylamino groups.
  • R 12 can have the meaning of R 11 and is preferably hydrogen, alkyl, aryl, a heterocyclic ring, alkoxycarbonyl, carbamoyl, sulfamoyl, sulfinyl, acyl or cyano.
  • R 13 can have the meaning of R 11 and is preferably hydrogen, alkyl, aryl, heterocyclic, alkoxy, aryloxy, alkylthio, arylthio, alkoxycarbonyl, carbamoyl or acyl, preferably alkyl, aryl, heterocyclic, alkylthio or arylthio.
  • Q is hydrogen or a leaving group such as halogen, alkoxy, aryloxy, acyloxy, Alkyl- or arylsulfonyloxy, acylamino, alkyl- or aryl-sulfonamido, alkoxycarbonyloxy, aryloxycarbonyloxy, alkyl-, aryl- or heterocyclyl-S-carbamoylamino, a 5- or 6-membered nitrogen-containing heterocyclic radical, imido and arylazo. These groups are optionally further substituted as shown for R 11 .
  • Q is halogen (e.g. fluorine, chlorine, bromine); Alkoxy (e.g. ethoxy, dodecyloxy, methoxyethylcarbamoylmethoxy, carboxypropyloxy, methylsulfonylethoxy, ethoxycarbonylmethoxy); Aryloxy (e.g. 4-methylphenoxy, 4-chlorophenoxy, 4-methoxyphenoxy, 4-carboxyphenoxy, 3-ethoxycarboxyphenoxy, 3-acetylaminophenoxy, 2-carboxyphenoxy); Acyloxy (e.g.
  • acetoxy, tetradecanoyloxy, benzoyloxy Alkyl or aryl sulfonyloxy (e.g. methanesulfonyloxy, toluenesulfonyloxy); Acylamino (e.g. dichloroacetylamino, heptafluorobutyrylamino); Alkyl or arylsulfonamido (e.g. methanesulfonamido, trifluoromethanesulfonamido, p-toluenesulfonylamido); Alkoxycarbonyloxy (e.g.
  • ethoxycarbonyloxy, benzyloxycarbonyloxy ethoxycarbonyloxy, benzyloxycarbonyloxy
  • Aryloxycarbonyloxy e.g. phenoxycarbonyloxy
  • Alkyl, aryl or heterocyclyl-S- e.g. dodecylthio, 1-carboxydodecylthio, phenylthio, 2-butoxy-5-t-octylphenylthio, tetrazolylthio
  • Carbamoylamino e.g. N-methylcarbamoylamino, N-phenylcarbamoylamino
  • 5- or 6-membered nitrogen-containing ring e.g.
  • Q can also form corresponding bis-compounds by condensing 4 equivalent couplers with an aldehyde or ketone. Furthermore, Q can contain photographically active groups such as development inhibitors or development accelerators. Q is preferably halogen, alkoxy, aryloxy, alkyl, arylthio, or a 5- or 6-membered nitrogen-containing heterocyclic group which is bonded to the coupling site via a nitrogen atom.
  • Pyrazolo-tetrazoles are described in JP-A-85/33552; Pyrazolo-pyrazole in JP-A-85 / 43,695; Pyrazolo-imidazoles in JP-A-85/35732, JP-A-86/18949 and US-A-4,500,630; Pyrazolo-triazoles in JP-A-85 / 186,567, JP-A-86/47957, JP-A-85 / 215,687, JP-A-85 / 197,688, JP-A-85 / 172,982, EP-A-119,860 , EP-A-173,256, EP-A-178,789, EP-A-178,788 and in Research Disclosure 84 / 24,624.
  • JP-A-86 / 28,947 JP-A-85 / 140,241, JP-A-85 / 262,160, JP-A-85 / 213,937, JP-A-87 / 278,552, JP-A-87 / 279,340, JP-A-88 / 100,457, EP-A-177,765, EP-A-176,804, EP-A-170,164, EP-A-164,130, EP-A-178,794, DE-A- 3,516,996, DE-A-3,508,766 and Research Disclosure 81/20919, 84/24531 and 85/25758.
  • Cyan couplers can be, for example, derivatives of phenol, 1-naphthol or pyrazoloquinazolone. Structures of the formula E are preferred, wherein R 21 , R 22 , R 23 and R 24 are hydrogen, halogen, alkyl, carbamoyl, amino, sulfonamido, phosphoramido or ureido. R 21 is preferably H or Cl, R 22 is preferably an alkyl or amino group. R 23 is preferably an amino group and R 24 is preferably hydrogen. Q "is hydrogen or a leaving group which is split off on reaction with the oxidized developer. A detailed list of cyan couplers can be found in US Pat. No. 4,456,681.
  • cyan couplers can be found in the following US-A-: 2,369,929, 2,423,730, 2,434,272, 2,474,293, 2,521,293, 2,521,908, 2,698,794, 2,706,684, 2,772,162, 2,801,171, 2,895,826, 2,908,573, 3,034,892, 3,046,129, 3,294,550, 3,253 3,311,476, 3,386,301, 3,419,390, 3,458,315, 3,476,560, 3,476,563, 3,516,831, 3,560,212, 3,582,322, 3,583,971, 3,591,383, 3,619,196, 3,632,347, 3,652,286, 3,737,326, 3,758,308, 3,839,044, 3,880,661, 4,004,929, 4,124,396, 4,333,999, 4,463,086, 4,456,681, 4,873,183 and 4,923,791 and in EP-A-354,549 and EP-A-398,664.
  • cyan couplers of the formula and / or or formula used, in which Z 1 is alkyl, aryl, Z 2 alkyl, cycloalkyl, aryl, a heterocyclic group or a ballast group, Z 3 is hydrogen or halogen, Z 1 and Z 3 together can form a ring, and Z 4 is hydrogen or a leaving group, and Z 5 is a ballast group, Z 6 is hydrogen or a leaving group and Zr is alkyl.
  • the color developers commonly used for color photographic materials are p-dialkylaminoanilines.
  • Examples include 4-amino-N, N-diethylaniline, 3-methyl-4, 4-amino-N, N-diethylaniline, 4-amino-N-ethyl-N- ⁇ -hydroxyethylaniline, 3-methyl-4-amino- N-ethyl-N- ⁇ -hydroxyethylaniline, 3-methyl-4-amino-N-ethyl-N- ⁇ -hydroxyethylaniline, 3-methyl-4-amino-N-ethyl-N- ⁇ -methanesulphonamidoethylaniline, 3-methyl 4-amino-N-ethyl-N- ⁇ -methoxyethyl-aniline, 3- ⁇ -methanesulphonamidoethyl-4-amino-N, N-diethylaniline, 3-methoxy-4-amino-N-ethyl-N
  • the UV absorbers of the formulas (I) and (III) used according to the invention can be incorporated into the color photographic material alone or together with the color coupler and, if appropriate, further additives, by pre-dissolving them in high-boiling organic solvents.
  • Solvents boiling above 160 ° C. are preferably used. Typical examples of such solvents are the esters of phthalic acid, phosphoric acid, citric acid, benzoic acid or of fatty acids, and also alkylamides and phenols.
  • a low-boiling solvent is also used to make it easier to incorporate the additives into the color photographic material.
  • solvents are esters such as e.g. Ethyl acetate, alcohols such as e.g. Butanol, ketones such as Methyl isobutyl ketone, chlorinated hydrocarbons such as e.g. Methylene chloride, or amides such as e.g. Dimethylformamide.
  • the additives themselves are liquid, they can also be incorporated into the photo material without the use of solvents.
  • UV absorbers according to the invention can optionally be dispersed without 0l in the gelatin layer; Research Disclosure 88/296017 and 89/303070.
  • Phosphates GB-A-791,219, BE-A-755,248, JP-A-76/76739, 78/27449, 78 / 218,252, 78/97573, 79 / 148,133, 82 / 216,177, 82/93323 and 83 / 216,177 and EP-A265,296.
  • Phthalates GB-A-791,219, JP-A-77/98050, 82/93322, 82 / 216,176, 82 / 218,251, 83/24321, 83/45699, 84/79888.
  • the amount of high-boiling solvent is, for example, in the range from 50 mg to 2 g per m 2 of carrier, preferably from 200 mg to 1 g per m 2 .
  • the photographic layers may also contain color fog inhibitors. These prevent the formation of color veils, such as those caused by the reaction of the coupler with inadvertently oxidized developer or with by-products of the color formation process.
  • color fog inhibitors are mostly hydroquinine derivatives, but can also be derivatives of aminophenols, gallic acid or ascorbic acid.
  • the photographic layers may also be so-called DIR couplers (DIR means D evelopment I nhibition R elease) contain give the colorless compounds with the oxidized developer. They are added to improve the sharpness and graininess of the color images.
  • DIR means D evelopment I nhibition R elease
  • the photographic layers in the material according to the invention can also contain further UV absorbers.
  • UV absorbers are benzotriazoles, 2-hydroxybenzophenones, salicylic acid esters, acrylonitrile derivatives or thiazolines.
  • Such UV absorbers are described in more detail, for example, in the following publications: US Pat. 4,749,643, GB-A-1,564,089, EP-A-190,003 and JP-A-71/2784, 81 / 111,826, 81/27, 146, 88 / 53,543 and 88 / 55,542.
  • Preferred UV absorbers are benzotriazoles, in particular 2- (2-hydroxyphenyl) benzotriazoles and preferably those of the formula (III) shown above.
  • the photographic layers can also contain phenolic compounds which act as light stabilizers for the color image and as agents against color fog. They can be contained in a light-sensitive layer (color layer) or in an intermediate layer, alone or together with other additives. Such connections are e.g.
  • the photographic layers can also contain certain phosphorus III compounds, especially phosphites and phosphonites. These act as light stabilizers for the color images and as a dark storage stabilizer for magenta couplers. They are preferably added to the high-boiling solvents together with the coupler.
  • phosphorus III compounds are e.g. described in more detail in the following publications: US-A-4,407,935, US-A-4,436,811, US-A-4,956,406, EP-A-181,289, JP-A-73/32728, JP-A-76/1420 and JP-A -55/66741.
  • the photographic layers can also contain organometallic complexes which are light stabilizers for the color images, in particular for the magenta dyes.
  • organometallic complexes which are light stabilizers for the color images, in particular for the magenta dyes.
  • Such compounds and their combination with other additives are e.g. described in more detail in the following publications: US Pat. JP-A-81 / 167,138, 81 / 168,652, 82/30834, 82 / 161,744; EP-A-137,271, 161,577, 185,506; DE-A-2,853,865.
  • the photographic layers can also contain hydroquinone compounds. These act as light stabilizers for the color couplers and for the color images and as scavengers for oxidized developers in the intermediate layers. You will mainly be in the Magenta layer used.
  • hydroquinone compounds and their combinations with other additives are described in more detail in, for example, the following publications: US Pat.
  • the photographic layers can also contain derivatives of hydroquinone ethers. These compounds act as light stabilizers and are particularly suitable for stabilizing magenta dyes. Such compounds and their combination with other additives are e.g. described in more detail in the following publications: US Pat , 4,207,111, 4,254,216, 4,134,011, 4,273,864, 4,264,720, 4,279,990, 4,332,886, 4,436,165, 4,360,589, 4,416,978, 4,385,111, 4,459,015, 4,559,297; GB-A 1,347,556, 1,366,441, 1,547,392, 1,557,237, 2,135,788; DE-A 3,214,567; DD-214,469, EP-A 161,577, 167,762, 164,130, 176,845; JP-A 76 / 123,642, 77/35633, 77 / 147,433, 78/126, 78/10430, 78/53321, 79
  • Usual silver chloride, bromide or iodide emulsions can be used as silver halide emulsions or mixtures thereof such as silver chlorobromide and silver chloroiodide emulsions, in which the silver halides can have all known crystal forms.
  • the use of silver chloride emulsions is of particular importance in the material according to the invention. The preparation of such emulsions and their sensitization are described in RESEARCH DISCLOSURE, November 1989, No. 307.105. This publication also mentions a number of binders for the emulsions mentioned, which can also be used in the materials according to the invention. The same applies to the carriers mentioned in the publication.
  • the silver halide emulsion which can be used in the practice of this invention can be sensitized for all desired wavelengths by means of sensitizing pigments.
  • sensitizing pigments cyanine pigments, merocyanine pigments, holopolar pigments, hemicyanine pigments, styryl pigments or hemioxanol pigments can be used.
  • Water-soluble dyes can be contained in the photosensitive material, for example to improve clarity by preventing radiation damage.
  • Oxonol dyes, hemioxonol dyes, styryl dyes, merocyanine dyes, cyanine dyes, anthraquinone dyes and azo dyes can be used for this.
  • EXAMPLE 1 A gelatin layer which contains silver bromide, a magenta coupler and a stabilizer is first applied to a carrier material coated with polyethylene, then a gelatin layer which contains the UV absorber of the formula (I) (top layer).
  • 2,4-dichloro-6-hydroxytriazine is used as the hardener and the sodium salt of diisobutylnaphthalenesulfonic acid as the wetting agent.
  • magenta coupler and stabilizer are given in Table 2.
  • a step wedge with a density difference of 0.15 logE per step is exposed on each of the samples thus obtained and then processed in accordance with the manufacturer's instructions in processing process E + 2 from Kodak for negative color papers.
  • the reflectance density in green is measured for the magenta step with a density between 0.9 and 1.1 of the wedge. Then the wedge is exposed in a Atlas exposure device with a total of 45 kJ / cm 2 and the remission density is measured again.
  • the dye loss (- ⁇ D) in% is given in Table 2.
  • Table 2 Sample No. Magenta Coupler (mg) Stabilizer (mg) UV absorber no. - ⁇ D 1 M-1 (329) ST-4 (118) (3) 64 2nd M-2 (417) ST-8 (144) (3) 61 3rd M-3 (394) ST-5 (128) (3) 54 4th M-4 (485) ST-1 (171) (3) 62 5 M-4 (485) ST-2 (171) (3) 65 6 M-4 (48-5) ST-3 (171) (3) 60 7 M-1 (329) ST-7 (118) (3) 74 8th M-1 (329) ST-6 (118) (3) 85 9 M-6 (306) ST-4 (107) (3) 36 10th M-6 (306) ST-1 (107) (3) 40 11 M-1 (329) ST-4 (118) (10) 69 12th M-6 (306) ST-4 (107) (10) 41 13 M-6 (306) ST-1 (107) (10) 47 14 M-6 (306) ST-4 (107) (12) 39 16 M-1 (329) ST-4 (118) - 87 17th M-2 (417) ST
  • Example 2 The procedure is as in Example 1, but without a stabilizer and using a cyan coupler.
  • a smaller decrease in the density of the cyan dye can be found in the samples which contain a UV absorber according to the invention.
  • Example 3 The procedure is as in Example 1, but without a stabilizer and using a yellow coupler.
  • Example 4 The procedure is as in Example 1.
  • magenta coupler and stabilizer are given in Table 5.
  • Example 5 The amount of UV absorber listed in the table below is dissolved in 2 ml of ethyl acetate. 1 ml of this solution is mixed with 9 ml of an aqueous gelatin solution (which contains 27.6 g / l gelatin and 6.8 g / l of an 8% aqueous solution of 4,8-diisobutylnaphthalene-2-sulfonic acid (sodium salt) as a wetting agent ) mixed. This mixture is emulsified with ultrasound for 3 minutes.
  • aqueous gelatin solution which contains 27.6 g / l gelatin and 6.8 g / l of an 8% aqueous solution of 4,8-diisobutylnaphthalene-2-sulfonic acid (sodium salt) as a wetting agent
  • UV absorber (mg) UV absorber loss DD (%) Atlas 60 kJ / cm 2 74 (3) (41) 0 75 (4) (49) 1 76 (5) (63) 1 77 (6) (42) 0 78 (7) (40) 0 79 (8th) (50) 3rd
  • Example 7 A gelatin layer containing silver bromide, a cyan coupler and a UV absorber of the formula (I) is applied to a carrier material coated with polyethylene.
  • the gelatin layer contains the following components (each m 2 carrier material)
  • Example 8 The procedure is as in Example 4, but the UV absorber of the invention (150 mg) is mixed with a hydroxybenzotriazole (150 mg)
  • Example 9 If the procedure is as in Example 4, but additionally a stabilizer of the following formula is added Sample No. Yellow coupler (mg) stabilizer (mg) UV absorber no. - ⁇ D% 99 Y-8 (927) ST-Y1 (273) - 31 100 Y-8 (927) ST-Y1 (273) (3) 10th
  • Example 10 If the procedure is as in Example 9, but the UV absorber of the invention (150 mg) is mixed with a hydroxybenzotriazole (150 mg)
  • Example 11 A photographic material with the following layer structure is produced:
  • the gelatin layers consist of the following components (each m 2 carrier material): Blue sensitive layer Yellow coupler Y-2 859 mg Tricresyl phosphate 286 mg gelatin 5.15 g Harder 300 mg Wetting agent 340 mg AgBr 520 mg First intermediate layer of gelatin gelatin 3.90 g Harder 230 mg Wetting agent 65 mg Green sensitive layer Magenta coupler M-6 306 mg Tricresyl phosphate 153 mg gelatin 5.15 g Harder 300 mg Wetting agent 85 mg AgBr 260 mg stabilizer 107 mg Second layer of gelatin gelatin 3.90 g Harder 230 mg Wetting agent 65 mg Red sensitive layer Cyan coupler E-6 331 mg Tricresyl phosphate 496 mg gelatin 5.15 g Harder 300mg Wetting agent 170 mg AgBr 260 mg
  • a protective layer is made with and without UV absorber with UV absorber without UV absorber gelatin 1.2 g 2.4 g UV absorber 300 mg --- Tricresyl phosphate 510 mg --- Hardening agent 40 mg 80 mg Wetting agent 100 mg 200 mg Sample No. UV absorber 104 - 105 (3) 106 (12)
  • Example 1 The corresponding compounds according to Example 1 are used as hardeners and wetting agents.
  • Three step wedges with a density difference of 0.15 kJ per step are exposed on the three samples 104-106 (with blue, green or red light).
  • the reflectance densities are measured in red for the cyan level, in green for the magenta level and in blue for the yellow level at a density between 0.9 and 1.1 of the wedges. Then the wedges are exposed in an Atlas exposure device with a total of 15 kJ / cm 2 and the reflectance densities are measured again.
  • the reflectance density is measured before and after the exposure in blue for yellowing.
  • UV absorbers reduces the loss of dye density of the cyan, magenta and yellow image dye and yellowing.
  • Example 12 A photographic material with the following layer structure is produced:
  • gelatin layers consist of the following components (each m 2 carrier material):
  • 2,4-dichloro-6-hydroxytriazine is used as the hardener and the sodium salt of diisobutylnaphthalenesulfonic acid as the wetting agent.
  • the reflectance densities are measured in red for the cyan level, in green for the magenta level and in blue for the yellow level at a density between 0.9 and 1.1 of the wedges. Then the wedges are exposed in an Atlas exposure device with a total of 15 kJ / cm 2 and the reflectance densities are measured again.
  • the reflectance density is measured before and after the exposure in blue for yellowing.
  • UV absorbers reduces the loss of dye density of the cyan, magenta and yellow image dye.
  • a mixture of 20.0 g of 2,4-bis [2,4-dihydroxyphenyl] -6-phenyl-1,3,5-triazine, 7.7 g of n-butyl glycidyl ether, 10.9 g of 2- Ethylhexyl glycidyl ether and 2.0 g of phosphorus triphenylethyl bromide are kept in 100 ml of mesitylene for 5 hours at 150 ° C.
  • Mesitylene is removed with the Rotavapor and the crude product is taken up in 50 ml of ethyl acetate.
  • the solution is poured onto a layer of silica gel (2 cm) and eluted with 200 ml of ethyl acetate.

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Description

Die vorliegende Erfindung betrifft neues photographisches Material, das UV-Absorber, insbesondere vom Bis-2-hydroxyphenyltriazinyltyp enthält.The present invention relates to new photographic material which contains UV absorbers, in particular of the bis-2-hydroxyphenyltriazinyl type.

Die Verwendung von 2-Hydroxyphenyl-1,3,5-triazinen als Stabilisierungsmittel gegen Ultraviolettstrahlung in photographischen Materialien ist bekannt, z. B. aus der DE-A-2 113 833.The use of 2-hydroxyphenyl-1,3,5-triazines as stabilizers against ultraviolet radiation in photographic materials is known, e.g. B. from DE-A-2 113 833.

Bisher in photographischen Materialien als UV-Absorber verwendete Hydroxyphenylbenztriazole zeigten den Nachteil, dass ihre eigene Stabilität gegen Licht unzureichend war. Aus diesem Grund nimmt die Wirksamkeit dieser UV-Absorber mit zunehmender Belichtung ab. Ferner haben in vielen Fällen mangelnde chemische Stabilität, geringe Löslichkeit, zu hohe Eigenfarbe oder zu niedriger Extinktionskoeffizient der Triazine ihre Anwendung in photographischen Materialien verhindert.Hydroxyphenylbenztriazoles previously used as UV absorbers in photographic materials showed the disadvantage that their own stability against light was insufficient. For this reason, the effectiveness of these UV absorbers decreases with increasing exposure. Furthermore, in many cases, poor chemical stability, low solubility, too high an inherent color or too low an extinction coefficient of the triazines have prevented their use in photographic materials.

Es wurde nun eine Gruppe von Triazin-UV-Absorbern gefunden, die sich überraschenderweise weitgehend frei von solchen Nachteilen erweisen. Sie zeigen eine verbesserte Eigenlichtstabilität und besitzen die Eigenschaft, Bildfarbstoffe und Farbkuppler besser gegen Lichteinwirkung zu schützen als dies mit den üblicherweise in photographischen Materialien verwendeten Hydroxyphenylbenztriazolen und Triazinen möglich war. Insbesondere ist diese Gruppe von Triazinen geeignet, die Stabilität der Magenta- und Cyanschicht photographischer Materialien zu erhöhen, indem sie z.B. in Schichten, welche über der Magenta- oder Cyanschicht angebracht sind, oder direkt in die Cyanschicht eingelagert werden.A group of triazine UV absorbers has now been found which, surprisingly, has proven to be largely free from such disadvantages. They show improved stability to natural light and have the property of better protecting image dyes and color couplers against exposure to light than was possible with the hydroxyphenylbenztriazoles and triazines conventionally used in photographic materials. In particular, this group of triazines is suitable for increasing the stability of the magenta and cyan layers of photographic materials, e.g. in layers, which are applied over the magenta or cyan layer, or directly embedded in the cyan layer.

Die erfindungsgemässen UV-Absorber können für alle Arten photosensitiven Materials verwendet werden. Beispielsweise können sie für Farbpapier, Farbumkehrpapier, Direkt-Positiv-Farbmaterial, Farbnegativfilm, Farbpositivfilm, Farbumkehrfilm und weitere eingesetzt werden. Unter anderem werden sie bevorzugt für photosensitives Farbmaterial, welches ein Umkehrsubstrat enthält oder welches Positive bildet, verwendet.The UV absorbers according to the invention can be used for all types of photosensitive material. For example, they can be used for color paper, color reversal paper, direct positive color material, color negative film, color positive film, color reversal film and others. Among other things, they are preferably used for photosensitive color material which contains a reversal substrate or which forms positives.

Ferner können diese Triazine mit Vorteil mit UV-Absorbern vom Hydroxyphenylbenztriazoltyp, insbesondere bei Raumtemperatur flüssigen Vertretern hiervon (vgl. beispielsweise US-A-4,853,471, US-A-4,973,702, US-A-4,921,966 und US-A-4,973,701) kombiniert werden. Solche Kombinationen erlauben eine beträchtliche Reduktion der Oelmenge, die zur Einarbeitung der UV-Absorber in die betreffende photographische Schicht notwendig ist. Daraus resultiert eine geringe Schichtdicke oder, bei konstant gehaltener Schichtdicke, eine höhere Konzentration an UV-Absorber.Furthermore, these triazines can advantageously be combined with UV absorbers of the hydroxyphenylbenztriazole type, in particular representatives thereof which are liquid at room temperature (cf. for example US Pat. Nos. 4,853,471, 4,973,702, 4,921,966 and 4,973,701). Such combinations allow considerable Reduction in the amount of oil required to incorporate the UV absorbers into the photographic layer in question. This results in a small layer thickness or, if the layer thickness is kept constant, a higher concentration of UV absorber.

Auch Kombinationen der Triazine mit anderen Typen von UV-Absorbern wie Benzophenonen, Oxaniliden, Cyanoacrylaten, Salicylsäureestem, Acrylnitrile oder Thiazolinen eignen sich zur Verwendung in photographischen Materialien.Combinations of the triazines with other types of UV absorbers such as benzophenones, oxanilides, cyanoacrylates, salicylic acid esters, acrylonitriles or thiazolines are also suitable for use in photographic materials.

Insbesondere lassen sich photographische Materialien ähnlich solchen, wie sie in US-A-4,518,686 beschrieben sind, mit gutem Erfolg stabilisieren.In particular, photographic materials similar to those described in US-A-4,518,686 can be stabilized with good success.

Gegenstand vorliegender Anmeldung ist somit photographisches Material enthaltend auf einem Träger eine blauempfindliche, eine grünempfindliche und/oder eine rotempfindliche Silberhalogenidemulsionsschicht sowie gegebenenfalls eine Protektionsschicht, wobei zwischen der obersten Silberhalogenidemulsionsschicht und der Protektionsschicht, beziehungsweise oberhalb der obersten Silberhalogenidemulsionsschicht, eine Schicht mit einem UV-Absorber angeordnet ist, dadurch gekennzeichnet, dass der UV-Absorber der Formel

Figure imgb0001
entspricht, worin
die Reste R1 unabhängig voneinander ein Rest der Formel -CH2-CH(ORx)Ry, -CH2CH(ORx)CH2ORz,
Figure imgb0002
-CH2CORy oder -CH2COCH2ORz bedeuten, wobei

  • RxH, -CORs, -COORw oder -SiRpRqRr,
  • Ry C1-C18-Alkyl oder Phenyl-C1-C4-Alkyl,
  • Rz C1-C18-Alkyl, C2-C18-Alkenyl, Phenyl-C1-C4-Alkyl, -CORs oder durch Sauerstoff unterbrochenes C1-C24-Alkyl oder C2-C24-Hydroxyalkyl,
  • Rs C1-C18-Alkyl, C2-C18-Alkenyl oder Phenyl,
  • Rw C1-C4-Alkyl und
  • Rp, Rq und Rr unabhängig voneinander C1-C6-Alkyl oder Phenyl
    bedeuten; oder
die Reste R1 unabhängig voneinander eine Gruppe G-II bedeuten,
wobei II eine Gruppe der Formel
Figure imgb0003
ist
und
G eine direkte Bindung oder eine zweiwertige Gruppe einer der folgenden Formeln ist:
-(CH2)q-, -(CH2)q-O-, -(CH2)q-O-R26-, -(CH2)q-CO-X-(CH2)r-, -(CH2)q-CO-X-(CH2)r-O-,
Figure imgb0004
Figure imgb0005
-CH2-CH(OH)-CH2-Y-(CH2)q-,
  • worin q und r unabhängig voneinander 1-4 und p 0-50 sind,
  • R26 C1-C12-Alkylen, Cyclohexylen oder Phenylen bedeutet,
  • R27 C1-C12-Alkyl, C5-C8-Cycloalkyl, Phenyl, C2-C13-Alkoxymethyl, C6-C9-Cycloalkoxymethyl oder Phenoxymethyl bedeutet,
  • R28 eine Gruppe der Formel G-II bedeutet,
  • R29 Waserstoff oder Methyl ist,
  • X -O- oder -NR23- bedeutet, worin R23 Wasserstoff, C1-C12-Alkyl oder eine Gruppe -(CH2)3-G-II oder -(CH2)3-O-G-II bedeutet,
  • Y -O- oder -NH- bedeutet,
  • R20, R21 und R22 unabhängig voneinander C1-C18-Alkyl, Cyclohexyl, Phenyl oder C1-C18-Alkoxy bedeuten; und
  • R12 Alkyl mit 1 bis 12 Kohlenstoffatomen oder eine Gruppe der Formel
    Figure imgb0006
    oder -OR16 ist, vorzugsweise ist R12 eine Gruppe der Formel
    Figure imgb0007
    worin
  • R13 und R14 unabhängig voneinander Wasserstoff, C1-C4-Alkyl oder Chlor sind, und
  • R16 Alkyl mit 1 bis 8 Kohlenstoffatomen oder durch Sauerstoff unterbrochenes Alkyl mit 3 bis 12 Kohlenstoffatomen ist.
The subject of the present application is therefore photographic material containing a blue-sensitive, a green-sensitive and / or a red-sensitive silver halide emulsion layer and optionally a protection layer, a layer with a UV absorber being arranged between the uppermost silver halide emulsion layer and the protection layer, or above the uppermost silver halide emulsion layer is characterized in that the UV absorber of the formula
Figure imgb0001
corresponds to what
the radicals R 1 independently of one another are a radical of the formula -CH 2 -CH (OR x ) R y , -CH 2 CH (OR x ) CH 2 OR z ,
Figure imgb0002
-CH 2 COR y or -CH 2 COCH 2 OR z mean, where
  • R x H, -COR s , -COOR w or -SiR p R q R r ,
  • R y C 1 -C 18 alkyl or phenyl-C 1 -C 4 alkyl,
  • R z C 1 -C 18 alkyl, C 2 -C 18 alkenyl, phenyl-C 1 -C 4 alkyl, -COR s or C 1 -C 24 alkyl interrupted by oxygen or C 2 -C 24 hydroxyalkyl ,
  • R s C 1 -C 18 alkyl, C 2 -C 18 alkenyl or phenyl,
  • R w C 1 -C 4 alkyl and
  • R p , R q and R r independently of one another C 1 -C 6 alkyl or phenyl
    mean; or
the radicals R 1 independently of one another represent a group G-II,
where II is a group of formula
Figure imgb0003
is
and
G is a direct bond or a divalent group of one of the following formulas:
- (CH 2 ) q -, - (CH 2 ) q -O-, - (CH 2 ) q -OR 26 -, - (CH 2 ) q -CO-X- (CH 2 ) r -, - (CH 2 ) q -CO-X- (CH 2 ) r -O-,
Figure imgb0004
Figure imgb0005
-CH 2 -CH (OH) -CH 2 -Y- (CH 2 ) q -,
  • wherein q and r are independently 1-4 and p 0-50,
  • R 26 is C 1 -C 12 alkylene, cyclohexylene or phenylene,
  • R 27 is C 1 -C 12 alkyl, C 5 -C 8 cycloalkyl, phenyl, C 2 -C 13 alkoxymethyl, C 6 -C 9 cycloalkoxymethyl or phenoxymethyl,
  • R 28 represents a group of the formula G-II,
  • R 29 is hydrogen or methyl,
  • X denotes -O- or -NR 23 -, in which R 23 denotes hydrogen, C 1 -C 12 -alkyl or a group - (CH 2 ) 3 -G-II or - (CH 2 ) 3 -OG-II,
  • Y means -O- or -NH-,
  • R 20 , R 21 and R 22 independently of one another are C 1 -C 18 alkyl, cyclohexyl, phenyl or C 1 -C 18 alkoxy; and
  • R 12 is alkyl having 1 to 12 carbon atoms or a group of the formula
    Figure imgb0006
    or -OR 16 , preferably R 12 is a group of the formula
    Figure imgb0007
    wherein
  • R 13 and R 14 are independently hydrogen, C 1 -C 4 alkyl or chlorine, and
  • R 16 is alkyl of 1 to 8 carbon atoms or oxygen interrupted alkyl of 3 to 12 carbon atoms.

Bedeuten Substituenten in den Verbindungen der Formel (I) Alkyl mit 1 bis 18 Kohlenstoffatomen, so kommen hierfür Reste wie Methyl, Aethyl, Propyl, Butyl, Pentyl, Hexyl, Heptyl, Octyl, Nonyl, Decyl, Undecyl, Dodecyl, Tetradecyl, Hexadecyl und Octadecyl sowie entsprechende verzweigte Isomeren in Frage. Alkylreste mit 3 bis 24 Kohlenstoffatomen, die durch Sauerstoff unterbrochen sind, sind beispielsweise

Figure imgb0008
oder
Figure imgb0009
If substituents in the compounds of the formula (I) are alkyl having 1 to 18 carbon atoms, radicals such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tetradecyl, hexadecyl and Octadecyl and corresponding branched isomers in question. Examples of alkyl radicals having 3 to 24 carbon atoms which are interrupted by oxygen are
Figure imgb0008
or
Figure imgb0009

Bevorzugt sind Verbindungen, bei welchen die Reste R1 unabhängig voneinander Reste der Formel -CH2-CH(ORx)Ry, -CH2CH(ORx)CH2X)z, -CH2CORy oder -CH2COCH2COz bedeuten, wobei

  • Rx H, -CORs, -COORw oder -SiRpRqRr,
  • Ry C1-C8-Alkyl,
  • Rz C1-C18-Alkyl, C2-C18-Alkenyl, Benzyl, -CORs oder durch Sauerstoff unterbrochenes C1-C24-Alkyl oder C2-C24-Hydroxyalkyl,
  • Rs C1-C18-Alkyl, C2-C18-Alkenyl oder Phenyl,
  • Rw C1-C4-Alkyl und
  • Rp, Rq und Rr unabhängig voneinander C1-C6-Alkyl
    bedeuten; oder
R1 eine Gruppe G-II bedeuten,
wobei II eine Gruppe der Formel
Figure imgb0010
ist
und
G eine direkte Bindung oder eine zweiwertige Gruppe einer der folgenden Formeln ist:
-(CH2)q-, -(CH2)q-O-, -(CH2)q-CO-X-(CH2)r-,
Figure imgb0011
oder
-CH2-CH(OH)-CH2-Y-(CH2)q-,
  • worin q und r unabhängig voneinander 1, 2 oder 3 und p 0-50 sind,
  • R27 Methyl, Phenyl, C3-C9-Alkoxymethyl oder Phenoxymethyl bedeutet,
  • R28 eine Gruppe der Formel G-II bedeutet,
  • X und Y -O- bedeuten,
  • R20, R21 und R22 unabhängig voneinander C1-C8-Alkyl, Phenyl oder C1-C8-Alkoxy bedeuten; und
  • R12 eine Gruppe der Formel
    Figure imgb0012
    ist, worin
  • R13 und R14 unabhängig voneinander Wasserstoff, C1-C4-Alkyl oder Chlor sind.
Preferred compounds are those in which the radicals R 1 independently of one another are radicals of the formula -CH 2 -CH (OR x ) R y , -CH 2 CH (OR x ) CH 2 X) z , -CH 2 COR y or -CH 2 COCH 2 CO z mean, where
  • R x H, -COR s , -COOR w or -SiR p R q R r ,
  • R y C 1 -C 8 alkyl,
  • R z C 1 -C 18 alkyl, C 2 -C 18 alkenyl, benzyl, -COR s or C 1 -C 24 alkyl interrupted by oxygen or C 2 -C 24 hydroxyalkyl,
  • R s C 1 -C 18 alkyl, C 2 -C 18 alkenyl or phenyl,
  • R w C 1 -C 4 alkyl and
  • R p , R q and R r independently of one another C 1 -C 6 alkyl
    mean; or
R 1 represents a group G-II,
where II is a group of formula
Figure imgb0010
is
and
G is a direct bond or a divalent group of one of the following formulas:
- (CH 2 ) q -, - (CH 2 ) q -O-, - (CH 2 ) q -CO-X- (CH 2 ) r -,
Figure imgb0011
or
-CH 2 -CH (OH) -CH 2 -Y- (CH 2 ) q -,
  • wherein q and r are independently 1, 2 or 3 and p are 0-50,
  • R 27 denotes methyl, phenyl, C 3 -C 9 alkoxymethyl or phenoxymethyl,
  • R 28 represents a group of the formula G-II,
  • X and Y mean -O-,
  • R 20 , R 21 and R 22 independently of one another are C 1 -C 8 alkyl, phenyl or C 1 -C 8 alkoxy; and
  • R 12 is a group of the formula
    Figure imgb0012
    is what
  • R 13 and R 14 are independently hydrogen, C 1 -C 4 alkyl or chlorine.

Besonders bevorzugt werden solche Verbindungen der Formel (I) verwendet, worin die Reste R1 unabhängig voneinander einen Rest der Formel -CH2-CH(ORx)Ry oder -CH2CH(ORx)CH2ORz bedeuten, wobei

  • Rx H, -CORs, -COOCH3 oder -Si(CH3)2Rr,
  • Ry C1-C8-Alkyl,
  • Rz C1-C18-Alkyl, C2-C18-Alkenyl, -CORs oder durch Sauerstoff unterbrochenes C1-C24-Alkyl oder C2-C24-Hydroxyalkyl,
  • Rs C1-C4-Alkyl oder C2-C4-Alkenyl und
  • Rr C1-C6-Alkyl
    bedeuten; oder
R1 eine Gruppe G-II ist,
wobei II eine Gruppe der Formel
Figure imgb0013
ist
und
p 0 ist,
G eine zweiwertige Gruppe einer der folgenden Formeln ist: -(CH2)3-, -(CH2)2-O-,
-CH2-CO-O-CH2-, -CH2-CH(CH2-O-C4H9)-O-,
Figure imgb0014
oder
-CH2-CH(OH)-CH2-O-(CH2)3-,
  • R28 -Si(CH3)2R22bedeutet,
  • R20 und R21 unabhängig voneinander Methyl oder Ethyl und
  • R22 C1-C8-Alkyl bedeuten; und
  • R12 eine Gruppe der Formel
    Figure imgb0015
    ist, worin
  • R13 und R14 unabhängig voneinander Wasserstoff, C1-C4-Alkyl oder Chlor sind.
Those compounds of the formula (I) are particularly preferably used in which the radicals R 1 independently of one another are a radical of the formula -CH 2 -CH (OR x ) R y or -CH 2 CH (OR x ) CH 2 OR z , where
  • R x H, -COR s , -COOCH 3 or -Si (CH 3 ) 2 R r ,
  • R y C 1 -C 8 alkyl,
  • R z C 1 -C 18 alkyl, C 2 -C 18 alkenyl, -COR s or C 1 -C 24 alkyl interrupted by oxygen or C 2 -C 24 hydroxyalkyl,
  • R s C 1 -C 4 alkyl or C 2 -C 4 alkenyl and
  • R r C 1 -C 6 alkyl
    mean; or
R 1 is a group G-II,
where II is a group of formula
Figure imgb0013
is
and
p is 0,
G is a divalent group of one of the following formulas: - (CH 2 ) 3 -, - (CH 2 ) 2 -O-,
-CH 2 -CO-O-CH 2 -, -CH 2 -CH (CH 2 -OC 4 H 9 ) -O-,
Figure imgb0014
or
-CH 2 -CH (OH) -CH 2 -O- (CH 2 ) 3 -,
  • R 28 denotes Si (CH 3 ) 2 R 22 ,
  • R 20 and R 21 independently of one another are methyl or ethyl and
  • R 22 is C 1 -C 8 alkyl; and
  • R 12 is a group of the formula
    Figure imgb0015
    is what
  • R 13 and R 14 are independently hydrogen, C 1 -C 4 alkyl or chlorine.

Ganz besonders bevorzugt werden solche Verbindungen der Formel (I) verwendet, worin die Reste R1 unabhängig voneinander einen Rest der Formel -CH2CH(ORx)CH2ORz bedeuten, wobei

  • Rx H, -CORs, -COOCH3 oder -Si(CH3)2Rr,
  • Rz C1-C18-Alkyl, C2-C18-Alkenyl, -CORs oder durch Sauerstoff unterbrochenes C1-C24-Alkyl oder C2-C24-Hydroxyalkyl,
  • Rs C1-C4-Alkyl oder C2-C4-Alkenyl und
  • Rr C1-C6-Alkyl
    bedeuten; und
  • R12 eine Gruppe der Formel
    Figure imgb0016
    ist, worin
  • R13 Wasserstoff und R14 Wasserstoff, Methyl oder Chlor sind.
Those compounds of the formula (I) are very particularly preferably used in which the radicals R 1 independently of one another are a radical of the formula -CH 2 CH (OR x ) CH 2 OR z ,
  • R x H, -COR s , -COOCH 3 or -Si (CH 3 ) 2 R r ,
  • R z C 1 -C 18 alkyl, C 2 -C 18 alkenyl, -COR s or C 1 -C 24 alkyl interrupted by oxygen or C 2 -C 24 hydroxyalkyl,
  • R s C 1 -C 4 alkyl or C 2 -C 4 alkenyl and
  • R r C 1 -C 6 alkyl
    mean; and
  • R 12 is a group of the formula
    Figure imgb0016
    is what
  • R 13 is hydrogen and R 14 is hydrogen, methyl or chlorine.

Vorzugsweise enthält das erfindungsgemässe Material zwischen den Silberhalogenidemulsionsschichten Gelatinezwischenschichten.The material according to the invention preferably contains intermediate gelatin layers between the silver halide emulsion layers.

In einer weiteren bevorzugten Ausführungsform enthält das erfindungsgemässe Material eine weitere Schicht mit einem UV-Absorber der Formel (I), welche zwischen der grün- und rotempfindlichen Silberhalogenidemulsionsschicht angeordnet ist.In a further preferred embodiment, the material according to the invention contains a further layer with a UV absorber of the formula (I), which is arranged between the green and red-sensitive silver halide emulsion layer.

Gute Ergebnisse werden auch erzielt, wenn der UV-Absorber der Formel (I) zusätzlich in der rotempfindlichen Silberhalogenidemulsionsschicht enthalten ist.Good results are also achieved if the UV absorber of the formula (I) is additionally contained in the red-sensitive silver halide emulsion layer.

In der Schicht zwischen der grün- und rotempfindlichen Schicht und/oder in der rotempfindlichen Schicht können mit Vorteil anstelle der UV-Absorber der Formel (I) Benztriazolverbindungen verwendet werden.In the layer between the green- and red-sensitive layer and / or in the red-sensitive layer, benzotriazole compounds can advantageously be used instead of the UV absorbers of the formula (I).

Vorzugsweise entsprechen diese Benztriazolverbindungen (HBT) der Formel

Figure imgb0017
worin T1, T2 und T3 unabhängig voneinander Wasserstoff, Halogen, Alkyl, Alkyl substituiert mit einer Carbonsäureestergruppe, Alkoxy, Aryloxy, Hydroxyl oder Acyloxy sind, und T4 Wasserstoff, Alkoxy, Aryloxy oder Acyloxy ist.These benzotriazole compounds (HBT) preferably correspond to the formula
Figure imgb0017
wherein T 1 , T 2 and T 3 are independently hydrogen, halogen, alkyl, alkyl substituted with a carboxylic acid ester group, alkoxy, aryloxy, hydroxyl or acyloxy, and T 4 is hydrogen, alkoxy, aryloxy or acyloxy.

Besonders bevorzugt sind solche Verbindungen der Formel (III), welche bei Zimmertemperatur flüssig sind.Those compounds of formula (III) which are liquid at room temperature are particularly preferred.

In einem weiteren Aspekt betrifft die vorliegende Erfindung auch photographisches Material enthaltend auf einem Träger eine blauempfindliche, eine grünempfindliche und/oder eine rotempfindliche Silberhalogenidemulsionsschicht sowie eine Protektionsschicht, wobei zwischen der obersten Silberhalogenidemulsionsschicht und der Protektionsschicht eine Schicht mit einem UV-Absorber angeordnet ist, dadurch gekennzeichnet, dass (a) der UV-Absorber der Formel

Figure imgb0018
entspricht, worin T1, T2 und T3 unabhängig voneinander Wasserstoff, Halogen, Alkyl, Alkyl substituiert mit einer Carbonsäureestergruppe, Alkoxy, Aryloxy, Hydroxyl oder Acyloxy sind und T4 Wasserstoff, Alkoxy, Aryloxy oder Acyloxy ist, und (b) das Material mindestens eine weitere Schicht aufweist, welche einen UV-Absorber der Formel (I) enthält.In a further aspect, the present invention also relates to photographic material containing, on a support, a blue-sensitive, a green-sensitive and / or a red-sensitive silver halide emulsion layer and a protection layer, a layer with a UV absorber being arranged between the uppermost silver halide emulsion layer and the protection layer that (a) the UV absorber of the formula
Figure imgb0018
where T 1 , T 2 and T 3 are independently hydrogen, halogen, alkyl, alkyl substituted with a carboxylic acid ester group, alkoxy, aryloxy, hydroxyl or acyloxy and T 4 is hydrogen, alkoxy, aryloxy or acyloxy, and (b) that Material has at least one further layer which contains a UV absorber of the formula (I).

Vorzugsweise ist die weitere Schicht zwischen der grün- und rotempfindlichen Silberhalogenidemulsionsschicht angeordnet.The further layer is preferably arranged between the green and red-sensitive silver halide emulsion layer.

In einer weiteren bevorzugten Ausführungsform enhält das photographische Material zusätzlich in der rotempfindlichen Schicht einen UV-Absorber der Formel (I). Es kann ferner vorteilhaft sein, wenn in der weiteren Schicht oder in der rotempfindlichen Schicht der UV-Absorber der Formel (I) durch einen solchen der Formel (III) ersetzt wird; dabei soll aber wenigstens eine Schicht einen UV-Absorber der Formel (I) enthalten.In a further preferred embodiment, the photographic material additionally contains a UV absorber of the formula (I) in the red-sensitive layer. It can also be advantageous if the UV absorber of the formula (I) is replaced by one of the formula (III) in the further layer or in the red-sensitive layer; but at least one layer should contain a UV absorber of the formula (I).

Bevorzugte photographische Materialien enthalten zwischen den Silberhalogenidemulsionsschichten Gelatinezwischenschichten.Preferred photographic materials contain intermediate gelatin layers between the silver halide emulsion layers.

In einer weiteren Ausführungsform der vorliegenden Erfindung enthält das photographische Material auf einem Träger mindestens 2 Silberhalogenidemulsionsschichten mit einer zwischen diesen Schichten liegenden Schicht mit einem UV-Absorber, dadurch gekennzeichnet, dass der UV-Absorber der Formel (I) entspricht. Vorzugsweise handelt es sich bei den beiden Silberhalogenidemulsionsschichten um eine grünempfindliche und eine rotempfindliche Silberhalogenidemulsionsschicht. Ferner wird ein entsprechendes Material bevorzugt, worin zusätzlich die rotempfindliche Silberhalogenidemulsionsschicht einen UV-Absorber der Formel (I) oder (III) enthält.In a further embodiment of the present invention, the photographic material contains at least 2 silver halide emulsion layers with a layer between these layers with a UV absorber, characterized in that the UV absorber corresponds to the formula (I). The two silver halide emulsion layers are preferably a green-sensitive and a red-sensitive silver halide emulsion layer. Furthermore, a corresponding material is preferred, in which the red-sensitive silver halide emulsion layer additionally contains a UV absorber of the formula (I) or (III).

Eine andere Ausführungsform der vorliegenden Erfindung betrifft photographisches Material, das auf einem Träger eine rotempfindliche Silberhalogenidemulsionsschicht sowie gegebenenfalls eine blauempfindliche und/oder grünempfindliche Silberhalogenidemulsionsschicht enthält, dadurch gekennzeichnet, dass die rotempfindliche Silberhalogenidemulsionsschicht einen UV-Absorber der Formel (I) enthält. Vorzugsweise enthält es zwischen der rotempfindlichen Silberhalogenidemulsionsschicht und dem Träger eine Schicht mit einem UV-Absorber der Formel (III).Another embodiment of the present invention relates to photographic material having a red sensitive silver halide emulsion layer on a support and optionally also contains a blue-sensitive and / or green-sensitive silver halide emulsion layer, characterized in that the red-sensitive silver halide emulsion layer contains a UV absorber of the formula (I). It preferably contains a layer with a UV absorber of the formula (III) between the red-sensitive silver halide emulsion layer and the support.

Des weiteren kann es vorteilhaft sein, wenn alle oder ein Teil der besagten Schichten, welche einen UV-Absorber enthalten können, eine Mischung aus den UV-Absorbern der Formeln (I) und (III) aufweisen.Furthermore, it can be advantageous if all or part of the layers which can contain a UV absorber have a mixture of the UV absorbers of the formulas (I) and (III).

Bevorzugt sind solche photographischen Materialien, welche als Silberhalogenid in der blauempfindlichen, grünempfindlichen und/oder rotempfindlichen Schicht Silberchloridbromid, welches mindestens zu 90 mol % aus Silberchlorid besteht, enthalten.Preferred photographic materials are those which contain silver chloride bromide, which consists of at least 90 mol% silver chloride, as silver halide in the blue-sensitive, green-sensitive and / or red-sensitive layer.

Desweiteren sind photographische Materialien bevorzugt, welche die Silberhalogenidemulsionsschichten in der Reihenfolge blauempfindliche, grünempfindliche und rotempfindliche Silberhalogenidemulsionsschicht enthalten.Furthermore, photographic materials are preferred which contain the silver halide emulsion layers in the order of blue-sensitive, green-sensitive and red-sensitive silver halide emulsion layers.

Die erfindungsgemässen photographischen Materialien bieten gegenüber Materialien mit Benztriazoll-UV-Absorbern den Vorteil, dass die UV-Absorber der Formel (I) in einer vergleichsweise geringen Menge benötigt werden, um einen ausreichenden Schutz gegen UV-Strahlung zu gewährleisten. Dies bedeutet, dass die Dicke der Schichten, in die die UV-Absorber der Formel (I) eingelagert werden, sehr dünn sein können, was sich z.B. auf die Schärfe der mit diesem Material hergestellten Abbildungen positiv auswirkt. Offensichtlich ergibt dann die Verwendung einer vergleichbaren Menge UV-Absorber einen noch besseren Schutz.The photographic materials according to the invention offer the advantage over materials with benzotriazole UV absorbers that the UV absorbers of the formula (I) are required in a comparatively small amount in order to ensure adequate protection against UV radiation. This means that the thickness of the layers in which the UV absorbers of the formula (I) are incorporated can be very thin, which is e.g. has a positive effect on the sharpness of the images made with this material. Obviously, the use of a comparable amount of UV absorber will result in even better protection.

Typische und bevorzugte Verbindungen der Formel (I) sind in der folgenden Tabelle zusammengestellt:

Figure imgb0019
Figure imgb0020
Figure imgb0021
Figure imgb0022
Figure imgb0023
Figure imgb0024
Typical and preferred compounds of the formula (I) are listed in the following table:
Figure imgb0019
Figure imgb0020
Figure imgb0021
Figure imgb0022
Figure imgb0023
Figure imgb0024

Beispiele der Verbindungen der Formel (III) sind:

Figure imgb0025
Examples of the compounds of the formula (III) are:
Figure imgb0025

Im erfindungsgemässen Material verwendbare Gelbkuppler sind vorzugsweise Verbindungen der Formel A

Figure imgb0026
worin R1 Alkyl oder Aryl ist, R2 Aryl ist und Q Wasserstoff oder eine Gruppe ist, die durch Reaktion mit dem oxidierten Entwickler abgespaltet werden kann.Yellow couplers which can be used in the material according to the invention are preferably compounds of the formula A.
Figure imgb0026
wherein R 1 is alkyl or aryl, R 2 is aryl and Q is hydrogen or a group that can be cleaved by reaction with the oxidized developer.

Eine Gruppe von Gelbkupplern sind solche Verbindungen der Formel A, in denen R1 t-Butyl ist und R2 eine Gruppe der Formel

Figure imgb0027
ist, worin R3 Wasserstoff, Halogen, Alkyl oder Alkoxy bedeutet und R4, R5 und R6 Wasserstoff, Halogen, Alkyl, Alkenyl, Alkoxy, Aryl, Carboxy, Alkoxycarbonyl, eine Carbamoylgruppe, eine Sulfon- oder Sulfamoylgruppe, eine Alkylsulfonaminogruppe, Acylaminogruppe, Ureidogruppe oder Aminogruppe bedeuten.A group of yellow couplers are those compounds of the formula A in which R 1 is t-butyl and R 2 is a group of the formula
Figure imgb0027
is where R 3 is hydrogen, halogen, alkyl or alkoxy and R 4 , R 5 and R 6 are hydrogen, halogen, alkyl, alkenyl, alkoxy, aryl, carboxy, alkoxycarbonyl, a carbamoyl group, a sulfone or sulfamoyl group, an alkylsulfonamino group, Acylamino group, ureido group or amino group.

Vorzugsweise sind R3 Chlor, R4 und R5 Wasserstoff und R6 eine Acylaminogruppe. Hierzu gehören auch die Verbindungen der Formel

Figure imgb0028
worin x 0-4 ist, R7 Wasserstoff oder Alkyl bedeutet und R8 und R9 Alkyl sind.R 3 is preferably chlorine, R 4 and R 5 are hydrogen and R 6 is an acylamino group. This also includes the compounds of the formula
Figure imgb0028
wherein x is 0-4, R 7 is hydrogen or alkyl and R 8 and R 9 are alkyl.

Eine andere Gruppe von Gelbkupplern entspricht der Formel B

Figure imgb0029
worin R10 Wasserstoff, Halogen oder Alkoxy ist,
R11, R12 und R13 Wasserstoff, Halogen, Alkyl, Alkenyl, Alkoxy, Aryl, Carboxyl, Alkoxycarbonyl, eine Carbamoylgruppe, eine Sulfongruppe, Sulfamoylgruppe, Sulfonamidogruppe, Acylaminogruppe, Ureidogruppe oder Aminogruppe bedeuten und R1 und Q die oben angegebene Bedeutung haben.Another group of yellow couplers corresponds to Formula B.
Figure imgb0029
where R 10 is hydrogen, halogen or alkoxy,
R 11 , R 12 and R 13 are hydrogen, halogen, alkyl, alkenyl, alkoxy, aryl, carboxyl, alkoxycarbonyl, a carbamoyl group, a sulfone group, sulfamoyl group, sulfonamido group, acylamino group, ureido group or amino group and R 1 and Q have the meaning given above .

Dazu gehören Verbindungen der Formel B, in denen R1 t-Butyl ist, R10 Chlor ist, R11 und R13 Wasserstoff sind und R12 Alkoxycarbonyl ist.These include compounds of formula B in which R 1 is t-butyl, R 10 is chlorine, R 11 and R 13 are hydrogen and R 12 is alkoxycarbonyl.

In den Verbindungen der Formel A und B kann die Abgangsgruppe Q Wasserstoff sein oder sie ist eine heterocyclische Gruppe

Figure imgb0030
worin R14 eine organische zweiwertige Gruppe ist, die den Ring zu einem 4-7-gliedrigen Ring ergänzt, oder Q ist eine Gruppe -OR15, worin R15 Alkyl, Aryl, Acyl oder ein heterocyclischer Rest ist.In the compounds of formula A and B the leaving group Q can be hydrogen or it is a heterocyclic group
Figure imgb0030
wherein R 14 is an organic divalent group that complements the ring to a 4-7 membered ring, or Q is a group -OR 15 , wherein R 15 is alkyl, aryl, acyl or a heterocyclic radical.

Typische Beispiele für gebräuchliche Gelbkuppler sind die Verbindungen der folgenden Formeln:

Figure imgb0031
Figure imgb0032
Figure imgb0033
Figure imgb0034
Figure imgb0035
Figure imgb0036
Figure imgb0037
Figure imgb0038
Figure imgb0039
Figure imgb0040
Typical examples of common yellow couplers are the compounds of the following formulas:
Figure imgb0031
Figure imgb0032
Figure imgb0033
Figure imgb0034
Figure imgb0035
Figure imgb0036
Figure imgb0037
Figure imgb0038
Figure imgb0039
Figure imgb0040

Weitere Beispiele für Gelbkuppler sind zu finden in den US-A 2,407,210, 2,778,658, 2,875,057, 2,908,513, 2,908,573, 3,227,155, 3,227,550, 3,253,924, 3,265,506, 3,277,155, 3,408,194, 3,341,331, 3,369,895, 3,384,657, 3,415,652, 3,447,928, 3,551,155, 3,582,322, 3,725,072, 3,891,445, 3,933,501, 4,115,121, 4,401,752 und 4,022,620, in den DE-A 1,547,868, 2,057,941, 2,162,899, 2,163,813, 2,213,461, 2,219,917, 2,261,361, 2,261,362, 2,263,875, 2,329,587, 2,414,006 und 2,422,812, in den GB-A 1,425,020 und 1,077,874 und in JP-A-88/123,047 und in EP-A-447,969.Further examples of yellow couplers can be found in US Pat. Nos. 2,407,210, 2,778,658, 2,875,057, 2,908,513, 2,908,573, 3,227,155, 3,227,550, 3,253,924, 3,265,506, 3,277,155, 3,408,194, 3,341,331, 3,369,895, 3,384,657, 3,415,652, 3,422,532, 3,584,357, 3,447,972, 3,547,325,372,052 3,891,445, 3,933,501, 4,115,121, 4,401,752 and 4,022,620, in DE-A 1,547,868, 2,057,941, 2,162,899, 2,163,813, 2,213,461, 2,219,917, 2,261,361, 2,261,362, 2,263,875, 2,329,587, 2,414,006 and 2,422,812 in GB-A and GB 1,042,812,0,04 and 1,077,812 in GB-A and GB-A 1,024, and 1,042,812, 1,420,874 and GB-A 1,024 and 1,422,812 in GB-A and GB-A -A-88 / 123,047 and in EP-A-447,969.

Die Gelbkuppler werden üblicherweise in einer Menge von 0,05-2 Mol und vorzugsweise 0,1-1 Mol pro Mol Silberhalogenid verwendet.The yellow couplers are usually used in an amount of 0.05-2 mol and preferably 0.1-1 mol per mol of silver halide.

Typische und bevorzugte Gelbkuppler entsprechen den Formeln:

Figure imgb0041
Figure imgb0042
Figure imgb0043
Figure imgb0044
Figure imgb0045
Figure imgb0046
Figure imgb0047
Figure imgb0048
Figure imgb0049
Typical and preferred yellow couplers correspond to the formulas:
Figure imgb0041
Figure imgb0042
Figure imgb0043
Figure imgb0044
Figure imgb0045
Figure imgb0046
Figure imgb0047
Figure imgb0048
Figure imgb0049

Magentakuppler können z.B. einfache 1-Aryl-5-pyrazolone sein oder mit 5-gliedrigen Heteroringen kondensierte Pyrazolderivate wie z.B. Imidazopyrazole, Pyrazolopyrazole, Pyrazolotriazole oder Pyrazolotetrazole.Magenta couplers can e.g. simple 1-aryl-5-pyrazolones or pyrazole derivatives condensed with 5-membered hetero rings, e.g. Imidazopyrazole, pyrazolopyrazole, pyrazolotriazole or pyrazolotetrazole.

Eine Gruppe von Magentakupplern sind 5-Pyrazolone der Formel C,

Figure imgb0050
wie sie in der Britischen Patentschrift 2,003,473 beschrieben sind. Darin ist R16 Wasserstoff, Alkyl, Aryl, Alkenyl oder eine heterocyclische Gruppe. R17 ist Wasserstoff, Alkyl Aryl, eine heterocyclische Gruppe, eine Estergruppe, Alkoxygruppe, Alkylthiogruppe, Carboxylgruppe, Arylaminogruppe, Acylaminogruppe, (Thio)-harnstoffgruppe, (Thio)-carbamoylgruppe, Guanidinogruppe oder Sulfonamidogruppe.A group of magenta couplers are 5-pyrazolones of the formula C,
Figure imgb0050
as described in British Patent 2,003,473. Here R 16 is hydrogen, alkyl, aryl, alkenyl or a heterocyclic group. R 17 is hydrogen, alkyl aryl, a heterocyclic group, an ester group, alkoxy group, alkylthio group, carboxyl group, arylamino group, acylamino group, (thio) urea group, (thio) carbamoyl group, guanidino group or sulfonamido group.

Bevorzugt ist R17 eine Gruppe

Figure imgb0051
worin R18 Imino, Acylamino oder Ureido ist, R19 Wasserstoff, Halogen, Alkyl oder Alkoxy ist, R20 Wasserstoff, Alkyl, Acylamino, Carbamoyl, Sulfamoyl, Sulfonamido, Alkoxycarbonyl, Acyloxy oder eine Urethangruppe ist.R 17 is preferably a group
Figure imgb0051
wherein R 18 is imino, acylamino or ureido, R 19 is hydrogen, halogen, alkyl or alkoxy, R 20 is hydrogen, alkyl, acylamino, carbamoyl, sulfamoyl, sulfonamido, alkoxycarbonyl, acyloxy or a urethane group.

Wenn Q' Wasserstoff ist, so ist der Magentakuppler tetraäquivalent in bezug auf das Silberhalogenid.If Q 'is hydrogen, the magenta coupler is tetra-equivalent to that Silver halide.

Typische Beispiele für diesen Typ von Magentakupplern sind Verbindungen der Formel

Figure imgb0052
worin R20 die oben genannten Bedeutungen hat, und Q', wie oben beschrieben, eine Abgangsgruppe ist. Diese Verbindungen liegen bevorzugt im erfindungsgemässen Material vor.Typical examples of this type of magenta coupler are compounds of the formula
Figure imgb0052
wherein R 20 has the meanings given above, and Q ', as described above, is a leaving group. These compounds are preferably present in the material according to the invention.

Weitere Beispiele solcher tetraäquivalenter Magentakuppler sind zu finden in den US-A 2,983,608, 3,061,432, 3,062,653, 3,127,269, 3,152,896, 3,311,476, 3,419,391, 3,519,429, 3,558,319, 3,582,322, 3,615,506, 3,684,514, 3,834,908, 3,888,680, 3,891,445, 3,907,571, 3,928,044, 3,930,861, 3,930,866 und 3,933,500 und in JP-A-89/309,058.Further examples of such tetra-equivalent magenta couplers can be found in US Pat and 3,933,500 and in JP-A-89 / 309,058.

Wenn Q' in Formel C nicht Wasserstoff ist sondern eine Gruppe, die bei der Reaktion mit dem oxidierten Entwickler eliminiert wird, so handelt es sich um einen diäquivalenten Magentakuppler. Q kann in diesem Fall z.B. Halogen oder eine über O, S oder N an den Pyrazolring gebundenen Gruppe sein. Solche diäquivalenten Kuppler ergeben eine höhere Farbdichte und sind reaktiver gegenüber dem oxidierten Entwickler als die entsprechenden tetraäquivalenten Magentakuppler.If Q 'in formula C is not hydrogen but a group that is eliminated in the reaction with the oxidized developer, then it is a equivalent magenta coupler. In this case, Q can e.g. Halogen or a group bonded to the pyrazole ring via O, S or N. Such equivalent couplers result in a higher color density and are more reactive towards the oxidized developer than the corresponding tetra-equivalent magenta couplers.

Beispiele für diäquivalente Magentakuppler sind beschrieben in den US-A 3,006,579, 3,419,391, 3,311,476, 3,432,521, 3,214,437, 4,032,346, 3,701,783, 4,351,897, 3,227,554, in den EP-A-133,503, DE-A-2,944,601, JP-A-78/34044, 74/53435, 74/53436, 75/53372 und 75/122935.Examples of equivalent magenta couplers are described in US-A 3,006,579, 3,419,391, 3,311,476, 3,432,521, 3,214,437, 4,032,346, 3,701,783, 4,351,897, 3,227,554, in EP-A-133,503, DE-A-2,944,601, JP-A-78/34044 , 74/53435, 74/53436, 75/53372 and 75/122935.

Typische und bevorzugte Magentakuppler entsprechen der Formeln

Figure imgb0053
Figure imgb0054
Figure imgb0055
Figure imgb0056
Figure imgb0057
Typical and preferred magenta couplers correspond to the formulas
Figure imgb0053
Figure imgb0054
Figure imgb0055
Figure imgb0056
Figure imgb0057

Ueber ein zweiwertiges Q' können 2 Pyrazolonringe verknüpft werden und man erhält dann sogenannte Bis-Kuppler. Solche sind z.B. beschrieben in den US-A-2,632,702, US-A-2,618,864, GB-A-968,461, GB-A-786,859, JP-A-76/37646, 59/4086, 69/16110, 69/26589, 74/37854 und 74/29638. Bevorzugt ist Y eine O-Alkoxyarylthio-Gruppe.Two pyrazolone rings can be linked via a divalent Q 'and so-called bis couplers are then obtained. Such are e.g. described in US-A-2,632,702, US-A-2,618,864, GB-A-968,461, GB-A-786,859, JP-A-76/37646, 59/4086, 69/16110, 69/26589, 74/37854 and 74/29638. Y is preferably an O-alkoxyarylthio group.

Wie vorstehend erwähnt, können als Magentakuppler auch mit 5-gliedrigen Heterocyclen kondensierte Pyrazole - sogenannte Pyrazoloazole - verwendet werden. Deren Vorteile gegenüber einfachen Pyrazolen ist, dass sie Farben von grösserer Formalin-Beständigkeit und reineren Absorptionsspektren aufweisen.As mentioned above, pyrazoles - so-called pyrazoloazoles - condensed with 5-membered heterocycles can also be used as magenta couplers. Their advantages over simple pyrazoles is that they have colors with greater formalin resistance and purer absorption spectra.

Magentakuppler vom Pyrazoloazoltyp, welche ebenfalls bevorzugt sind, können durch die Formeln

Figure imgb0058
dargestellt werden, worin R1 Wasserstoff oder ein Substituent ist, Z die zur Vervollständigung eines 5-gliedrigen Ringes mit 2 oder 3 Stickstoffatomen notwendigen nicht-metallischen Atome darstellt, wobei dieser Ring substituiert sein kann, und Q Wasserstoff oder eine Abgangsgruppe ist.Pyrazoloazole type magenta couplers, which are also preferred, can be represented by the formulas
Figure imgb0058
in which R 1 is hydrogen or a substituent, Z represents the non-metallic atoms necessary to complete a 5-membered ring with 2 or 3 nitrogen atoms, which ring may be substituted, and Q is hydrogen or a leaving group.

Bevorzugt hiervon sind Magentakuppler der Formeln

Figure imgb0059
R11, R12 und R13 bedeuten unabhängig voneinander beispielsweise Wasserstoff, Halogen, eine Gruppe der Formel -CR3, worin die Reste R unabhängig voneinander Wasserstoff oder Alkyl sind, Aryl, Heterocyclyl, Cyano, Hydroxy, Nitro, Carboxyl, Amino, Alkoxy, Aryloxy, Acylamino, Alkylamino, Anilino, Ureido, Sulfamoylamino, Alkylthio, Arylthio, Alkoxycarbonylamino, Sulfonamido, Carbamoyl, Sulfamoyl, Sulfonyl, Alkoxycarbonyl, Heterocyclyl-oxy, Azo, Acyloxy, Carbamoyloxy, Silyloxy, Aryloxycarbonylamino, Imido, heterocyclische Ring-thio, Sulfinyl, Phosphonyl, Aryloxycarbonyl, Acyl oder Azolyl, und vorzugsweise Wasserstoff; Halogen (z.B. Chlor, Brom), eine Gruppe der Formel -CR3, worin die Reste R unabhängig voneinander Wasserstoff oder Alkyl sind, Aralkyl, Alkenyl, Alkinyl, Cycloalkyl oder Cycloalkenyl und besonders bevorzugt Methyl, Ethyl, Propyl, Isopropyl, t-Butyl, Tridecyl, 2-Methansulfonylethyl, 3-(3-Pentadecylphenoxy)propyl, 3-(4-(2-(4-(4-Hydroxyphenylsulfonyl)phenoxy)dodecanamido)phenyl)propyl, 2-Ethoxytridecyl, Trifluoromethyl, Cyclopentyl, 3-(2,4-Di-t-Amylphenoxy)propyl); Aryl (z.B. Phenyl, 4-t-Butylphenyl, 2,4-Di-t-amylphenyl, 4-Tetradecaneamidophenyl); Heterocyclyl (z.B. 2-Furyl, 2-Thienyl, 2-Pyrimidinyl, 2-Benzothiazolyl); Cyano; Hydroxy, Nitro; Carboxy; Amino; Alkoxy (z.B. Methoxy, Ethoxy, 2-Methoxyethoxy; 2-Dodecylethoxy, 2-Methansulfonylethoxy); Aryloxy (z.B. Phenoxy, 2-Methylphenoxy, 4-t-Butylphenoxy , 3-Nitrophenoxy, 3-t-Butyloxycarbamoylphenoxy, 3-Methoxycarbamoyl); Acylamino (z.B. Acetoamido, Benzamido, Tetradecanamido, 2-(2,4-Di-t-amylphenoxy)-butanamido, 4-(3-t-Butyl-4-hydroxyphenoxy)butanamido, 2-(4-(4-Hydroxyphenylsulfonyl)phenoxy)decanamido); Methylbutylamino); Anilino (z.B. Phenylamino, 2-Chloranilino, 2-Chloro-5-tetradecanaminoanilino, 2-Chloro-5-dodecyloxycarbonylanilino, N-Acetylanilino, 2-Chloro-5-(alpha-(3-t-butyl-4-hydroxyphenoxy)dodecanamido-anilino); Ureido (z.B. Phenylureido, Methylureido, N,N-Dibutylureido); Sulfamoylamino (z.B. N,N-Dipropylsulfamoylamino, N-Methyl-N-decylsulfamoylamino); Alkylthio (z.B. Methylthio, Octylthio, Tetradecylthio, 2-Phenoxyethylthio, 3-Phenoxypropylthio, 3-(4-t-Butylphenoxy)propylthio); Arylthio (z.B. Phenylthio, 2-Butoxy-5-t-octylphenylthio, 3-Pentadecylphenylthio, 2-Carboxyphenylthio, 4-Tetradecanamidophenylthio); Alkoxycarbonylamino (z.B. Methoxycarbonylamino, Tetradecyloxycarbonylamino); Sulfonamido (z.B. Methansulfonamido, Hexadecansulfonamido, Benzolsulfonamido, p-Toluolsulfonamido, Octadecansulfonamido, 2-Methyloxy-5-t-butylbenzolsulfonamido); Carbamoyl (z.B. N-Ethylcarbamoyl, N,N-Dibutylcarbamoyl, N-(2-Dodecyloxyethyl)carbamoyl, N-Methyl-N-dodecylcarbamoyl, N-(3-(2,4-Di-t-Amylphenoxy)propyl)carbamoyl); Sulfamoyl (z.B. N-Ethylsulfamoyl, N,N-Dipropylsulfamoyl, N-2(-Dodecyloxyethyl)sulfamoyl, N-Ethyl-N-dodecylsulfamoyl, N,N-Diethylsulfamoyl); Sulfonyl (z.B. Methansulfonyl, Octansulfonyl, Benzolsulfonyl, Toluolsulfonyl); Alkoxycarbonyl (z.B. Methoxycarbonyl, Butoxycarbonyl, Dodecyloxycarbonyl, Octadecyloxycarbonyl); heterocyclische Ringoxy (z.B. 1-Phenyltetrazol-5-oxy, 2-Tetrahydropyranyloxy); Azo (z.B. Phenylazo, 4-Methoxyphenylazo, 4-Pivaloylaminophenylazo, 2-Hydroxy-4-propanoylphenylazo); Acyloxy (z.B. Acetoxy); Carbamoyloxy (z.B. N-Methylcarbamoyloxy, N-Phenylcarbamoyloxy); Silyloxy (z.B. Trimethylsilyloxy, Dibutylmethylsilyloxy); Aryloxycarbonylamino (z.B. Phenoxycarbonylamino); Imido (z.B. N-Succinimido, N-Phthalimido, 3-Octadecenylsuccinimido); heterocyclische Ring-thio (z.B. 2-Benzothiazolylthio, 2,4-Diphenyloxy- 1,3,5-triazol-6-thio, 2-Pyridylthio); Sulfinyl (z.B. Dodecansulfinyl, 3-Pentadecylphenylsulfinyl, 3-Phenoxypropylsulfinyl); Phosphonyl (z.B. Phenoxyphosphonyl, Octyloxyphosphonyl, Phenylphosphonyl); Aryloxycarbonyl (z.B. Phenoxycarbonyl); Acyl (z.B. Acetyl, 3-Phenylpropanoyl, Benzoyl, 4-Dodecyloxybenzoyl); Azolyl (z.B. Imidazolyl, Pyrazolyl, 3-Chloro-pyrazol-1-yl).Of these, magenta couplers of the formulas are preferred
Figure imgb0059
R 11 , R 12 and R 13 independently of one another are, for example, hydrogen, halogen, a group of the formula —CR 3 , in which the radicals R are independently of one another hydrogen or alkyl, aryl, heterocyclyl, cyano, hydroxy, nitro, carboxyl, amino, alkoxy , Aryloxy, acylamino, alkylamino, anilino, ureido, sulfamoylamino, alkylthio, arylthio, alkoxycarbonylamino, sulfonamido, carbamoyl, sulfamoyl, sulfonyl, alkoxycarbonyl, heterocyclyloxy, azo, acyloxy, carbamoyloxy, silylamino, imylyloxy, aryloxy, aryloxy, aryloxy, aryloxy, aryloxy, aryloxy, aryloxy, aryloxy, aryloxy Sulfinyl, phosphonyl, aryloxycarbonyl, acyl or azolyl, and preferably hydrogen; Halogen (e.g. chlorine, bromine), a group of the formula -CR 3 , in which the radicals R are independently hydrogen or alkyl, aralkyl, alkenyl, alkynyl, cycloalkyl or cycloalkenyl and particularly preferably methyl, ethyl, propyl, isopropyl, t-butyl , Tridecyl, 2-methanesulfonylethyl, 3- (3-pentadecylphenoxy) propyl, 3- (4- (2- (4- (4-hydroxyphenylsulfonyl) phenoxy) dodecanamido) phenyl) propyl, 2-ethoxytridecyl, trifluoromethyl, cyclopentyl, 3- (2,4-di-t-amylphenoxy) propyl); Aryl (e.g. phenyl, 4-t-butylphenyl, 2,4-di-t-amylphenyl, 4-tetradecaneamidophenyl); Heterocyclyl (e.g. 2-furyl, 2-thienyl, 2-pyrimidinyl, 2-benzothiazolyl); Cyano; Hydroxy, nitro; Carboxy; Amino; Alkoxy (e.g. methoxy, ethoxy, 2-methoxyethoxy; 2-dodecylethoxy, 2-methanesulfonylethoxy); Aryloxy (e.g. phenoxy, 2-methylphenoxy, 4-t-butylphenoxy, 3-nitrophenoxy, 3-t-butyloxycarbamoylphenoxy, 3-methoxycarbamoyl); Acylamino (e.g. acetoamido, benzamido, tetradecanamido, 2- (2,4-di-t-amylphenoxy) butanamido, 4- (3-t-butyl-4-hydroxyphenoxy) butanamido, 2- (4- (4-hydroxyphenylsulfonyl) phenoxy) decanamido); Methylbutylamino); Anilino (e.g. phenylamino, 2-chloroanilino, 2-chloro-5-tetradecanaminoanilino, 2-chloro-5-dodecyloxycarbonylanilino, N-acetylanilino, 2-chloro-5- (alpha- (3-t-butyl-4-hydroxyphenoxy) dodecanamido -anilino); ureido (e.g. phenylureido, methylureido, N, N-dibutylureido); sulfamoylamino (e.g. N, N-dipropylsulfamoylamino, N-methyl-N-decylsulfamoylamino); alkylthio (e.g. methylthio, octylthio, tetradecylthio, 3-phenoxyethyl -Phenoxypropylthio, 3- (4-t-butylphenoxy) propylthio); arylthio (e.g. phenylthio, 2-butoxy-5-t-octylphenylthio, 3-pentadecylphenylthio, 2-carboxyphenylthio, 4-tetradecanamidophenylthio); Alkoxycarbonylamino (e.g. methoxycarbonylamino, tetradecyloxycarbonylamino); Sulfonamido (e.g. methanesulfonamido, hexadecanesulfonamido, benzenesulfonamido, p-toluenesulfonamido, octadecanesulfonamido, 2-methyloxy-5-t-butylbenzenesulfonamido); Carbamoyl (e.g. N-ethylcarbamoyl, N, N-dibutylcarbamoyl, N- (2-dodecyloxyethyl) carbamoyl, N-methyl-N-dodecylcarbamoyl, N- (3- (2,4-di-t-amylphenoxy) propyl) carbamoyl) ; Sulfamoyl (e.g. N-ethylsulfamoyl, N, N-dipropylsulfamoyl, N-2 (-dodecyloxyethyl) sulfamoyl, N-ethyl-N-dodecylsulfamoyl, N, N-diethylsulfamoyl); Sulfonyl (e.g. methanesulfonyl, octanesulfonyl, benzenesulfonyl, toluenesulfonyl); Alkoxycarbonyl (e.g. methoxycarbonyl, butoxycarbonyl, dodecyloxycarbonyl, octadecyloxycarbonyl); heterocyclic ringoxy (e.g. 1-phenyltetrazole-5-oxy, 2-tetrahydropyranyloxy); Azo (e.g. phenylazo, 4-methoxyphenylazo, 4-pivaloylaminophenylazo, 2-hydroxy-4-propanoylphenylazo); Acyloxy (e.g. acetoxy); Carbamoyloxy (e.g. N-methylcarbamoyloxy, N-phenylcarbamoyloxy); Silyloxy (e.g. trimethylsilyloxy, dibutylmethylsilyloxy); Aryloxycarbonylamino (e.g. phenoxycarbonylamino); Imido (e.g. N-succinimido, N-phthalimido, 3-octadecenylsuccinimido); heterocyclic ring thio (e.g. 2-benzothiazolylthio, 2,4-diphenyloxy-1,3,5-triazol-6-thio, 2-pyridylthio); Sulfinyl (e.g. dodecanesulfinyl, 3-pentadecylphenylsulfinyl, 3-phenoxypropylsulfinyl); Phosphonyl (e.g. phenoxyphosphonyl, octyloxyphosphonyl, phenylphosphonyl); Aryloxycarbonyl (e.g. phenoxycarbonyl); Acyl (e.g. acetyl, 3-phenylpropanoyl, benzoyl, 4-dodecyloxybenzoyl); Azolyl (e.g. imidazolyl, pyrazolyl, 3-chloropyrazol-1-yl).

Diese Substituenten sind gegebenenfalls weiter substituiert, beispielsweise durch Halogen oder durch einen über ein C-, O-, N- oder S-Atom gebundenen organischen Rest.These substituents are optionally further substituted, for example by halogen or by an organic radical bonded via a C, O, N or S atom.

Die bevorzugten Gruppen R11 sind Alkyl, Aryl, Alkoxy, Aryloxy, Alkylthio, Ureido, Urethan und Acylaminogruppen.The preferred groups R 11 are alkyl, aryl, alkoxy, aryloxy, alkylthio, ureido, urethane and acylamino groups.

R12 kann die Bedeutung von R11 besitzen und ist vorzugsweise Wasserstoff, Alkyl, Aryl, ein heterocyclischer Ring, Alkoxycarbonyl, Carbamoyl, Sulfamoyl, Sulfinyl, Acyl oder Cyano.R 12 can have the meaning of R 11 and is preferably hydrogen, alkyl, aryl, a heterocyclic ring, alkoxycarbonyl, carbamoyl, sulfamoyl, sulfinyl, acyl or cyano.

R13 kann die Bedeutung von R11 haben und ist vorzugsweise Wasserstoff, Alkyl,Aryl, Heterocyclic, Alkoxy, Aryloxy, Alkylthio, Arylthio, Alkoxycarbonyl, Carbamoyl oder Acyl, vorzugsweise Alkyl, Aryl, Heterocyclic, Alkylthio oder Arylthio.R 13 can have the meaning of R 11 and is preferably hydrogen, alkyl, aryl, heterocyclic, alkoxy, aryloxy, alkylthio, arylthio, alkoxycarbonyl, carbamoyl or acyl, preferably alkyl, aryl, heterocyclic, alkylthio or arylthio.

Q ist Wasserstoff oder eine Abgangsgruppe wie Halogen, Alkoxy, Aryloxy, Acyloxy, Alkyl- oder Arylsulfonyloxy, Acylamino, Alkyl- oder Aryl-sulfonamido, Alkoxycarbonyloxy, Aryloxycarbonyloxy, Alkyl-, Aryl- oder Heterocyclyl-S-Carbamoylamino, ein 5-oder 6-gliedriger stickstoffhaltiger heterocyclischer Rest, Imido und Arylazo. Diese Gruppen sind gegebenenfalls wie für R11 gezeigt weiter substituiert.Q is hydrogen or a leaving group such as halogen, alkoxy, aryloxy, acyloxy, Alkyl- or arylsulfonyloxy, acylamino, alkyl- or aryl-sulfonamido, alkoxycarbonyloxy, aryloxycarbonyloxy, alkyl-, aryl- or heterocyclyl-S-carbamoylamino, a 5- or 6-membered nitrogen-containing heterocyclic radical, imido and arylazo. These groups are optionally further substituted as shown for R 11 .

Vorzugsweise ist Q Halogen (z.B. Fluor, Chlor, Brom); Alkoxy (z.B. Ethoxy, Dodecyloxy, Methoxyethylcarbamoylmethoxy, Carboxypropyloxy, Methylsulfonylethoxy, Ethoxycarbonylmethoxy); Aryloxy (z.B. 4-Methylphenoxy, 4-Chlorphenoxy, 4-Methoxyphenoxy, 4-Carboxyphenoxy, 3-Ethoxycarboxyphenoxy, 3-Acetylaminophenoxy, 2-Carboxyphenoxy); Acyloxy (z.B. Acetoxy, Tetradecanoyloxy, Benzoyloxy); Alkyl- oder Aryl-sulfonyloxy (z.B. Methansulfonyloxy, Toluolsulfonyloxy); Acylamino (z.B. Dichloracetylamino, Heptafluorobutyrylamino); Alkyl- oder Arylsulfonamido (z.B. Methanesulfonamido, Trifluoromethansulfonamido, p-Toluolsulfonylamido); Alkoxycarbonyloxy (z.B. Ethoxycarbonyloxy, Benzyloxycarbonyloxy); Aryloxycarbonyloxy (z.B. Phenoxycarbonyloxy); Alkyl-, Aryl- oder Heterocyclyl-S- (z.B. Dodecylthio, 1-Carboxydodecylthio, Phenylthio, 2-Butoxy-5-t-octylphenylthio, Tetrazolylthio); Carbamoylamino (z.B. N-Methylcarbamoylamino, N-Phenylcarbamoylamino); 5- oder 6-gliedriger stickstoffhaltiger Ring (z.B. Imidazolyl, Pyrazolyl, Triazolyl, Tetrazolyl, 1,2-Dihydro-2-oxo-1-pyridyl); Imido (z.B. Succinimido, Hydantoinyl); Arylazo (z.B. Phenylazo, 4-Methoxyphenylazo).Preferably Q is halogen (e.g. fluorine, chlorine, bromine); Alkoxy (e.g. ethoxy, dodecyloxy, methoxyethylcarbamoylmethoxy, carboxypropyloxy, methylsulfonylethoxy, ethoxycarbonylmethoxy); Aryloxy (e.g. 4-methylphenoxy, 4-chlorophenoxy, 4-methoxyphenoxy, 4-carboxyphenoxy, 3-ethoxycarboxyphenoxy, 3-acetylaminophenoxy, 2-carboxyphenoxy); Acyloxy (e.g. acetoxy, tetradecanoyloxy, benzoyloxy); Alkyl or aryl sulfonyloxy (e.g. methanesulfonyloxy, toluenesulfonyloxy); Acylamino (e.g. dichloroacetylamino, heptafluorobutyrylamino); Alkyl or arylsulfonamido (e.g. methanesulfonamido, trifluoromethanesulfonamido, p-toluenesulfonylamido); Alkoxycarbonyloxy (e.g. ethoxycarbonyloxy, benzyloxycarbonyloxy); Aryloxycarbonyloxy (e.g. phenoxycarbonyloxy); Alkyl, aryl or heterocyclyl-S- (e.g. dodecylthio, 1-carboxydodecylthio, phenylthio, 2-butoxy-5-t-octylphenylthio, tetrazolylthio); Carbamoylamino (e.g. N-methylcarbamoylamino, N-phenylcarbamoylamino); 5- or 6-membered nitrogen-containing ring (e.g. imidazolyl, pyrazolyl, triazolyl, tetrazolyl, 1,2-dihydro-2-oxo-1-pyridyl); Imido (e.g. succinimido, hydantoinyl); Arylazo (e.g. phenylazo, 4-methoxyphenylazo).

Q kann auch entsprechende Bisverbindungen bilden durch Kondensation von 4 äquivalenten Kuppler mit einem Aldehyd oder Keton. Des weiteren kann Q photographisch wirksame Gruppen enthalten wie Entwicklungsinhibitoren oder Entwicklungsbeschleuniger. Vorzugsweise ist Q Halogen, Alkoxy, Aryloxy, Alkyl-, Aryl-thio, oder eine 5- oder 6-gliedrige stickstoffhaltige heterocyclische Gruppe, die an den Ort der Kupplung über ein Stickstoffatom gebunden ist.Q can also form corresponding bis-compounds by condensing 4 equivalent couplers with an aldehyde or ketone. Furthermore, Q can contain photographically active groups such as development inhibitors or development accelerators. Q is preferably halogen, alkoxy, aryloxy, alkyl, arylthio, or a 5- or 6-membered nitrogen-containing heterocyclic group which is bonded to the coupling site via a nitrogen atom.

Pyrazolo-tetrazole sind beschrieben in der JP-A-85/33552; Pyrazolo-pyrazole in der JP-A-85/43,695; Pyrazolo-imidazole in den JP-A-85/35732, JP-A-86/18949 und US-A-4,500,630; Pyrazolo-triazole in den JP-A-85/186,567, JP-A-86/47957, JP-A-85/215,687, JP-A-85/197,688, JP-A-85/172,982, EP-A-119,860, EP-A-173,256, EP-A-178,789, EP-A-178,788 und in Research Disclosure 84/24,624.Pyrazolo-tetrazoles are described in JP-A-85/33552; Pyrazolo-pyrazole in JP-A-85 / 43,695; Pyrazolo-imidazoles in JP-A-85/35732, JP-A-86/18949 and US-A-4,500,630; Pyrazolo-triazoles in JP-A-85 / 186,567, JP-A-86/47957, JP-A-85 / 215,687, JP-A-85 / 197,688, JP-A-85 / 172,982, EP-A-119,860 , EP-A-173,256, EP-A-178,789, EP-A-178,788 and in Research Disclosure 84 / 24,624.

Weitere Pyrazoloazol-Magentakuppler sind beschrieben in: JP-A-86/28,947, JP-A-85/140,241, JP-A-85/262,160, JP-A-85/213,937, JP-A-87/278,552, JP-A-87/279,340, JP-A-88/100,457, EP-A-177,765, EP-A-176,804, EP-A-170,164, EP-A-164,130, EP-A-178,794, DE-A-3,516,996, DE-A-3,508,766 und Research Disclosure 81/20919, 84/24531 und 85/25758.Further pyrazoloazole magenta couplers are described in: JP-A-86 / 28,947, JP-A-85 / 140,241, JP-A-85 / 262,160, JP-A-85 / 213,937, JP-A-87 / 278,552, JP-A-87 / 279,340, JP-A-88 / 100,457, EP-A-177,765, EP-A-176,804, EP-A-170,164, EP-A-164,130, EP-A-178,794, DE-A- 3,516,996, DE-A-3,508,766 and Research Disclosure 81/20919, 84/24531 and 85/25758.

Geeignete Beispiele solcher Kuppler sind:

Figure imgb0060
Figure imgb0061
Figure imgb0062
Figure imgb0063
Figure imgb0064
Figure imgb0065
Figure imgb0066
Figure imgb0067
Figure imgb0068
Figure imgb0069
Figure imgb0070
Figure imgb0071
Figure imgb0072
Figure imgb0073
Figure imgb0074
Figure imgb0075
Figure imgb0076
Figure imgb0077
Figure imgb0078
Figure imgb0079
Figure imgb0080
Figure imgb0081
Figure imgb0082
Figure imgb0083
Figure imgb0084
Figure imgb0085
Figure imgb0086
Figure imgb0087
Figure imgb0088
Figure imgb0089
Figure imgb0090
Figure imgb0091
Figure imgb0092
Figure imgb0093
Figure imgb0094
Figure imgb0095
Figure imgb0096
Figure imgb0097
Figure imgb0098
Figure imgb0099
Figure imgb0100
Figure imgb0101
Figure imgb0102
Figure imgb0103
Figure imgb0104
Figure imgb0105
Figure imgb0106
Figure imgb0107
Figure imgb0108
Figure imgb0109
Figure imgb0110
Figure imgb0111
Figure imgb0112
Figure imgb0113
Figure imgb0114
Figure imgb0115
Figure imgb0116
Figure imgb0117
Figure imgb0118
Figure imgb0119
Figure imgb0120
Suitable examples of such couplers are:
Figure imgb0060
Figure imgb0061
Figure imgb0062
Figure imgb0063
Figure imgb0064
Figure imgb0065
Figure imgb0066
Figure imgb0067
Figure imgb0068
Figure imgb0069
Figure imgb0070
Figure imgb0071
Figure imgb0072
Figure imgb0073
Figure imgb0074
Figure imgb0075
Figure imgb0076
Figure imgb0077
Figure imgb0078
Figure imgb0079
Figure imgb0080
Figure imgb0081
Figure imgb0082
Figure imgb0083
Figure imgb0084
Figure imgb0085
Figure imgb0086
Figure imgb0087
Figure imgb0088
Figure imgb0089
Figure imgb0090
Figure imgb0091
Figure imgb0092
Figure imgb0093
Figure imgb0094
Figure imgb0095
Figure imgb0096
Figure imgb0097
Figure imgb0098
Figure imgb0099
Figure imgb0100
Figure imgb0101
Figure imgb0102
Figure imgb0103
Figure imgb0104
Figure imgb0105
Figure imgb0106
Figure imgb0107
Figure imgb0108
Figure imgb0109
Figure imgb0110
Figure imgb0111
Figure imgb0112
Figure imgb0113
Figure imgb0114
Figure imgb0115
Figure imgb0116
Figure imgb0117
Figure imgb0118
Figure imgb0119
Figure imgb0120

Cyankuppler können z.B. Derivate von Phenol, von 1-Naphthol oder von Pyrazolochinazolon sein. Bevorzugt sind Strukturen der Formel E,

Figure imgb0121
worin R21, R22, R23 und R24 Wasserstoff, Halogen, Alkyl, Carbamoyl, Amino, Sulfonamido, Phosphoramido oder Ureido sind. R21 ist vorzugsweise H oder Cl, R22 ist vorzugsweise eine Alkyl- oder Aminogruppe. R23 ist vorzugsweise eine Aminogruppe und R24 ist vorzugsweise Wasserstoff. Q" ist Wasserstoff oder eine Abgangsgruppe, die bei der Reaktion mit den oxidierten Entwickler abgespalten wird. Eine ausführliche Aufzählung von Cyankupplern ist im US-A-4,456,681 zu finden.Cyan couplers can be, for example, derivatives of phenol, 1-naphthol or pyrazoloquinazolone. Structures of the formula E are preferred,
Figure imgb0121
wherein R 21 , R 22 , R 23 and R 24 are hydrogen, halogen, alkyl, carbamoyl, amino, sulfonamido, phosphoramido or ureido. R 21 is preferably H or Cl, R 22 is preferably an alkyl or amino group. R 23 is preferably an amino group and R 24 is preferably hydrogen. Q "is hydrogen or a leaving group which is split off on reaction with the oxidized developer. A detailed list of cyan couplers can be found in US Pat. No. 4,456,681.

Beispiele von gebräuchlichen Cyankupplern sind die folgenden:

Figure imgb0122
Figure imgb0123
Figure imgb0124
Figure imgb0125
Figure imgb0126
Figure imgb0127
Examples of common cyan couplers are the following:
Figure imgb0122
Figure imgb0123
Figure imgb0124
Figure imgb0125
Figure imgb0126
Figure imgb0127

Weitere Beispiele von Cyankupplern sind in folgenden US-A- zu finden: 2,369,929, 2,423,730, 2,434,272, 2,474,293, 2,521,293, 2,521,908, 2,698,794, 2,706,684, 2,772,162, 2,801,171, 2,895,826, 2,908,573, 3,034,892, 3,046,129, 3,227,550, 3,253,294, 3,311,476, 3,386,301, 3,419,390, 3,458,315, 3,476,560, 3,476,563, 3,516,831, 3,560,212, 3,582,322, 3,583,971, 3,591,383, 3,619,196, 3,632,347, 3,652,286, 3,737,326, 3,758,308, 3,839,044, 3,880,661, 4,004,929, 4,124,396, 4,333,999, 4,463,086, 4,456,681, 4,873,183 und 4,923,791 und in den EP-A-354,549 und EP-A-398,664.Further examples of cyan couplers can be found in the following US-A-: 2,369,929, 2,423,730, 2,434,272, 2,474,293, 2,521,293, 2,521,908, 2,698,794, 2,706,684, 2,772,162, 2,801,171, 2,895,826, 2,908,573, 3,034,892, 3,046,129, 3,294,550, 3,253 3,311,476, 3,386,301, 3,419,390, 3,458,315, 3,476,560, 3,476,563, 3,516,831, 3,560,212, 3,582,322, 3,583,971, 3,591,383, 3,619,196, 3,632,347, 3,652,286, 3,737,326, 3,758,308, 3,839,044, 3,880,661, 4,004,929, 4,124,396, 4,333,999, 4,463,086, 4,456,681, 4,873,183 and 4,923,791 and in EP-A-354,549 and EP-A-398,664.

In der rotempfindlichen Silberhalogenidemulsionsschicht des erfindungsgemässen Materials kommen vorzugsweise Cyankuppler der Formel

Figure imgb0128
und/oder oder Formel
Figure imgb0129
zum Einsatz, worin
Z1 Alkyl, Aryl, Z2 Alkyl, Cycloalkyl, Aryl, eine heterocyclische Gruppe, oder eine Ballastgruppe, Z3 Wasserstoff oder Halogen ist, Z1 und Z3 zusammen einen Ring bilden können, und Z4 Wasserstoff oder eine Abgangsgruppe ist, und Z5 eine Ballastgruppe, Z6 Wasserstoff oder eine Abgangsgruppe und Zr Alkyl ist.In the red-sensitive silver halide emulsion layer of the material according to the invention there are preferably cyan couplers of the formula
Figure imgb0128
and / or or formula
Figure imgb0129
used, in which
Z 1 is alkyl, aryl, Z 2 alkyl, cycloalkyl, aryl, a heterocyclic group or a ballast group, Z 3 is hydrogen or halogen, Z 1 and Z 3 together can form a ring, and Z 4 is hydrogen or a leaving group, and Z 5 is a ballast group, Z 6 is hydrogen or a leaving group and Zr is alkyl.

Die für farbfotographische Materialien üblicherweise verwendeten Farbentwickler sind p-Dialkylaminoaniline. Beispiele hierfür sind 4-Amino-N,N-diethylanilin, 3-Methyl-4 4-amino-N,N-diethylanilin, 4-Amino-N-ethyl-N-α-hydroxyethylanilin, 3-Methyl-4-amino-N-ethyl-N-α-hydroxyethylanilin, 3-Methyl-4-amino-N-ethyl-N-α-hydroxyethylanilin, 3-Methyl-4-amino-N-ethyl-N-α-methansulphonamidoethylanilin, 3-Methyl-4-amino-N-ethyl-N-α-methoxyethyl-anilin, 3-α-Methansulphonamidoethyl-4-amino-N,N-diethylanilin, 3-Methoxy-4-amino-N-ethyl-N-α-hydroxyethylanilin, 3-Methoxy-4-amino-N-ethyl-N-α-methoxyethylanilin, 3-Acetamido-4-amino-N,N-diethylanilin, 4-Amino-N,N-dimethylanilin, N-Ethyl-N-α-[α'-(α"-methoxyethoxy)ethoxy]ethyl-3-methyl-4-aminoanilin, N-Ethyl-N-α-(α'-methoxyethoxy)ethyl-3-methyl-4-aminoanilin, sowie die Salze solcher Verbindungen, wie z.B. Sulfate, Hydrochloride oder Toluolsulfonate.The color developers commonly used for color photographic materials are p-dialkylaminoanilines. Examples include 4-amino-N, N-diethylaniline, 3-methyl-4, 4-amino-N, N-diethylaniline, 4-amino-N-ethyl-N-α-hydroxyethylaniline, 3-methyl-4-amino- N-ethyl-N-α-hydroxyethylaniline, 3-methyl-4-amino-N-ethyl-N-α-hydroxyethylaniline, 3-methyl-4-amino-N-ethyl-N-α-methanesulphonamidoethylaniline, 3-methyl 4-amino-N-ethyl-N-α-methoxyethyl-aniline, 3-α-methanesulphonamidoethyl-4-amino-N, N-diethylaniline, 3-methoxy-4-amino-N-ethyl-N-α-hydroxyethylaniline, 3-methoxy-4-amino-N-ethyl-N-α-methoxyethylaniline, 3-acetamido-4-amino-N, N-diethylaniline, 4-amino-N, N-dimethylaniline, N-ethyl-N-α- [α '- (α "-methoxyethoxy) ethoxy] ethyl-3-methyl-4-aminoaniline, N-ethyl-N-α- (α '-methoxyethoxy) ethyl-3-methyl-4-aminoaniline, and the salts of such compounds, such as sulfates, hydrochlorides or toluenesulfonates.

Die erfindungsgemäss verwendeten UV-Absorber der Formel (I) und (III) können allein oder zusammen mit dem Farbkuppler und gegebenenfalls weiteren Zusätzen in das farbphotographische Material eingearbeitet werden, indem man sie in hochsiedenden organischen Lösungsmitteln vorlöst. Vorzugsweise verwendet man Lösungsmittel, die höher als 160°C sieden. Typische Beispiele solcher Lösungsmittel sind die Ester von Phthalsäure, Phosphorsäure, Zitronensäure, Benzoesäure oder von Fettsäuren, sowie Alkylamide und Phenole.The UV absorbers of the formulas (I) and (III) used according to the invention can be incorporated into the color photographic material alone or together with the color coupler and, if appropriate, further additives, by pre-dissolving them in high-boiling organic solvents. Solvents boiling above 160 ° C. are preferably used. Typical examples of such solvents are the esters of phthalic acid, phosphoric acid, citric acid, benzoic acid or of fatty acids, and also alkylamides and phenols.

Meist verwendet man zusätzlich noch ein niedrig siedendes Lösungsmittel, um das Einarbeiten der Zusätze in das farbphotographische Material zu erleichtern. Beispiele für solche Lösungsmittel sind Ester wie z.B. Ethylacetat, Alkohole wie z.B. Butanol, Ketone wie z.B. Methyl-isobutyl-keton, Chlorkohlenwasserstoffe wie z.B. Methylenchlorid, oder Amide wie z.B. Dimethylformamid. Sind die Zusätze selbst flüssig, so kann man sie auch ohne Zuhilfenahme von Lösungsmitteln in das Photomaterial einarbeiten.Usually, a low-boiling solvent is also used to make it easier to incorporate the additives into the color photographic material. Examples of such solvents are esters such as e.g. Ethyl acetate, alcohols such as e.g. Butanol, ketones such as Methyl isobutyl ketone, chlorinated hydrocarbons such as e.g. Methylene chloride, or amides such as e.g. Dimethylformamide. If the additives themselves are liquid, they can also be incorporated into the photo material without the use of solvents.

Die erfindungsgemässen UV-Absorber können gegebenenfalls ohne 0l in der Gelatineschicht dispergiert werden; Research Disclosure 88/296017 und 89/303070.The UV absorbers according to the invention can optionally be dispersed without 0l in the gelatin layer; Research Disclosure 88/296017 and 89/303070.

Weitere Details über verwendbare hochsiedende Lösungsmittel sind in den folgenden Veröffentlichungen zu finden:Further details on usable high-boiling solvents can be found in the following publications:

Phosphate: GB-A-791,219, BE-A-755,248, JP-A-76/76739, 78/27449, 78/218,252, 78/97573, 79/148,133, 82/216,177, 82/93323 und 83/216,177 und EP-A265,296. Phthalate: GB-A-791,219, JP-A-77/98050, 82/93322, 82/216,176, 82/218,251, 83/24321, 83/45699, 84/79888.
Amide: GB-A-791,129, JP-A-76/105,043, 77/13600, 77/61089, 84/189,556, 87/239,149, US-A-928,741, EP-A-270,341, WO 88/00723.
Phenole: GB-A-820,329, FR-A-1,220,657, JP-A-69/69946, 70/3818, 75/123,026, 75/82078, 78/17914, 78/21166, 82/212,114 und 83/45699.
Phosphates: GB-A-791,219, BE-A-755,248, JP-A-76/76739, 78/27449, 78 / 218,252, 78/97573, 79 / 148,133, 82 / 216,177, 82/93323 and 83 / 216,177 and EP-A265,296. Phthalates: GB-A-791,219, JP-A-77/98050, 82/93322, 82 / 216,176, 82 / 218,251, 83/24321, 83/45699, 84/79888.
Amides: GB-A-791,129, JP-A-76 / 105,043, 77/13600, 77/61089, 84 / 189,556, 87 / 239,149, US-A-928,741, EP-A-270,341, WO 88/00723.
Phenols: GB-A-820,329, FR-A-1,220,657, JP-A-69/69946, 70/3818, 75 / 123,026, 75/82078, 78/17914, 78/21166, 82 / 212,114 and 83/45699.

Andere sauerstoffhaltige Verbindungen: US-A-3,748,141, 3,779,765, JP-A-73/75126,
74/101,114, 74/10115, 75/101,625, 76/76740, 77/61089, EP-A-304,810 und BE-A-826,039.
Other oxygen-containing compounds: US-A-3,748,141, 3,779,765, JP-A-73/75126,
74 / 101,114, 74/10115, 75 / 101,625, 76/76740, 77/61089, EP-A-304,810 and BE-A-826,039.

Sonstige Verbindungen: JP-A-72/115,369, 72/130,258, 73/127,521, 73/76592, 77/13193, 77/36294, 79/95233, 91/2,748, 83/105,147 und Research Disclosure 82/21918.Other compounds: JP-A-72 / 115,369, 72 / 130,258, 73 / 127,521, 73/76592, 77/13193, 77/36294, 79/95233, 91 / 2,748, 83 / 105,147 and Research Disclosure 82/21918.

Die Menge an hochsiedendem Lösungsmittel liegt z.B. im Bereich von 50 mg bis 2 g pro m2 Träger, vorzugsweise von 200 mg bis 1 g pro m 2.The amount of high-boiling solvent is, for example, in the range from 50 mg to 2 g per m 2 of carrier, preferably from 200 mg to 1 g per m 2 .

Die photographischen Schichten können ferner Farbschleier-Inhibitoren enthalten. Diese verhindern das Entstehen von Farbschleiern, wie sie beispielsweise durch Reaktion des Kupplers mit unabsichtlich oxidiertem Entwickler oder mit Nebenprodukten des Farbbildungsprozesses entstehen. Solche Farbschleierinhibitoren sind meist Hydrochininderivate, können aber auch Derivate von Aminophenolen, von Gallussäure oder von Ascorbinsäure sein. Typische Beispiele hierfür sind in folgenden Veröffentlichungen zu finden:
US-A-2,360,290, 2,336,327, 2,403,721, 2,418,613, 2,675,314, 2,701,197, 2,704,713, 2,728,659, 2,732,300, 2,735,365; EP-A-124,877, EP-A-277,589, EP-A-338,785; JP-A-75/92988, 75/92989, 75/93928, 75/110,337, 84/5,247 und 77/146,235.
The photographic layers may also contain color fog inhibitors. These prevent the formation of color veils, such as those caused by the reaction of the coupler with inadvertently oxidized developer or with by-products of the color formation process. Such color fog inhibitors are mostly hydroquinine derivatives, but can also be derivatives of aminophenols, gallic acid or ascorbic acid. Typical examples of this can be found in the following publications:
US-A-2,360,290, 2,336,327, 2,403,721, 2,418,613, 2,675,314, 2,701,197, 2,704,713, 2,728,659, 2,732,300, 2,735,365; EP-A-124,877, EP-A-277,589, EP-A-338,785; JP-A-75/92988, 75/92989, 75/93928, 75 / 110,337, 84 / 5,247 and 77 / 146,235.

Die photographischen Schichten können auch sogenannte DIR-Kuppler (DIR bedeutet Development Inhibition Release) enthalten, die mit dem oxidierten Entwickler farblose Verbindungen ergeben. Sie werden zugesetzt zur Verbesserung der Schärfe und der Körnigkeit der Farbbilder.The photographic layers may also be so-called DIR couplers (DIR means D evelopment I nhibition R elease) contain give the colorless compounds with the oxidized developer. They are added to improve the sharpness and graininess of the color images.

Die photographischen Schichten im erfindungsgemässen Material können auch weitere UV-Absorber enthalten. Beispiele für solche UV-Absorber sind Benztriazole, 2-Hydroxybenzophenone, Salicylsäureester, Acrylnitrilderivate oder Thiazoline. Solche UV-Absorber sind z.B. in folgenden Veröffenlichungen näher erläutert: US-A-3,314,794, 3,352,681, 3,705,805, 3,707,375, 4,045,229, 3,700,455, 3,533,794, 3,698,907, 3,705,805, 3,738,837, 3,762,272, 4,163,671, 4,195,999, 4,309,500, 4,431,726, 4,443,543, 4,576,908, 4,749,643, GB-A-1,564,089, EP-A-190,003 und JP-A-71/2784, 81/111,826, 81/27, 146, 88/53,543 und 88/55,542. Bevorzugte UV-Absorber sind Benztriazole, insbesondere 2-(2-Hydroxyphenyl)-benztriazole und vorzugsweise solche der oben gezeigten Formel (III).The photographic layers in the material according to the invention can also contain further UV absorbers. Examples of such UV absorbers are benzotriazoles, 2-hydroxybenzophenones, salicylic acid esters, acrylonitrile derivatives or thiazolines. Such UV absorbers are described in more detail, for example, in the following publications: US Pat. 4,749,643, GB-A-1,564,089, EP-A-190,003 and JP-A-71/2784, 81 / 111,826, 81/27, 146, 88 / 53,543 and 88 / 55,542. Preferred UV absorbers are benzotriazoles, in particular 2- (2-hydroxyphenyl) benzotriazoles and preferably those of the formula (III) shown above.

Die photographischen Schichten können auch phenolische Verbindungen enthalten, die als Lichtschutzmittel für das Farbbild sowie als Mittel gegen Farbschleier wirken. Sie können in einer lichtempfindlichen Schicht (Farbschicht) oder in einer Zwischenschicht enthalten sein, allein oder zusammen mit anderen Additiven. Solche Verbindungen sind z.B. in den folgenden Veröffentlichungen näher beschrieben: US-A-3,700,455, 3,591,381, 3,573,052, 4,030,931, 4,174,220, 4,178, 184, 4,228,235, 4,279,990, 4,346,165, 4,366,226, 4,447,523, 4,528,264, 4,581,326, 4,562,146, 4,559,297, GB-A-1,309,277, 1,547,302, 2,023,862, 2,135,788, 2,139,370, 2,156,091; DE-A-2,301,060, 2,347,708, 2,526,468, 2,621,203, 3,323,448; DD-A-200,691, 214,468; EP-A-106,799, 113,124, 125,522, 159,912, 161,577, 164,030, 167,762, 176,845, 246,766, 320,776; JP-A-74/134,326, 76/127,730, 76/30462, 77/3822, 77/154,632, 78/10842, 79/48535, 79/70830, 79/73032, 79/147,038, 79/154,325, 79/155,836, 82/142,638, 83/224,353, 84/5246, 84/72443, 84/87456, 84/192,246, 84/192,247, 84/204,039, 84/204,040, 84/212,837, 84/220,733, 84/222,836, 84/228,249, 86/2540, 86/8843, 86/18835, 86/18836, 87/11456, 87/42245, 87/62157, 86/6652, 89/137,258 sowie in Research Disclosure 79/17804.The photographic layers can also contain phenolic compounds which act as light stabilizers for the color image and as agents against color fog. They can be contained in a light-sensitive layer (color layer) or in an intermediate layer, alone or together with other additives. Such connections are e.g. described in more detail in the following publications: US-A-3,700,455, 3,591,381, 3,573,052, 4,030,931, 4,174,220, 4,178, 184, 4,228,235, 4,279,990, 4,346,165, 4,366,226, 4,447,523, 4,528,264, 4,581,326, 4,562,146, 4,559,297, GB-A-1,302,277 , 2,023,862, 2,135,788, 2,139,370, 2,156,091; DE-A-2,301,060, 2,347,708, 2,526,468, 2,621,203, 3,323,448; DD-A-200,691, 214,468; EP-A-106,799, 113,124, 125,522, 159,912, 161,577, 164,030, 167,762, 176,845, 246,766, 320,776; JP-A-74 / 134,326, 76 / 127,730, 76/30462, 77/3822, 77 / 154,632, 78/10842, 79/48535, 79/70830, 79/73032, 79 / 147,038, 79 / 154,325, 79 / 155.836, 82 / 142.638, 83 / 224.353, 84/5246, 84/72443, 84/87456, 84 / 192.246, 84 / 192.247, 84 / 204.039, 84 / 204.040, 84 / 212.837, 84 / 220.733, 84 / 222.836, 84 / 228,249, 86/2540, 86/8843, 86/18835, 86/18836, 87/11456, 87/42245, 87/62157, 86/6652, 89 / 137,258 and in Research Disclosure 79/17804.

Die photographischen Schichten können auch gewisse Phosphor-III-Verbindungen, insbesondere Phosphite und Phosponite, enthalten. Diese fungieren als Lichtschutzmittel für die Farbbilder sowie als Dunkellager-Stabilisator für Magentakuppler. Man setzt sie vorzugsweise den hochsiedenden Lösungsmitteln zu, zusammen mit dem Kuppler. Solche Phosphor-III-Verbindungen sind z.B. in den folgenden Veröffentlichungen näher beschrieben: US-A-4,407,935, US-A-4,436,811, US-A-4,956,406, EP-A-181,289, JP-A-73/32728, JP-A-76/1420 und JP-A-55/66741.The photographic layers can also contain certain phosphorus III compounds, especially phosphites and phosphonites. These act as light stabilizers for the color images and as a dark storage stabilizer for magenta couplers. They are preferably added to the high-boiling solvents together with the coupler. Such phosphorus III compounds are e.g. described in more detail in the following publications: US-A-4,407,935, US-A-4,436,811, US-A-4,956,406, EP-A-181,289, JP-A-73/32728, JP-A-76/1420 and JP-A -55/66741.

Die photographischen Schichten können auch metallorganische Komplexe enthalten, die Lichtschutzmittel für die Farbbilder sind, insbesondere für die Magenta-Farbstoffe. Solche Verbindungen und deren Kombination mit anderen Additiven sind z.B. in folgenden Veröffentlichungen näher beschrieben: US-A-4,050,938, 4,239,843, 4,241,154, 4,242,429, 4,241,155, 4,242,430, 4,273,854, 4,246,329, 4,271,253, 4,242,431, 4,248,949, 4,245,195, 4,268,605, 4,246,330, 4,269,926, 4,245,018, 4,301,223, 4,343,886, 4,346,165, 4,590,153; JP-A-81/167,138, 81/168,652, 82/30834, 82/161,744; EP-A-137,271, 161,577, 185,506; DE-A-2,853,865.The photographic layers can also contain organometallic complexes which are light stabilizers for the color images, in particular for the magenta dyes. Such compounds and their combination with other additives are e.g. described in more detail in the following publications: US Pat. JP-A-81 / 167,138, 81 / 168,652, 82/30834, 82 / 161,744; EP-A-137,271, 161,577, 185,506; DE-A-2,853,865.

Die photographischen Schichten können auch Hydrochinonverbindungen enthalten. Diese wirken als Lichtschutzmittel für die Farbkuppler und für die Farbbilder sowie als Abfänger von oxidiertem Entwickler in Zwischenschichten. Sie werden vor allem in der Magentaschicht verwendet. Solche Hydrochinon-Verbindungen und deren Kombinationen mit anderen Additiven sind z.B. in folgenden Veröffentlichungen näher beschrieben: US-A-2,360,290, 2,336,327, 2,403,721, 2,418,613, 2,675,314, 2,701,197, 2,710,801, 2,732,300, 2,728,659, 2,735,765, 2,704,713, 2,937,086, 2,816,028, 3,582,333, 3,637,393, 3,700,453, 3,960,570, 3,935,016, 3,930,866, 4,065,435, 3,982,944, 4,232,114, 4,121,939, 4,175,968, 4,179,293, 3,591,381, 3,573,052, 4,279,990, 4,429,031, 4,346,165, 4,360,589, 4,346,167, 4,385,111, 4,416,978, 4,430,425, 4,277,558, 4,489,155, 4,504,572, 4,559,297, FR-A-885,982; GB-A-891,158, 1,156,167, 1,363,921, 2,022,274, 2,066,975, 2,071,348, 2,081,463, 2,117,526, 2,156,091; DE-A-2,408,168, 2,726,283, 2,639,930, 2,901,520, 3,308,766, 3,320,483, 3,323,699; DD-A-216,476, 214,468, 214,469, EP-A-84290, 110,214, 115,305, 124,915, 124,877, 144,288, 147,747, 178,165, 161,577; JP-A-75/33733, 75/21249, 77/128,130, 77/146,234, 79/70036, 79/133,131, 81/83742, 81/87040, 81/109,345, 83/134,628, 82/22237, 82/112,749, 83/17431, 83/21249, 84/75249, 84/149,348, 84/182,785, 84/180,557, 84/189,342, 84/228,249, 84/101,650, 79/24019, 79/25823, 86/48856, 86/48857, 86/27539, 86/6652, 86/72040, 87/11455, 87/62157, sowie in Research Disclosure 79/17901, 79/17905, 79/18813, 83/22827 und 84/24014.The photographic layers can also contain hydroquinone compounds. These act as light stabilizers for the color couplers and for the color images and as scavengers for oxidized developers in the intermediate layers. You will mainly be in the Magenta layer used. Such hydroquinone compounds and their combinations with other additives are described in more detail in, for example, the following publications: US Pat. 3,637,393, 3,700,453, 3,960,570, 3,935,016, 3,930,866, 4,065,435, 3,982,944, 4,232,114, 4,121,939, 4,175,968, 4,179,293, 3,591,381, 3,573,052, 4,279,990, 4,429,031, 4,346,165, 4,360,589, 4,346,167, 4,385,111, 4,416,978, 4,430,425, 4,277,558, 4,489,155, 4,504,572, 4,559,297, FR-A-885,982; GB-A-891,158, 1,156,167, 1,363,921, 2,022,274, 2,066,975, 2,071,348, 2,081,463, 2,117,526, 2,156,091; DE-A-2,408,168, 2,726,283, 2,639,930, 2,901,520, 3,308,766, 3,320,483, 3,323,699; DD-A-216,476, 214,468, 214,469, EP-A-84290, 110,214, 115,305, 124,915, 124,877, 144,288, 147,747, 178,165, 161,577; JP-A-75/33733, 75/21249, 77 / 128,130, 77 / 146,234, 79/70036, 79 / 133,131, 81/83742, 81/87040, 81 / 109,345, 83 / 134,628, 82/22237, 82 / 112.749, 83/17431, 83/21249, 84/75249, 84 / 149.348, 84 / 182.785, 84 / 180.557, 84 / 189.342, 84 / 228.249, 84 / 101.650, 79/24019, 79/25823, 86/48856, 86/48857, 86/27539, 86/6652, 86/72040, 87/11455, 87/62157, as well as in Research Disclosure 79/17901, 79/17905, 79/18813, 83/22827 and 84/24014.

Die photographischen Schichten können auch Derivate von Hydrochinonethern enthalten. Diese Verbindungen wirken als Lichtschutzmittel und sind besonders geeignet zur Stabilisierung von Magenta-Farbstoffen. Solche Verbindungen und deren Kombination mit anderen Additiven sind z.B. in folgenden Veröffentlichungen näher beschrieben: US-A 3,285,937, 3,432,300, 3,519,429, 3,476,772, 3,591,381, 3,573,052, 3,574,627, 3,573,050, 3,698,909, 3,764,337, 3,930,866, 4,113,488, 4,015,990, 4,113,495, 4,120,723, 4,155,765, 4,159,910, 4,178,184, 4,138,259, 4,174,220, 4,148,656, 4,207,111, 4,254,216, 4,134,011, 4,273,864, 4,264,720, 4,279,990, 4,332,886, 4,436,165, 4,360,589, 4,416,978, 4,385,111, 4,459,015, 4,559,297; GB-A 1,347,556, 1,366,441, 1,547,392, 1,557,237, 2,135,788; DE-A 3,214,567; DD-214,469, EP-A 161,577, 167,762, 164,130, 176,845; JP-A 76/123,642, 77/35633, 77/147,433, 78/126, 78/10430, 78/53321, 79/24019, 79/25823, 79/48537, 79/44521, 79/56833, 79/70036, 79/70830, 79/73032, 79/95233, 79/145,530, 80/21004, 80/50244, 80/52057, 80/70840, 80/139,383, 81/30125, 81/151,936, 82/34552, 82/ 82/68833, 204,306 82/204,037, 83/134,634, 83/207,039, 84/60434, 84/101,650, 84/87450, 84/149,348, 84/182,785, 86/72040, 87/11455, 87/62157, 87/63149, 86/2151, 86/6652, 86/48855, 89/309,058 sowie in Research Disclosure 78/17051.The photographic layers can also contain derivatives of hydroquinone ethers. These compounds act as light stabilizers and are particularly suitable for stabilizing magenta dyes. Such compounds and their combination with other additives are e.g. described in more detail in the following publications: US Pat , 4,207,111, 4,254,216, 4,134,011, 4,273,864, 4,264,720, 4,279,990, 4,332,886, 4,436,165, 4,360,589, 4,416,978, 4,385,111, 4,459,015, 4,559,297; GB-A 1,347,556, 1,366,441, 1,547,392, 1,557,237, 2,135,788; DE-A 3,214,567; DD-214,469, EP-A 161,577, 167,762, 164,130, 176,845; JP-A 76 / 123,642, 77/35633, 77 / 147,433, 78/126, 78/10430, 78/53321, 79/24019, 79/25823, 79/48537, 79/44521, 79/56833, 79/70036 , 79/70830, 79/73032, 79/95233, 79 / 145,530, 80/21004, 80/50244, 80/52057, 80/70840, 80 / 139,383, 81/30125, 81 / 151,936, 82/34552, 82 / 82/68833, 204.306 82 / 204.037, 83 / 134.634, 83 / 207.039, 84/60434, 84 / 101.650, 84/87450, 84 / 149.348, 84 / 182.785, 86/72040, 87/11455, 87/62157, 87/63149, 86/2151, 86/6652, 86/48855, 89 / 309,058 and in Research Disclosure 78/17051.

Als Stabilisatoren für die Magentakuppler kommen beispielsweise in Frage:

Figure imgb0130
Figure imgb0131
Figure imgb0132
Figure imgb0133
Figure imgb0134
Figure imgb0135
Figure imgb0136
Figure imgb0137
Examples of stabilizers for the magenta couplers are:
Figure imgb0130
Figure imgb0131
Figure imgb0132
Figure imgb0133
Figure imgb0134
Figure imgb0135
Figure imgb0136
Figure imgb0137

Als Silberhalogenidemulsionen können übliche Silberchlorid, -bromid oder -jodid- emulsionen verwendet werden oder Mischungen hiervon wie Silberchlorobromid- und Silberchloriodidemulsionen, worin die Silberhalogenide alle bekannten Kistallformen aufweisen können. Der Verwendung von Silberchloridemulsionen kommt im erfindungsgemässen Material besondere Bedeutung zu. Die Herstellung solcher Emulsionen sowie deren Sensibilisierung sind in RESEARCH DISCLOSURE, November 1989, Nr. 307,105 beschrieben. Diese Publikation erwähnt ferner eine Reihe von Bindemitteln für die genannten Emulsionen, welche auch in den erfindungsgemässen Materialien Anwendung finden können. Dasselbe gilt für die in der Publikation genannten Träger.Usual silver chloride, bromide or iodide emulsions can be used as silver halide emulsions or mixtures thereof such as silver chlorobromide and silver chloroiodide emulsions, in which the silver halides can have all known crystal forms. The use of silver chloride emulsions is of particular importance in the material according to the invention. The preparation of such emulsions and their sensitization are described in RESEARCH DISCLOSURE, November 1989, No. 307.105. This publication also mentions a number of binders for the emulsions mentioned, which can also be used in the materials according to the invention. The same applies to the carriers mentioned in the publication.

Die Silberhalogenidemulsion, welche zur Durchführung dieser Erfindung verwendbar ist, kann für alle gewünschten Wellenlängen sensibilisiert werden mit Hilfe von Sensibilisierungspigmenten. Es können hierfür Cyanin-Pigmente, Merocyanin-Pigmente, holopolare Pigmente, Hemicyanin-Pigmente, Styryl-Pigmente oder Hemioxanol-Pigmente verwendet werden.The silver halide emulsion which can be used in the practice of this invention can be sensitized for all desired wavelengths by means of sensitizing pigments. For this purpose, cyanine pigments, merocyanine pigments, holopolar pigments, hemicyanine pigments, styryl pigments or hemioxanol pigments can be used.

In dem photosensitiven Material können wasserlösliche Farbstoffe enthalten sein, um beispielsweise die Klarheit zu verbessern, indem sie die Strahlenschädigung verhindern. Es können hierfür Oxonol-Farbstoffe, Hemioxonol-Farbstoffe, Styryl-Farbstoffe, Merocyanin-Farbstoffe, Cyanin-Farbstoffe, Anthrachinon-Farbstoffe und Azo-Farbstoffe verwendet werden.Water-soluble dyes can be contained in the photosensitive material, for example to improve clarity by preventing radiation damage. Oxonol dyes, hemioxonol dyes, styryl dyes, merocyanine dyes, cyanine dyes, anthraquinone dyes and azo dyes can be used for this.

Es können mit dem erfindungsgemässen Material auch weitere Materialien wie beispielsweise in JP-A-87/215,272, 92/9,035, 92/21,840 und EP-A-429,240 beschrieben verwendet werden.Other materials, such as those described in JP-A-87 / 215,272, 92 / 9,035, 92 / 21,840 and EP-A-429,240, can also be used with the material according to the invention.

Ein weiterer Gegenstand der vorliegenden Erfindung sind Verbindungen der Formel

Figure imgb0138
worin R1 unabhängig voneinander einen Rest der Formel -CH2-CH(ORx)Ry,
-CH2CH(ORx)CH2ORz,
Figure imgb0139
-CH2CORy oder -CH2COCH2ORz bedeuten,
wobei

  • Rx -CORs, -COORw oder -SiRpRqRr,
  • Ry C1-C18-Alkyl oder Phenyl-C1-C4-Alkyl,
  • Rz C1-C18-Alkyl, C2-C18-Alkenyl, Phenyl-C1-C4-Alkyl, -CORs oder durch Sauerstoff unterbrochenes C1-C24-Alkyl oder C2-C24-Hydroxyalkyl,
  • Rs C1-C18-Alkyl, C2-C18-Alkenyl oder Phenyl,
  • Rw C1-C4-Alkyl und
  • Rp, Rq und Rr unabhängig voneinander C1-C6-Alkyl oder Phenyl
    bedeuten; oder
die Reste R1 unabhängig voneinander eine Gruppe G-II bedeuten,
wobei II eine Gruppe der Formel
Figure imgb0140
ist
und
G eine direkte Bindung oder eine zweiwertige Gruppe einer der folgenden Formeln ist:
-(CH2)q-, -(CH2)q-O-,-(CH2)q-O-R26-,-(CH2)q-CO-X-(CH2)r-,-(CH2)q-CO(X-(CH2)r-O-,
Figure imgb0141
Figure imgb0142
-CH2-CH(OH)-CH2-Y-(CH2)q-,
  • worin q und r unabhängig voneinander 1-4 und p 0-50 sind,
  • R26 C1-C12-Alkylen, Cyclohexylen oder Phenylen bedeutet,
  • R27 C1-C12-Alkyl, C5-C8-Cycloalkyl, Phenyl, C2-C13-Alkoxymethyl, C6-C9-Cycloalkoxymethyl oder Phenoxymethyl bedeutet,
  • R28 eine Gruppe der Formel G-II bedeutet,
  • R29 Waserstoff oder Methyl ist,
  • X -O- oder -NR23- bedeutet, worin R23 Wasserstoff, C1-C12-Alkyl oder eine Gruppe -(CH2)3-G-II oder -(CH2)3-O-G-II bedeutet,
  • Y -O- oder -NH- bedeutet,
  • R20, R21 und R22 unabhängig voneinander C1-C18-Alkyl, Cyclohexyl, Phenyl oder C1-C18-Alkoxy bedeuten; und
  • R12 Alkyl mit 1 bis 12 Kohlenstoffatomen oder eine Gruppe der Formel
    Figure imgb0143
    oder -OR16 ist, vorzugsweise ist R12 eine Gruppe der Formel
    Figure imgb0144
    worin
  • R13 und R14 unabhängig voneinander Wasserstoff oder C1-C4-Alky sind und für den Fall, dass R1 nicht -CH2CH(OCORs)CH3 bedeutet, auch Chlor sein können, und
  • R16 Alkyl mit 1 bis 8 Kohlenstoffatomen oder durch Sauerstoff unterbrochenes Alkyl mit 3 bis 12 Kohlenstoffatomen ist.
The present invention further provides compounds of the formula
Figure imgb0138
wherein R 1 independently of one another is a radical of the formula -CH 2 -CH (OR x ) R y ,
-CH 2 CH (OR x ) CH 2 OR z ,
Figure imgb0139
-CH 2 COR y or -CH 2 COCH 2 OR z mean
in which
  • R x -COR s , -COOR w or -SiR p R q R r ,
  • R y C 1 -C 18 alkyl or phenyl-C 1 -C 4 alkyl,
  • R z C 1 -C 18 alkyl, C 2 -C 18 alkenyl, phenyl-C 1 -C 4 alkyl, -COR s or C 1 -C 24 alkyl interrupted by oxygen or C 2 -C 24 hydroxyalkyl ,
  • R s C 1 -C 18 alkyl, C 2 -C 18 alkenyl or phenyl,
  • R w C 1 -C 4 alkyl and
  • R p , R q and R r independently of one another C 1 -C 6 alkyl or phenyl
    mean; or
the radicals R 1 independently of one another represent a group G-II,
where II is a group of formula
Figure imgb0140
is
and
G is a direct bond or a divalent group of one of the following formulas:
- (CH 2 ) q -, - (CH 2 ) q -O -, - (CH 2 ) q -OR 26 -, - (CH 2 ) q -CO-X- (CH 2 ) r -, - (CH 2 ) q -CO (X- (CH 2 ) r -O-,
Figure imgb0141
Figure imgb0142
-CH 2 -CH (OH) -CH 2 -Y- (CH 2 ) q -,
  • wherein q and r are independently 1-4 and p 0-50,
  • R 26 is C 1 -C 12 alkylene, cyclohexylene or phenylene,
  • R 27 is C 1 -C 12 alkyl, C 5 -C 8 cycloalkyl, phenyl, C 2 -C 13 alkoxymethyl, C 6 -C 9 cycloalkoxymethyl or phenoxymethyl,
  • R 28 represents a group of the formula G-II,
  • R 29 is hydrogen or methyl,
  • X denotes -O- or -NR 23 -, in which R 23 denotes hydrogen, C 1 -C 12 -alkyl or a group - (CH 2 ) 3 -G-II or - (CH 2 ) 3 -OG-II,
  • Y means -O- or -NH-,
  • R 20 , R 21 and R 22 independently of one another are C 1 -C 18 alkyl, cyclohexyl, phenyl or C 1 -C 18 alkoxy; and
  • R 12 is alkyl having 1 to 12 carbon atoms or a group of the formula
    Figure imgb0143
    or -OR 16 , preferably R 12 is a group of the formula
    Figure imgb0144
    wherein
  • R 13 and R 14 are, independently of one another, hydrogen or C 1 -C 4 -alkyl and, in the event that R 1 is not -CH 2 CH (OCOR s ) CH 3 , can also be chlorine, and
  • R 16 is alkyl of 1 to 8 carbon atoms or oxygen interrupted alkyl of 3 to 12 carbon atoms.

Besonders bevorzugt sind die Verbindungen, worin die Reste R1 unabhängig voneinander Reste der Formel -CH2-CH(ORx)Ry, -CH2CH(ORx)CH2ORz, -CH2CORy oder -CH2COCH2ORz bedeuten, wobei

  • Rx -CORs, -COORw oder -SiRpRqRr,
  • Ry C1-C8-Alkyl,
  • Rz C1-C18-Alkyl, C2-C18-Alkenyl, Benzyl, -CORs oder durch Sauerstoff unterbrochenes C1-C24-Alkyl oder C2-C24-Hydroxyalkyl,
  • Rs C1-C18-Alkyl, C2-C18-Alkenyl oder Phenyl,
  • Rw C1-C4-Alkyl und
  • Rp, Rq und Rr unabhängig voneinander C1-C6-Alkyl
    bedeuten; oder
R1 eine Gruppe G-II bedeuten,
wobei II eine Gruppe der Formel
Figure imgb0145
ist
und
G eine direkte Bindung oder eine zweiwertige Gruppe einer der folgenden Formeln ist:
-(CH2)q-, -(CH2)q-O-, -(CH2)q-CO-X-(CH2)r-,
Figure imgb0146
oder
-CH2-CH(OH)-CH2-Y-(CH2)q-,
  • worin q und r unabhängig voneinander 1, 2 oder 3 und p 0-50 sind,
  • R27 Methyl, Phenyl, C3-C9-Alkoxymethyl oder Phenoxymethyl bedeutet,
  • R28 eine Gruppe der Formel G-II bedeutet,
  • X und Y -O- bedeuten,
  • R20, R21 und R22 unabhängig voneinander C1-C8-Alkyl, Phenyl oder C1-C8-Alkoxy bedeuten; und
  • R12 eine Gruppe der Formel
    Figure imgb0147
    ist, worin
  • R13 und R14 unabhängig voneinander Wasserstoff oder C1-C4-Alkyl sind und für den Fall, dass R1 nicht -CH2CH(OCORs)CH3 bedeutet, auch Chlor sein können.
Particularly preferred are the compounds in which the radicals R 1 independently of one another are radicals of the formula -CH 2 -CH (OR x ) R y , -CH 2 CH (OR x ) CH 2 OR z , -CH 2 COR y or -CH 2 COCH 2 OR z mean, where
  • R x -COR s , -COOR w or -SiR p R q R r ,
  • R y C 1 -C 8 alkyl,
  • R z C 1 -C 18 alkyl, C 2 -C 18 alkenyl, benzyl, -COR s or C 1 -C 24 alkyl interrupted by oxygen or C 2 -C 24 hydroxyalkyl,
  • R s C 1 -C 18 alkyl, C 2 -C 18 alkenyl or phenyl,
  • R w C 1 -C 4 alkyl and
  • R p , R q and R r independently of one another C 1 -C 6 alkyl
    mean; or
R 1 represents a group G-II,
where II is a group of formula
Figure imgb0145
is
and
G is a direct bond or a divalent group of one of the following formulas:
- (CH 2 ) q -, - (CH 2 ) q -O-, - (CH 2 ) q -CO-X- (CH 2 ) r -,
Figure imgb0146
or
-CH 2 -CH (OH) -CH 2 -Y- (CH 2 ) q -,
  • wherein q and r are independently 1, 2 or 3 and p are 0-50,
  • R 27 denotes methyl, phenyl, C 3 -C 9 alkoxymethyl or phenoxymethyl,
  • R 28 represents a group of the formula G-II,
  • X and Y mean -O-,
  • R 20 , R 21 and R 22 independently of one another are C 1 -C 8 alkyl, phenyl or C 1 -C 8 alkoxy; and
  • R 12 is a group of the formula
    Figure imgb0147
    is what
  • R 13 and R 14 are independently hydrogen or C 1 -C 4 alkyl and, in the event that R 1 is not -CH 2 CH (OCOR s ) CH 3 , can also be chlorine.

Weiter bevorzugte Verbindungen sind solche, wie sie bei der Beschreibung des fotografischen Materials erwähnt sind.Further preferred compounds are those as mentioned in the description of the photographic material.

Die nachfolgenden Beispiele erläutern die Erfindung weiter.The following examples further illustrate the invention.

Beispiel 1: Auf ein mit Polyethylen beschichtetes Trägermaterial wird zuerst eine Gelatineschicht aufgetragen, die Silberbromid, einen Magentakuppler und einen Stabilisator enthält, dann eine Gelatineschicht, die den UV-Absorber der Formel (I) enthält (Deckschicht).EXAMPLE 1 A gelatin layer which contains silver bromide, a magenta coupler and a stabilizer is first applied to a carrier material coated with polyethylene, then a gelatin layer which contains the UV absorber of the formula (I) (top layer).

Die Gelatineschichten enthalten folgende Komponenten (je m2 Trägermaterial): Komponente AgBr-Schicht Deckschicht Gelatine 5.15 g 1.2 g Härtungsmittel 300 mg 40 mg Netzmittel 85 mg 100 mg Silberbromid 520 mg* -- 260 mg** -- Isononylphosphat A 510 mg Magentakuppler 0.535 mM -- UV-Absorber -- 300 mg Stabilisator B -- * bei Verwendung von 4-Aequivalentkupplern, ** bei Verwendung von
2-Aequivalentkupplern
A (Oelmenge) = 50 % der Magentakuppler-Menge,
B (Stabilisatormenge) = 35 % der Magentakuppler-Menge
The gelatin layers contain the following components (each m 2 carrier material): component AgBr layer Top layer gelatin 5.15 g 1.2 g Hardening agent 300 mg 40 mg Wetting agent 85 mg 100 mg Silver bromide 520 mg * - 260 mg ** - Isononyl phosphate A 510 mg Magenta coupler 0.535 mM - UV absorber - 300 mg stabilizer B - * when using 4-equivalent couplers, ** when using
2-equivalent couplers
A (amount of oil) = 50% of the amount of magenta coupler,
B (amount of stabilizer) = 35% of the amount of magenta coupler

Als Härter wird 2,4-Dichlor-6-hydroxytriazin verwendet, als Netzmittel das Natriumsalz der Diisobutylnaphthalinsulfonsäure.2,4-dichloro-6-hydroxytriazine is used as the hardener and the sodium salt of diisobutylnaphthalenesulfonic acid as the wetting agent.

Die Mengen von Magentakuppler und Stabilisator sind in Tabelle 2 angegeben.The amounts of magenta coupler and stabilizer are given in Table 2.

Auf die so erhaltenen Proben wird jeweils ein Stufenkeil mit einem Dichteunterschied von 0,15 logE pro Stufe aufbelichtet und anschliessend gemäss den Vorschriften des Herstellers im Verarbeitungsprozess E+2 der Firma Kodak für Negativ-Farbpapiere verarbeitet.A step wedge with a density difference of 0.15 logE per step is exposed on each of the samples thus obtained and then processed in accordance with the manufacturer's instructions in processing process E + 2 from Kodak for negative color papers.

Nach Belichtung und Verarbeitung wird die Remissionsdichte im grün für die Magentastufe mit einer Dichte zwischen 0,9 und 1,1 des Keils gemessen. Dann wird der Keil in einem Atlas-Belichungsgerät mit total 45 kJ/cm2 belichtet und erneut die Remissionsdichte gemessen.After exposure and processing, the reflectance density in green is measured for the magenta step with a density between 0.9 and 1.1 of the wedge. Then the wedge is exposed in a Atlas exposure device with a total of 45 kJ / cm 2 and the remission density is measured again.

Der Farbstoffverlust (-ΔD) in % ist in Tabelle 2 angegeben. Tabelle 2 Probe Nr. Magentakuppler (mg) Stabilisator (mg) UV-Absorber Nr. -ΔD 1 M-1 (329) ST-4 (118) (3) 64 2 M-2 (417) ST-8 (144) (3) 61 3 M-3 (394) ST-5 (128) (3) 54 4 M-4 (485) ST-1 (171) (3) 62 5 M-4 (485) ST-2 (171) (3) 65 6 M-4 (48-5) ST-3 (171) (3) 60 7 M-1 (329) ST-7 (118) (3) 74 8 M-1 (329) ST-6 (118) (3) 85 9 M-6 (306) ST-4 (107) (3) 36 10 M-6 (306) ST-1 (107) (3) 40 11 M-1 (329) ST-4 (118) (10) 69 12 M-6 (306) ST-4 (107) (10) 41 13 M-6 (306) ST-1 (107) (10) 47 14 M-6 (306) ST-4 (107) (12) 39 16 M-1 (329) ST-4 (118) - 87 17 M-2 (417) ST-8 (144) - 91 18 M-3 (394) ST-5 (128) - 84 19 M-4 (485) ST-1 (170) - 89 20 M-4 (485) ST-2 (171) - 87 21 M-4 (485) ST-3 (171) - 90 22 M-1 (329) ST-7 (118) - 89 23 M-1 (329) ST-6 (118) - 92 24 M-6 (306) ST-4 (107) - 65 25 M-6 (306) ST-1 (107) - 78 The dye loss (-ΔD) in% is given in Table 2. Table 2 Sample No. Magenta Coupler (mg) Stabilizer (mg) UV absorber no. -ΔD 1 M-1 (329) ST-4 (118) (3) 64 2nd M-2 (417) ST-8 (144) (3) 61 3rd M-3 (394) ST-5 (128) (3) 54 4th M-4 (485) ST-1 (171) (3) 62 5 M-4 (485) ST-2 (171) (3) 65 6 M-4 (48-5) ST-3 (171) (3) 60 7 M-1 (329) ST-7 (118) (3) 74 8th M-1 (329) ST-6 (118) (3) 85 9 M-6 (306) ST-4 (107) (3) 36 10th M-6 (306) ST-1 (107) (3) 40 11 M-1 (329) ST-4 (118) (10) 69 12th M-6 (306) ST-4 (107) (10) 41 13 M-6 (306) ST-1 (107) (10) 47 14 M-6 (306) ST-4 (107) (12) 39 16 M-1 (329) ST-4 (118) - 87 17th M-2 (417) ST-8 (144) - 91 18th M-3 (394) ST-5 (128) - 84 19th M-4 (485) ST-1 (170) - 89 20th M-4 (485) ST-2 (171) - 87 21 M-4 (485) ST-3 (171) - 90 22 M-1 (329) ST-7 (118) - 89 23 M-1 (329) ST-6 (118) - 92 24th M-6 (306) ST-4 (107) - 65 25th M-6 (306) ST-1 (107) - 78

In den Proben, die einen erfindungsgemässen UV-Absorber enthalten, wird eine geringere Abnahme der Magentadichte festgestellt.A smaller decrease in the magenta density is found in the samples which contain a UV absorber according to the invention.

Beispiel 2: Es wird wie in Beispiel 1 vorgegangen, jedoch ohne Stabilisator und unter Verwendung eines Cyankupplers. Die Zusammensetzung der Gelatineschichten (pro m2) ist folgende: Komponente AgBr-Schicht Deckschicht Gelatine 5.15 g 1.2 g Härter 300 mg 40 mg Netzmittel 170 mg 100 mg Silberbromid 260 mg -- Trikresylphosphat A 510 mg Cyankuppler 0.535 mM -- UV-Absorber -- 300 mg A (Oelmenge) = 1,5 x Cyankupplermenge Example 2: The procedure is as in Example 1, but without a stabilizer and using a cyan coupler. The composition of the gelatin layers (per m 2 ) is as follows: component AgBr layer Top layer gelatin 5.15 g 1.2 g Harder 300 mg 40 mg Wetting agent 170 mg 100 mg Silver bromide 260 mg - Tricresyl phosphate A 510 mg Cyan couplers 0.535 mM - UV absorber - 300 mg A (amount of oil) = 1.5 x amount of cyan couplers

Die Mengen am Cyankuppler sind in Tabelle 3 angegeben:The amounts of the cyan coupler are given in Table 3:

Nach Belichtung und Verarbeitung wie in Beispiel 1 beschrieben, wird die Remissionsdichte im Rot für die Cyanstufe mit einer Dichte zwischen 0,9 und 1,1 des Keils gemessen. Dann wird der Keil in einem Atlas-Belichtungsgerät mit total 30 kJ/cm2 belichtet und erneut die Remissionsdichte gemessen. Der Farbstoffdichteverlust (-ΔD) in % ist in Tabelle 3 angegeben. Tabelle 3 Probe Nr. Cyankuppler (mg) UV-Absorber Nr. -ΔD 26 E-1 (264) (3) 12 27 E-2 (272) (3) 19 28 E-5 (358) (3) 26 29 E-6 (33) (3) 28 30 E-1 (264) (10) 14 31 E-3 (272) (10) 19 32 E-5 (358) (10) 28 33 E-6 (331) (10) 29 34 E-2 (272) (12) 19 37 E-1 (264) - 20 38 E-2 (272) - 25 39 E-3 (272) - 23 40 E-5 (358) - 39 41 E-6 (331) - 42 After exposure and processing as described in Example 1, the reflectance density in red for the cyan stage is measured with a density between 0.9 and 1.1 of the wedge. Then the wedge is exposed in a Atlas exposure device with a total of 30 kJ / cm 2 and the remission density is measured again. The dye density loss (-ΔD) in% is given in Table 3. Table 3 Sample No. Cyan couplers (mg) UV absorber no. -ΔD 26 E-1 (264) (3) 12th 27 E-2 (272) (3) 19th 28 E-5 (358) (3) 26 29 E-6 (33) (3) 28 30th E-1 (264) (10) 14 31 E-3 (272) (10) 19th 32 E-5 (358) (10) 28 33 E-6 (331) (10) 29 34 E-2 (272) (12) 19th 37 E-1 (264) - 20th 38 E-2 (272) - 25th 39 E-3 (272) - 23 40 E-5 (358) - 39 41 E-6 (331) - 42

In den Proben, die einen erfindungsgemässen UV-Absorber enthalten, ist eine geringere Abnahme in der Dichte des Cyanfarbstoffs festzustellen.A smaller decrease in the density of the cyan dye can be found in the samples which contain a UV absorber according to the invention.

Beispiel 3: Es wird wie in Beispiel 1 vorgegangen, jedoch ohne Stabilisator und unter Verwendung eines Gelbkupplers. Example 3: The procedure is as in Example 1, but without a stabilizer and using a yellow coupler.

Die Zusammensetzung der Gelatineschichten (pro m2) ist folgende: Komponente AgBr-Schicht Deckschicht Gelatine 5.15 g 1.2 g Härtungsmittel 300 mg 40 mg Netzmittel (anionisch) 340 mg 100 mg Silberbromid 520 mg -- Trikresylphosphat A 510 mg Gelbkuppler 1.07 mM -- UV-Absorber -- 300 mg A (Oelmenge) = 33 % der Gelbkuppler-Menge The composition of the gelatin layers (per m 2 ) is as follows: component AgBr layer Top layer gelatin 5.15 g 1.2 g Hardening agent 300 mg 40 mg Wetting agent (anionic) 340 mg 100 mg Silver bromide 520 mg - Tricresyl phosphate A 510 mg Yellow coupler 1.07 mM - UV absorber - 300 mg A (amount of oil) = 33% of the amount of yellow coupler

Die Menge an Gelbkuppler ist in Tabelle 4 angegeben.The amount of yellow coupler is given in Table 4.

Nach Belichtung und Verarbeitung wie in Beispiel 1 beschrieben, wird die Remissionsdichte im Blau für die Gelbstufe mit einer Dichte zwischen 0,9 und 1,1 des Keils gemessen. Dann wird der Keil in einem Atlas-Belichtungsgerät mit total 15 kJ/cm2 belichtet und erneut die Remissionsdichte gemessen. Der Farbstoffverlust (-ΔD) in % ist in Tabelle 4 angegeben. Tabelle 4 Probe Nr. Gelbkuppler (mg) UV-Absorber Nr. -ΔD 42 Y-1 (819) (3) 25 43 Y-2 (859) (3) 16 44 Y-3 (973) (3) 20 45 Y-4 (812) (3) 22 46 Y-6 (813) (3) 27 47 Y-7 (835) (3) 28 48 Y-1 (819) (10) 30 49 Y-3 (973) (10) 24 50 Y-7 (835) (10) 33 51 Y-1 (819) - 49 52 Y-2 (859) - 36 53 Y-3 (973) - 52 54 Y-4 (812) - 44 55 Y-6 (813) - 51 56 Y-7 (835) - 52 56a Y-8 (927) - 57 56b Y-8 (927) (3) 33 56c Y-8 (927) (12) 35 After exposure and processing as described in Example 1, the reflectance density in blue is measured for the yellow level with a density between 0.9 and 1.1 of the wedge. Then the wedge is exposed in a Atlas exposure device with a total of 15 kJ / cm 2 and the remission density is measured again. The dye loss (-ΔD) in% is given in Table 4. Table 4 Sample No. Yellow coupler (mg) UV absorber no. -ΔD 42 Y-1 (819) (3) 25th 43 Y-2 (859) (3) 16 44 Y-3 (973) (3) 20th 45 Y-4 (812) (3) 22 46 Y-6 (813) (3) 27 47 Y-7 (835) (3) 28 48 Y-1 (819) (10) 30th 49 Y-3 (973) (10) 24th 50 Y-7 (835) (10) 33 51 Y-1 (819) - 49 52 Y-2 (859) - 36 53 Y-3 (973) - 52 54 Y-4 (812) - 44 55 Y-6 (813) - 51 56 Y-7 (835) - 52 56a Y-8 (927) - 57 56b Y-8 (927) (3) 33 56c Y-8 (927) (12) 35

In den Proben, die einen erfindungsgemässen UV-Absorber enthalten, ist eine geringere Abnahme in der Gelbfarbstoffdichte festzustellen.A smaller decrease in the yellow dye density can be found in the samples which contain a UV absorber according to the invention.

Beispiel 4: Es wird wie in Beispiel 1 vorgegangen. Example 4: The procedure is as in Example 1.

Die Mengen an Magentakuppler und Stabilisator sind in Tabelle 5 angegeben.The amounts of magenta coupler and stabilizer are given in Table 5.

Es wird die Remissionsdichte im Blau für die Vergilbung gemessen. Dann wird der Keil in einem Atlas-Belichtungsgerät mit total 15 kJ/cm2 belichtet, erneut die Remissionsdichte (in Blau) gemessen und die Gelbfarbstoffzunahme (-ΔDB) berechnet. Die Vergilbung ist in Tabelle 5 angegeben. Tabelle 5 Probe Nr. Magentakuppler (mg) Stabilisator (mg) UV-Absorber Nr. -ΔDB 57 M-1 (329) ST-4 (118) (3) 10 58 M-1 ST-4 (118) (12) 14 59 M-1 ST-4 (118) - 33 60 M-1 ST-7 (118) (3) 8 61 M-1 ST-7 (118) - 28 62 M-1 ST-6 (118) (3) 3 63 M-1 ST-6 (118) - 31 64 M-2 (417) ST-8 (144) (3) 13 65 M-2 ST-8 (144) - 25 66 M-3 (394) ST-5 (128) (3) 8 67 M-3 ST-5 (128) - 21 68 M-4 (485) ST-1 (171) (3) 14 69 M-4 ST-1 (171) - 30 70 M-4 ST-2 (171) (3) 2 71 M-4 ST-2 (171) - 25 72 M-4 ST-3 (171) (3) 12 73 M-4 ST-3 (171) - 24 The reflectance density in blue for yellowing is measured. The wedge is then exposed in a Atlas exposure device with a total of 15 kJ / cm 2 , the reflectance density (in blue) is measured again and the yellow dye increase (-ΔD B ) is calculated. The yellowing is shown in Table 5. Table 5 Sample No. Magenta Coupler (mg) Stabilizer (mg) UV absorber no. -ΔD B 57 M-1 (329) ST-4 (118) (3) 10th 58 M-1 ST-4 (118) (12) 14 59 M-1 ST-4 (118) - 33 60 M-1 ST-7 (118) (3) 8th 61 M-1 ST-7 (118) - 28 62 M-1 ST-6 (118) (3) 3rd 63 M-1 ST-6 (118) - 31 64 M-2 (417) ST-8 (144) (3) 13 65 M-2 ST-8 (144) - 25th 66 M-3 (394) ST-5 (128) (3) 8th 67 M-3 ST-5 (128) - 21 68 M-4 (485) ST-1 (171) (3) 14 69 M-4 ST-1 (171) - 30th 70 M-4 ST-2 (171) (3) 2nd 71 M-4 ST-2 (171) - 25th 72 M-4 ST-3 (171) (3) 12th 73 M-4 ST-3 (171) - 24th

In den Proben, die einen erfindungsgemässen UV-Absorber enthalten, ist eine geringere Vergilbung festzustellen.Less yellowing is found in the samples which contain a UV absorber according to the invention.

Beispiel 5: Die in der nachstehenden Tabelle aufgeführte Menge von UV-Absorber wird in 2 ml Essigester gelöst. 1 ml von dieser Lösung wird mit 9 ml einer wässrigen Gelatinelösung (welche 27,6 g/l Gelatine und 6,8 g/l einer 8%igen wässrigen Lösung von 4,8-Diisobutylnaphthalen-2-sulfonsäure (Natriumsalz) als Netzmittel enthält) gemischt. Diese Mischung wird 3 Minuten mit Ultraschall emulgiert. 7,5 ml dieser UV-Absorber Emulsion wird mit 4,5 ml einer wässrigen Härterlösung (bestehend aus 0,24 % von 2-Hydroxy-4,6-dichlor-1,3,5-triazin, Kaliumsalz) gemischt. 8 ml dieser Emulsion werden auf einen Polyesterträger (13x18 cm) gegossen. Der Guss wird 7 Tage bei Raumtemperatur gehärtet. Mit einem UV-Spektrometer werden nun Werte für die maximale Dichte im Bereich von 330-380 nm erfasst. Dann wird die Probe in einem Atlas-Belichtungsgerät mit insgesamt 60 kJ/cm2 belichtet, erneut die maximale Dichte bestimmt und die Differenz (-DD in %) zwischen den entsprechenden Werten berechnet: Tabelle 6 Probe Nr. UV-Absorber (mg) UV-Absorberverlust-DD (%) Atlas 60 kJ/cm2 74 (3) (41) 0 75 (4) (49) 1 76 (5) (63) 1 77 (6) (42) 0 78 (7) (40) 0 79 (8) (50) 3 Example 5: The amount of UV absorber listed in the table below is dissolved in 2 ml of ethyl acetate. 1 ml of this solution is mixed with 9 ml of an aqueous gelatin solution (which contains 27.6 g / l gelatin and 6.8 g / l of an 8% aqueous solution of 4,8-diisobutylnaphthalene-2-sulfonic acid (sodium salt) as a wetting agent ) mixed. This mixture is emulsified with ultrasound for 3 minutes. 7.5 ml of this UV absorber emulsion is mixed with 4.5 ml of an aqueous hardener solution (consisting of 0.24% of 2-hydroxy-4,6-dichloro-1,3,5-triazine, potassium salt). 8 ml of this emulsion are poured onto a polyester carrier (13x18 cm). The cast is hardened for 7 days at room temperature. Values for the maximum density in the range of 330-380 nm are now recorded with a UV spectrometer. Then the sample is exposed in an Atlas exposure device with a total of 60 kJ / cm 2 , the maximum density is determined again and the difference (-DD in%) between the corresponding values is calculated: Table 6 Sample No. UV absorber (mg) UV absorber loss DD (%) Atlas 60 kJ / cm 2 74 (3) (41) 0 75 (4) (49) 1 76 (5) (63) 1 77 (6) (42) 0 78 (7) (40) 0 79 (8th) (50) 3rd

Beispiel 6: Führt man wie in Beispiel 1 aber

  • ① belichtet man nur 30 kJ/cm2
  • ② mischt man UV-Absorber der Erfindung (150 mg) mit Hydroxybenztriazole (150 mg)
Figure imgb0148
Example 6: Carrying out as in Example 1 but
  • ① exposure is only 30 kJ / cm 2
  • Man mixing the UV absorber of the invention (150 mg) with hydroxybenzotriazoles (150 mg)
Figure imgb0148

Beispiel 7: Auf ein mit Polyethylen beschichtetes Trägermaterial wird eine Gelatineschicht aufgetragen, die Silberbromid, einen Cyankuppler und einen UV-Absorber der Formel (I) enthalten. Die Gelatineschicht enthält folgende Komponenten (je m2 Trägermaterial)

Figure imgb0149
Figure imgb0150
Example 7: A gelatin layer containing silver bromide, a cyan coupler and a UV absorber of the formula (I) is applied to a carrier material coated with polyethylene. The gelatin layer contains the following components (each m 2 carrier material)
Figure imgb0149
Figure imgb0150

Nach Belichtung und Verarbeitung wie in Beispiel 1 beschrieben, wird die Remissionsdichte im Rot für die Cyanstufe mit einer Dichte zwischen 0,9 und 1,1 des Keils gemessen. Dann wird er Keil in einem Atlas-Belichtungsgerät mit 30 kJ/cm2 belichtet und erneut die Remissionsdichte gemessen. Der Farbstoffverlust (-ΔD) in % ist in Tabelle Y angegeben. Tabelle Y Probe Nr. Cyankuppler (mg) UV-Absorber Nr. (mg) -ΔD 90 E-5 (358) - 41 91 " " (3) (358) 29 92 " " (10) (358) 30 93 E-6 (321) - 44 94 " " (3) (331) 35 95 " " (10) (331) 36 After exposure and processing as described in Example 1, the reflectance density in red for the cyan stage is measured with a density between 0.9 and 1.1 of the wedge. Then it is exposed to wedge in an Atlas exposure device with 30 kJ / cm 2 and the remission density is measured again. The dye loss (-ΔD) in% is given in Table Y. Table Y Sample No. Cyan couplers (mg) UV absorber No. (mg) -ΔD 90 E-5 (358) - 41 91 " " (3) (358) 29 92 " " (10) (358) 30th 93 E-6 (321) - 44 94 " " (3) (331) 35 95 " " (10) (331) 36

Beispiel 8: Führt man wie in Beispiel 4 aber man mischt UV-Absorber der Erfindung (150 mg) mit einem Hydroxybenztriazol (150 mg)

Figure imgb0151
Example 8: The procedure is as in Example 4, but the UV absorber of the invention (150 mg) is mixed with a hydroxybenzotriazole (150 mg)
Figure imgb0151

Beispiel 9: Führt man wie in Beispiel 4 aber gibt man zusätzlich einen Stabilisator der folgenden Formel zu

Figure imgb0152
Probe Nr. Gelbkuppler (mg) Stabilisator (mg) UV-Absorber Nr. -ΔD % 99 Y-8 (927) ST-Y1 (273) - 31 100 Y-8 (927) ST-Y1 (273) (3) 10 Example 9: If the procedure is as in Example 4, but additionally a stabilizer of the following formula is added
Figure imgb0152
Sample No. Yellow coupler (mg) stabilizer (mg) UV absorber no. -ΔD% 99 Y-8 (927) ST-Y1 (273) - 31 100 Y-8 (927) ST-Y1 (273) (3) 10th

Beispiel 10: Führt man wie in Beispiel 9 aber mischt man UV-Absorber der Erfindung (150 mg) mit einem Hydroxybenztriazol (150 mg)

Figure imgb0153
Example 10: If the procedure is as in Example 9, but the UV absorber of the invention (150 mg) is mixed with a hydroxybenzotriazole (150 mg)
Figure imgb0153

Beispiel 11: Es wird ein photographisches Material mit folgendem Schichtbau hergestellt:

Figure imgb0154
Example 11: A photographic material with the following layer structure is produced:
Figure imgb0154

Die Gelatineschichten bestehen aus folgenden Komponenten (je m2 Trägermaterial): Blauempfindliche Schicht Gelbkuppler Y-2 859 mg Trikresylphosphat 286 mg Gelatine 5,15 g Härter 300 mg Netzmittel 340 mg AgBr 520 mg Erste Gelatinezwischenschicht Gelatine 3,90 g Härter 230 mg Netzmittel 65 mg Grünempfindliche Schicht Magentakuppler M-6 306 mg Trikresylphosphat 153 mg Gelatine 5,15 g Härter 300 mg Netzmittel 85 mg AgBr 260 mg Stabilisator 107 mg Zweite Gelatinezwischenschicht Gelatine 3,90 g Härter 230 mg Netzmittel 65 mg Rotempfindliche Schicht Cyankuppler E-6 331 mg Trikresylphosphat 496 mg Gelatine 5,15 g Härter 300mg Netzmittel 170 mg AgBr 260 mg The gelatin layers consist of the following components (each m 2 carrier material): Blue sensitive layer Yellow coupler Y-2 859 mg Tricresyl phosphate 286 mg gelatin 5.15 g Harder 300 mg Wetting agent 340 mg AgBr 520 mg First intermediate layer of gelatin gelatin 3.90 g Harder 230 mg Wetting agent 65 mg Green sensitive layer Magenta coupler M-6 306 mg Tricresyl phosphate 153 mg gelatin 5.15 g Harder 300 mg Wetting agent 85 mg AgBr 260 mg stabilizer 107 mg Second layer of gelatin gelatin 3.90 g Harder 230 mg Wetting agent 65 mg Red sensitive layer Cyan coupler E-6 331 mg Tricresyl phosphate 496 mg gelatin 5.15 g Harder 300mg Wetting agent 170 mg AgBr 260 mg

Eine Schutzschicht wird mit und ohne UV-Absorber hergestellt mit UV-Absorber ohne UV-Absorber Gelatine 1,2 g 2,4 g UV-Absorber 300 mg --- Trikresylphosphat 510 mg --- Härtungsmittel 40 mg 80 mg Netzmittel 100 mg 200 mg Probe Nr. UV-Absorber 104 - 105 (3) 106 (12) A protective layer is made with and without UV absorber with UV absorber without UV absorber gelatin 1.2 g 2.4 g UV absorber 300 mg --- Tricresyl phosphate 510 mg --- Hardening agent 40 mg 80 mg Wetting agent 100 mg 200 mg Sample No. UV absorber 104 - 105 (3) 106 (12)

Als Härter und Netzmittel werden die entsprechenden Verbindungen gemäss Beispiel 1 verwendet.The corresponding compounds according to Example 1 are used as hardeners and wetting agents.

Auf die 3 Proben 104- 106 werden (mit blauem, grünem bzw. rotem Licht) jeweils drei Stufenkeile mit einem Dichteunterschied von 0,15 kJ pro Stufe aufbelichtet.Three step wedges with a density difference of 0.15 kJ per step are exposed on the three samples 104-106 (with blue, green or red light).

Anschliessend wird gemäss Verarbeitungsprozess EP2 (Kodak) für Negativ-Farbpapiere verfahren.The process is then carried out in accordance with processing process EP2 (Kodak) for negative color papers.

Nach Belichtung und Verarbeitung werden die Remissionsdichten im Rot für die Cyanstufe, im Grün für die Magentastufe und im Blau für die Gelbstufe bei einer Dichte zwischen 0,9 und 1,1 der Keile gemessen. Dann werden die Keile in einem Atlas-Belichtungsgerät mit insgesamt 15 kJ/cm2 belichtet und es werden erneut die Remissionsdichten gemessen.After exposure and processing, the reflectance densities are measured in red for the cyan level, in green for the magenta level and in blue for the yellow level at a density between 0.9 and 1.1 of the wedges. Then the wedges are exposed in an Atlas exposure device with a total of 15 kJ / cm 2 and the reflectance densities are measured again.

Auch bei dem Magentakeil wird die Remissionsdichte vor und nach der Belichtung im Blau für die Vergilbung gemessen.For the magenta wedge, the reflectance density is measured before and after the exposure in blue for yellowing.

Die Anwesenheit der UV-Absorber reduziert den Farbstoffdichteverlust des Cyan-, Magenta- und Gelbbildfarbstoffs sowie die Vergilbung.The presence of the UV absorbers reduces the loss of dye density of the cyan, magenta and yellow image dye and yellowing.

Beispiel 12: Es wird ein photographisches Material mit folgendem Schichtbau hergestellt:

Figure imgb0155
Example 12: A photographic material with the following layer structure is produced:
Figure imgb0155

Die Gelatineschichten bestehen aus folgenden Komponenten (je m2 Trägermaterial):The gelatin layers consist of the following components (each m 2 carrier material):

Blauempfindliche SchichtBlue sensitive layer

  • α-(3-Benzyl-4-ethoxyhydantoin-1-yl)-α-pivaloyl-2-chloro-5-[α-(2,4-di-t-amylphenoxy)butanamido]acetanilid    (400 mg)α- (3-Benzyl-4-ethoxyhydantoin-1-yl) -α-pivaloyl-2-chloro-5- [α- (2,4-di-t-amylphenoxy) butanamido] acetanilide (400 mg)
  • α-(1-Butyl-phenylurazol-4-yl)-α-pivaloyl-5-(3-dodecansulfonyl-2-methylpropanamido)-2-methoxyacetamid    (400 mg)α- (1-Butyl-phenylurazol-4-yl) -α-pivaloyl-5- (3-dodecanesulfonyl-2-methylpropanamido) -2-methoxyacetamide (400 mg)
  • Dibutylphthalat    (130 mg)Dibutyl phthalate (130 mg)
  • Dinonylphthalat    (130 mg)Dinonyl phthalate (130 mg)
  • Gelatine    (1200 mg)Gelatin (1200 mg)
  • 1,5-Dioxa-3-ethyl-3-[β-(3,5-di-t-butyl-4-hydroxyphenyl)-propionyloxymethyl]-8,10-diphenyl-9-thia-[5,5]spiroundecan    (150 mg)1,5-dioxa-3-ethyl-3- [β- (3,5-di-t-butyl-4-hydroxyphenyl) propionyloxymethyl] -8,10-diphenyl-9-thia- [5,5] spiroundecane (150 mg)
  • Bis(1-acryloyl-2,2,6,6-tetramethyl-4-piperidyl)2,2-bis-(3,5-di-t-butyl-4-hydroxybenzyl)malonate    (150 mg)Bis (1-acryloyl-2,2,6,6-tetramethyl-4-piperidyl) 2,2-bis (3,5-di-t-butyl-4-hydroxybenzyl) malonate (150 mg)
  • 3,5-Di-t-butyl-4-hydroxy-(2,4-di-t-amylphenyl) -benzoate    (150 mg)3,5-di-t-butyl-4-hydroxy- (2,4-di-t-amylphenyl) benzoate (150 mg)
  • Poly(N-t-butylacrylamid)    (50 mg)Poly (N-t-butylacrylamide) (50 mg)
  • blauempfindliche Silberchlorobromid-emulsion    (240 mg)blue-sensitive silver chlorobromide emulsion (240 mg)
Erste GelatinezwischenschichtFirst intermediate layer of gelatin

  • Gelatine    (1000 mg)Gelatin (1000 mg)
  • 2,5-Di-t-octylhydrochinon    (100 mg)2,5-di-t-octylhydroquinone (100 mg)
  • 5-[2,5-Dihydroxy-4-(4-hexyloxycarbonyl-1,1-dimethylbutyl)-phenyl]-5-methylhexansäurehexylester    (100 mg)5- [2,5-Dihydroxy-4- (4-hexyloxycarbonyl-1,1-dimethylbutyl) phenyl] -5-methylhexanoic acid hexyl ester (100 mg)
  • Dibutylphthalat    (200 mg)Dibutyl phthalate (200 mg)
  • Diisodecylphthalat    (200 mg)Diisodecyl phthalate (200 mg)
Grünempfindliche SchichtGreen sensitive layer

  • 7-Chloro-2-(2-[2-(2,4-di-t-amylphenoxy)octanamido]-1-methylethyl}-6-methyl-1H-pyrazolo[1,5-b][1,2,4]triazol    (100 mg)7-chloro-2- (2- [2- (2,4-di-t-amylphenoxy) octanamido] -1-methylethyl} -6-methyl-1H-pyrazolo [1,5-b] [1,2, 4] triazole (100 mg)
  • 6-t-Butyl-7-chloro-3-(3-dodecansulfonylpropyl)-1H-pyrazolo[5,1-o][1,2,4]triazol    (100 mg)6-t-Butyl-7-chloro-3- (3-dodecanesulfonylpropyl) -1H-pyrazolo [5,1-o] [1,2,4] triazole (100 mg)
  • Dibutylphthalat    (100 mg)Dibutyl phthalate (100 mg)
  • Dikresylphosphat    (100 mg)Dicresyl phosphate (100 mg)
  • Trioctylphosphat    (100 mg)Trioctyl phosphate (100 mg)
  • Gelatine    (1400 mg)Gelatin (1400 mg)
  • 3,3,3',3'-Tetramethyl-5,5',6,6'-tetrapropoxy-1,1'-spirobiindane    (100 mg)3,3,3 ', 3'-tetramethyl-5,5', 6,6'-tetrapropoxy-1,1'-spirobiindane (100 mg)
  • 4- (1-Tridecyloxyphenyl)thiomorpholine-1,1-dioxide    (100 mg)4- (1-tridecyloxyphenyl) thiomorpholine-1,1-dioxide (100 mg)
  • 4,4'-Butyliden-bis(3-methyl-6-t-butylphenol)    (50 mg)4,4'-butylidene-bis (3-methyl-6-t-butylphenol) (50 mg)
  • 2,2'-Isobutyliden-bis (4, 6-dimethylphenol)    (10 mg)2,2'-isobutylidene-bis (4,6-dimethylphenol) (10 mg)
  • 3,5-Dichloro-4-(hexadecyloxycarbonyloxy)ethylbenzoat    (20 mg)3,5-dichloro-4- (hexadecyloxycarbonyloxy) ethylbenzoate (20 mg)
  • 3,5-Bis[3-(2,4-di-t-amylphenoxy)propylcarbamoyl]natriumbenzolsulfinat    (20 mg)3,5-bis [3- (2,4-di-t-amylphenoxy) propylcarbamoyl] sodium benzenesulfinate (20 mg)
  • grünempfindliche Silberchlorobromid-emulsion    (150 mg)green-sensitive silver chlorobromide emulsion (150 mg)
Zweite GelatinezwischenschichtSecond layer of gelatin

  • Gelatine    (1000 mg)Gelatin (1000 mg)
  • 5-Chloro-2-(3,5-di-t-butyl-2-hydroxyphenyl)benz-1,2,3-triazol    (200 mg)5-chloro-2- (3,5-di-t-butyl-2-hydroxyphenyl) benz-1,2,3-triazole (200 mg)
  • 2-(3-Dodecyl-2-hydroxy-5-methylphenyl)benz-1,2,3-triazol    (200 mg)2- (3-dodecyl-2-hydroxy-5-methylphenyl) benz-1,2,3-triazole (200 mg)
  • Trinonylphosphat    (300 mg)Trinonyl phosphate (300 mg)
  • 2,5-Di-t-octylhydrochinon    (50 mg)2,5-di-t-octylhydroquinone (50 mg)
  • 5-[2,5-Dihydroxy-4-(4-hexyloxycarbonyl-1,1-dimethylbutyl)phenyl]-5-methylhexansäurehexylester   (50 mg)5- [2,5-Dihydroxy-4- (4-hexyloxycarbonyl-1,1-dimethylbutyl) phenyl] -5-methylhexanoic acid hexyl ester (50 mg)
Rotempfindliche SchichtRed sensitive layer

  • 2-[α-(2,4-Di-t-amylphenoxy)butanamido]-4,6-di-chloro-5-ethylphenol   (150 mg)2- [α- (2,4-di-t-amylphenoxy) butanamido] -4,6-di-chloro-5-ethylphenol (150 mg)
  • 2,4-Dichloro-3-ethyl-6-hexadecanamidophenol    (150 mg)2,4-dichloro-3-ethyl-6-hexadecanamidophenol (150 mg)
  • 4-Chloro-2-(1,2,3,4,5-pentafluorobenzamido)-5-[2-(2,4-di-t-amylphenoxy)-3-methylbutanamido]phenol   (100 mg)4-chloro-2- (1,2,3,4,5-pentafluorobenzamido) -5- [2- (2,4-di-t-amylphenoxy) -3-methylbutanamido] phenol (100 mg)
  • Dioctylphthalat    (100 mg)Dioctyl phthalate (100 mg)
  • Dicyclohexylphthalat    (100 mg)Dicyclohexyl phthalate (100 mg)
  • Gelatine    (1200 mg)Gelatin (1200 mg)
  • 5-Chloro-2-(3,5-di-t-butyl-2-hydroxyphenyl)benz-1,2,3-triazol    (100 mg)5-chloro-2- (3,5-di-t-butyl-2-hydroxyphenyl) benz-1,2,3-triazole (100 mg)
  • 2-(3-Dodecyl-2-hydroxy-5-methylphenyl)benz-1,2,3-triazol    (100 mg)2- (3-dodecyl-2-hydroxy-5-methylphenyl) benz-1,2,3-triazole (100 mg)
  • 3,5-Di-t-butyl-4-hydroxy-(2,4-di-t-amylphenyl)-benzoate    (50 mg)3,5-di-t-butyl-4-hydroxy- (2,4-di-t-amylphenyl) benzoate (50 mg)
  • Poly(N-t-butylacrylamid)    (300 mg)Poly (N-t-butylacrylamide) (300 mg)
  • N,N-Diethyl-2,4-di-t-amylphenoxyacetamid    (100 mg)N, N-diethyl-2,4-di-t-amylphenoxyacetamide (100 mg)
  • 2,5-Di-t-octylhydrochinon    (50 mg)2,5-di-t-octylhydroquinone (50 mg)
  • rotempfindliche Silberchlorobromid-emulsion   (200 mg)red sensitive silver chlorobromide emulsion (200 mg)

Die oberste Schicht wird mit und ohne UV-Absorber hergestellt
mit UV-Absorber:

  • 2,5-Di-t-octylhydrochinon    (20 mg)
  • 5-[2,5-Dihydroxy-4-(4-hexyloxycarbonyl-1,1-dimethylbutyl)phenyl]-5-methylhexansäurehexylester   (20 mg)
  • Gelatine    (400 mg)
  • Trinonylphosphat    (120 mg)
  • UV-Absorber Verb. Nr. (3)    (200 mg)
  • ohne UV-Absorber:
  • Gelatine    (800 mg)
The top layer is made with and without UV absorber
with UV absorber:
  • 2,5-di-t-octylhydroquinone (20 mg)
  • 5- [2,5-Dihydroxy-4- (4-hexyloxycarbonyl-1,1-dimethylbutyl) phenyl] -5-methylhexanoic acid hexyl ester (20 mg)
  • Gelatin (400 mg)
  • Trinonyl phosphate (120 mg)
  • UV absorber compound no. (3) (200 mg)
  • without UV absorber:
  • Gelatin (800 mg)

Als Härter wird 2,4-Dichlor-6-hydroxytriazin verwendet, als Netzmittel das Natriumsalz der Diisobutylnaphthalinsulfonsäure.2,4-dichloro-6-hydroxytriazine is used as the hardener and the sodium salt of diisobutylnaphthalenesulfonic acid as the wetting agent.

Auf die 2 Proben werden (mit blauem, grünem bzw. rotem Licht) jeweils drei Stufenkeile mit einem Dichteunterschied von 0, 15 kJ pro Stufe aufbelichtet.Three step wedges with a density difference of 0.15 kJ per step are exposed on the 2 samples (with blue, green or red light).

Anschliessend wird gemäss Verarbeitungsprozess RA-4 (Kodak) für Farbpapiere verfahren.The process is then carried out in accordance with processing process RA-4 (Kodak) for colored papers.

Nach Belichtung und Verarbeitung werden die Remissionsdichten im Rot für die Cyanstufe, im Grün für die Magentastufe und im Blau für die Gelbstufe bei einer Dichte zwischen 0,9 und 1,1 der Keile gemessen. Dann werden die Keile in einem Atlas-Belichtungsgerät mit insgesamt 15 kJ/cm2 belichtet und es werden erneut die Remissionsdichten gemessen.After exposure and processing, the reflectance densities are measured in red for the cyan level, in green for the magenta level and in blue for the yellow level at a density between 0.9 and 1.1 of the wedges. Then the wedges are exposed in an Atlas exposure device with a total of 15 kJ / cm 2 and the reflectance densities are measured again.

Auch bei dem Magentakeil wird die Remissionsdichte vor und nach der Belichtung im Blau für die Vergilbung gemessen.For the magenta wedge, the reflectance density is measured before and after the exposure in blue for yellowing.

Die Anwesenheit der UV-Absorber reduziert den Farbstoffdichteverlust des Cyan-, Magenta- und Gelbbildfarbstoffs.The presence of the UV absorbers reduces the loss of dye density of the cyan, magenta and yellow image dye.

Beispiel 13:Example 13: Herstellung von 2,4-Di-[2-hydroxy-4-(3-butoxy-2-hydroxypropoxy)phenyl]-6-methoxy-1,3,5-triazinPreparation of 2,4-di- [2-hydroxy-4- (3-butoxy-2-hydroxypropoxy) phenyl] -6-methoxy-1,3,5-triazine

10 g 2,4-Di-(2,4-dihydroxyphenyl)-6-methoxy-1,3,5-triazin werden mit 100 ml Butylglycidylether und 0,20 g Tetrabutylammoniumbromid drei Stunden bei 130°C gerührt. Anschliessend lässt man auf 80°C abkühlen, versetzt mit 100 ml Essigester und 2,0 g Prolith Rapid, filtriert über Kieselgur und entfernt das Lösungsmittel unter reduziertem Druck. Danach destilliert man den überschüssigen Butylglycidylether unter Vakuum ab. So erhält man 2,4-Di-[2-hydroxy-4-(3-butoxy-2-hydroxypropoxy)phenyl]-6-methoxy-1,3,5-triazin, dass nach Umkristallisierung aus Ethanol einen Schmelzpunkt von 108-109°C besitzt.10 g of 2,4-di- (2,4-dihydroxyphenyl) -6-methoxy-1,3,5-triazine are stirred for three hours at 130 ° C. with 100 ml of butyl glycidyl ether and 0.20 g of tetrabutylammonium bromide. The mixture is then allowed to cool to 80 ° C., mixed with 100 ml of ethyl acetate and 2.0 g of Prolith Rapid, filtered through diatomaceous earth and the solvent is removed under reduced pressure. The excess butyl glycidyl ether is then distilled off in vacuo. This gives 2,4-di- [2-hydroxy-4- (3-butoxy-2-hydroxypropoxy) phenyl] -6-methoxy-1,3,5-triazine that, after recrystallization from ethanol, has a melting point of 108- 109 ° C.

Verwendet man anstelle Butylglycidylether 2-Aethylhexylglycidylether, so erhält man 2,4-Di-{2-hydroxy-4-[3-(2-ethylhexoxy)-2-hydroxypropoxy]phenyl}-6-methoxy-1,3,5-triazin mit einem Schmelzpunkt von 98-99°C.If 2-ethylhexylglycidyl ether is used instead of butylglycidyl ether, 2,4-di- {2-hydroxy-4- [3- (2-ethylhexoxy) -2-hydroxypropoxy] phenyl} -6-methoxy-1,3,5- triazine with a melting point of 98-99 ° C.

Beispiel 14:Example 14:

Herstellung von

Figure imgb0156
wobei R100
Figure imgb0157
entsprichtProduction of
Figure imgb0156
where R 100
Figure imgb0157
corresponds

Zu einer Lösung von 15 g 2,4-Bis[2-hydroxy-4-(2-hydroxy-3-butoxypropyloxy)-phenyl]-6-phenyl-1,3,5-triazin und 7,15 g Imidazol in 100 ml N,N'-Dimethylacetamid wird unter Stickstoff 9,4 g Thexyl-dimethylchlorsilan getropft. Nach 12 Stunden bei Zimmertemperatur wird das Reaktionsgemisch im Rotavapor eingedampft. Der Rückstand wird in 200 ml Essigsäureethylesteraufgenommen. Nach der Filtration wird das Filtrat eingeengt und das erhaltene Rohprodukt auf Kieselgel (Laufmittel: Hexan/Essigsäureethylester 20:1) gereinigt. Man erhält 3,5 g der Verbindung als leicht gelbes Harz. Elementaranalyse:C51H79N3O8Si2 Berechnet: C 66,7; H 8,67; N 4,57 % Gefunden: C 66,38; H 8,80; N 4,42 % To a solution of 15 g of 2,4-bis [2-hydroxy-4- (2-hydroxy-3-butoxypropyloxy) phenyl] -6-phenyl-1,3,5-triazine and 7.15 g of imidazole in 100 ml of N, N'-dimethylacetamide is added dropwise under nitrogen to 9.4 g of thexyl-dimethylchlorosilane. After 12 hours at room temperature, the reaction mixture is evaporated in a Rotavapor. The residue is taken up in 200 ml of ethyl acetate. After the filtration, the filtrate is concentrated and the crude product obtained is purified on silica gel (eluent: hexane / ethyl acetate 20: 1). 3.5 g of the compound are obtained as a slightly yellow resin. Elemental analysis: C 51 H 79 N 3 O 8 Si 2 Calculated: C 66.7; H 8.67; N 4.57% Found: C 66.38; H 8.80; N 4.42%

Beispiel 15:Example 15: Herstellung einer Mischung von 2,4-Bis[2-hydroxy-4-(3'-n-butoxy-2'-hydroxy-propyloxy)phenyl]-6-phenyl-1,3,5-triazin und 2,4-Bis[2-hydroxy-4-(3'-(2-ethyl-hexyloxy)-2'-hydroxy-propyloxy)phenyl]-6-phenyl-1,3,5-triazinPreparation of a mixture of 2,4-bis [2-hydroxy-4- (3'-n-butoxy-2'-hydroxypropyloxy) phenyl] -6-phenyl-1,3,5-triazine and 2,4- Bis [2-hydroxy-4- (3 '- (2-ethylhexyloxy) -2'-hydroxypropyloxy) phenyl] -6-phenyl-1,3,5-triazine

Eine Mischung von 20,0 g 2,4-Bis[2,4-dihydroxy-phenyl]-6-phenyl-1,3,5-triazin, 7,7 g n-Butyl-glycidylether, 10,9 g 2-Ethylhexyl-glycidylether und 2,0 g Phosphor-triphenylethyl-bromid wird in 100 ml Mesitylen während 5 Stunden bei 150°C gehalten. Mesitylen wird mit dem Rotavapor entfernt und das Rohprodukt in 50 ml Ethylacetat aufgenommen. Man gibt die Lösung auf eine Kieselgelschicht (2 cm) und eluiert mit 200 ml Ethylacetat. Nach dem Entfernen des Lösungsmittels kristallisiert man in 60 ml Ethylacetat um und erhält 28,9 g der Mischung der Verbindungen als einen hellgelben Feststoff (Smp. 66-70°C). Elementaranalyse:C39H51N3O8 Berechnet: C 67,90; H 7,45; N 6,09 % Gefunden: C 67,64; H 7,43; N 6,02 % A mixture of 20.0 g of 2,4-bis [2,4-dihydroxyphenyl] -6-phenyl-1,3,5-triazine, 7.7 g of n-butyl glycidyl ether, 10.9 g of 2- Ethylhexyl glycidyl ether and 2.0 g of phosphorus triphenylethyl bromide are kept in 100 ml of mesitylene for 5 hours at 150 ° C. Mesitylene is removed with the Rotavapor and the crude product is taken up in 50 ml of ethyl acetate. The solution is poured onto a layer of silica gel (2 cm) and eluted with 200 ml of ethyl acetate. After removal of the solvent, the product is recrystallized from 60 ml of ethyl acetate and 28.9 g of the mixture of the compounds are obtained as a light yellow solid (mp. 66-70 ° C.). Elemental analysis: C 39 H 51 N 3 O 8 Calculated: C 67.90; H 7.45; N 6.09% Found: C 67.64; H 7.43; N 6.02%

Beispiel 16:Example 16: Herstellung von 2,4-Bis[2-hydroxy-4-(3'-n-butoxy-2'-methoxycarbonyloxy-propoxy)-phenyl]-6-phenyl-1,3,5-triazinPreparation of 2,4-bis [2-hydroxy-4- (3'-n-butoxy-2'-methoxycarbonyloxypropoxy) phenyl] -6-phenyl-1,3,5-triazine

Eine Mischung von 5,0 g 2,4-Bis[2-hydroxy-4-(3'-n-butoxy-2'-hydroxy-propyloxy)-phenyl]-6-phenyl-1,3,5-triazin, 8,7 g Methylchlorformiat und 2 Tropfen Pyridin wird in 50 ml Toluol während 40 Stunden bei 100°C gehalten. Die Mischung wird am Rotavapor eingedampft und auf einer Kieselgelsäule mit Ethylacetat/Petrolether (1:1) gereinigt. Man erhält 3,3 g der Verbindung als leicht gelbes Harz. Elementaranalyse:C39H47N3O12 Berechnet: C 62,47; H 6,32; N 5,60 % Gefunden: C 62,34; H 6,41; N 5,39 % A mixture of 5.0 g of 2,4-bis [2-hydroxy-4- (3'-n-butoxy-2'-hydroxypropyloxy) phenyl] -6-phenyl-1,3,5-triazine, 8.7 g of methyl chloroformate and 2 drops of pyridine are kept in 50 ml of toluene at 100 ° C. for 40 hours. The mixture is evaporated on a Rotavapor and purified on a silica gel column with ethyl acetate / petroleum ether (1: 1). 3.3 g of the compound are obtained as a slightly yellow resin. Elemental analysis: C 39 H 47 N 3 O 12 Calculated: C 62.47; H 6.32; N 5.60% Found: C 62.34; H 6.41; N 5.39%

Beispiel 17:Example 17: Herstellung von 2,4-Bis[2-hydroxy-4-(3'-n-butoxy-2'-valeroyloxy-propoxy)-phenyl]-6-phenyl-1,3,5-triazinPreparation of 2,4-bis [2-hydroxy-4- (3'-n-butoxy-2'-valeroyloxypropoxy) phenyl] -6-phenyl-1,3,5-triazine

Eine Mischung von 5,0 g 2,4-Bis[2-hydroxy-4-(3'-n-butoxy-2'-hydroxy-propyloxy)-phenyl]-6-phenyl-1,3,5-triazin, 2,2 g Valeroylchlorid und 5 Tropfen Pyridin wird in 50 ml Toluol während 5 Stunden bei 80-85°C gehalten, wobei HCl entweicht. Die Mischung wird am Rotavapor eingedampft und auf einer Kieselgelsäule (Kieselgel 60, 230-400 mesh) mit Ethylacetat/Petrolether (4:1) gereinigt. Man erhält 4,4 g der Verbindung als leicht gelbes dickes Öl. Elementaranalyse:C45H59N3O10 Berechnet: C 67,40; H 7,41; N 5,23 % Gefunden: C 67,32; H 7,61; N 5,14 % A mixture of 5.0 g of 2,4-bis [2-hydroxy-4- (3'-n-butoxy-2'-hydroxypropyloxy) phenyl] -6-phenyl-1,3,5-triazine, 2.2 g of valeroyl chloride and 5 drops of pyridine are kept in 50 ml of toluene at 80-85 ° C. for 5 hours, during which HCl escapes. The mixture is evaporated on a Rotavapor and purified on a silica gel column (silica gel 60, 230-400 mesh) with ethyl acetate / petroleum ether (4: 1). 4.4 g of the compound are obtained as a slightly yellow, thick oil. Elemental analysis: C 45 H 59 N 3 O 10 Calculated: C 67.40; H 7.41; N 5.23% Found: C 67.32; H 7.61; N 5.14%

Beispiel 18:Example 18: Herstellung von 2,4-Bis[2-hydroxy-4-(3'-n-butoxy-2'-acetoxy-propoxy)-phenyl]-6-phenyl-1,3,5-triazinPreparation of 2,4-bis [2-hydroxy-4- (3'-n-butoxy-2'-acetoxypropoxy) phenyl] -6-phenyl-1,3,5-triazine

Eine Mischung von 4,0 g 2,4-Bis[2-hydroxy-4-(3'-n-butoxy-2'-hydroxy-propyloxy)-phenyl]-6-phenyl-1,3,5-triazin, 1,6 g Acetylchlorid und 2 Tropfen Pyridin wird in 50 ml Toluol während 4 Stunden bei 60°C gehalten, wobei HCl entweicht. Die Mischung wird am Rotavapor eingedampft, mit 300 ml Ethylacetat aufgenommen und durch eine Kieselgelschicht (1 cm; Kieselgel 60, 230-400 mesh) filtriert. Nach dem Abziehen des Lösungsmittels erhält man 4,4 g der Verbindung als leicht gelbes Harz. Elementaranalyse:C39H47N3O10 Berechnet: C 65,26; H 6,60; N 5,85 % Gefunden: C 64,85; H 6,76; N 5,60 % A mixture of 4.0 g of 2,4-bis [2-hydroxy-4- (3'-n-butoxy-2'-hydroxypropyloxy) phenyl] -6-phenyl-1,3,5-triazine, 1.6 g of acetyl chloride and 2 drops of pyridine are kept in 50 ml of toluene at 60 ° C. for 4 hours, during which HCl escapes. The mixture is evaporated on a Rotavapor, taken up with 300 ml of ethyl acetate and filtered through a layer of silica gel (1 cm; silica gel 60, 230-400 mesh). After the solvent has been stripped off, 4.4 g of the compound are obtained as a slightly yellow resin. Elemental analysis: C 39 H 47 N 3 O 10 Calculated: C 65.26; H 6.60; N 5.85% Found: C 64.85; H 6.76; N 5.60%

Claims (12)

  1. A photographic material comprising, on a base, blue-sensitive, green-sensitive and/or red-sensitive silver-halide emulsion layers and, if desired, a protection layer, a layer containing a UV absorber being arranged between the uppermost silver-halide emulsion layer and the protection layer or on top of the uppermost silver-halide emulsion layer, wherein the UV absorber conforms to the formula
    Figure imgb0184
    in which the radicals R1, independently of one another, are radicals of the formula
    -CH2-CH(ORx)Ry, -CH2CH(ORx)CH2ORz,
    Figure imgb0185
    -CH2CORy or -CH2COCH2ORz, where Rx is H, -CORs, -COORw or -SiRpRqRr, Ry is C1-C18alkyl or phenyl-C1-C4alkyl, Rz is C1-C18alkyl, C2-C18alkenyl, phenyl-C1-C4alkyl, -CORs or oxygen-interrupted C1-C24alkyl or C2-C24hydroxyalkyl, Rs is C1-C18alkyl, C2-C18alkenyl or phenyl, Rw is C1-C4alkyl and Rp, Rq and Rr, independently of one another, are C1-C6alkyl or phenyl;
    or the radicals R1, independently of one another, are G-II groups, where II is a group of the formula
    Figure imgb0186
    and G is a direct bond or a divalent group of one of the following formulae:
    -(CH2)q-, -(CH2)q-O-, -(CH2)q-O-R26-, -(CH2)q-CO-X-(CH2)r-, -(CH2)q-CO-X-(CH2)r-O-,
    Figure imgb0187
    Figure imgb0188
    or -CH2-CH(OH)-CH2-Y-(CH2)q-, in which q and r, independently of one another, are 1-4 and p is 0-50, R26 is C1-C12alkylene, cyclohexylene or phenylene, R27 is C1-C12alkyl, C5-C8cycloalkyl, phenyl, C2-C13alkoxymethyl, C6-C9cycloalkoxymethyl or phenoxymethyl, R28 is a group of the formula G-II, R29 is hydrogen or methyl, X is -O- or -NR23-, in which R23 is hydrogen, C1-C12alkyl or a -(CH2)3-G-II or -(CH2)3-O-G-II group, Y is -O- or -NH-, and R20, R21 and R22, independently of one another, are C1-C18alkyl, cyclohexyl, phenyl or C1-C18alkoxy and
    R12 is alkyl having 1 to 12 carbon atoms or a group of the formula
    Figure imgb0189
    or
    -OR16 , preferably a group of the formula
    Figure imgb0190
    in which R13 and R14,
    independently of one another, are hydrogen, C1-C4alkyl or chlorine, and R16 is alkyl having 1 to 8 carbon atoms or oxygen-interrupted alkyl having 3 to 12 carbon atoms.
  2. A photographic material as claimed in claim 1, wherein the radicals R1, independently of one another, are radicals of the formula -CH2-CH(ORx)Ry, -CH2CH(ORx)CH2X)z, -CH2CORy or -CH2COCH2ORz , where Rx is H, -CORs, -COORw or -SiRpRqRr, Ry is C1-C8alkyl, Rz is C1-C18alkyl, C2-C18alkenyl, benzyl, -CORs or oxygen-interrupted C1-C24alkyl or C2-C24hydroxyalkyl, Rs is C1-C18alkyl, C2-C18alkenyl or phenyl, Rw is C1-C4alkyl, and Rp, Rq and Rr, independently of one another, are C1-C6alkyl; or R1 is a G-II group, where II is a group of the formula
    Figure imgb0191
    and G is a direct bond or a divalent group of one of the following formulae: -(CH2)q-, -(CH2)q-O-, -(CH2)q-CO-X-(CH2)r-,
    Figure imgb0192
    or
    -CH2-CH(OH)-CH2-Y-(CH2)q-, in which q and r, independently of one another, are 1, 2 or 3 and p is 0-50, R27 is methyl, phenyl, C3-C9alkoxymethyl or phenoxymethyl, R28 is a group of the formula G-II, X and Y are -O-, R20, R21 and R22, independently of one another, are C1-C8alkyl, phenyl or C1-C8alkoxy; and R12 is a group of the formula
    Figure imgb0193
    in which R13 and R14, independently of one another, are hydrogen, C1-C4alkyl or chlorine.
  3. A photographic material as claimed in claim 1, which includes a further layer containing a UV absorber of the formula (I), which is arranged between the green-sensitive and red-sensitive silver-halide emulsion layers, or where the UV absorber of the formula (I) is additionally present in the red-sensitive silver-halide emulsion layer, wherein a UV absorber of the benzotriazole type, in particular of the formula
    Figure imgb0194
    in which T1, T2 and T3, independently of one another, are hydrogen, halogen, alkyl, carboxylate-substituted alkyl, alkoxy, aryloxy, hydroxyl or acyloxy, and T4 is hydrogen, alkoxy, aryloxy or acyloxy,
    replaces the UV absorber of the formula (I) in the further layer and/or in the red-sensitive silver-halide emulsion layer.
  4. A photographic material comprising, on a base, blue-sensitive, green-sensitive and/or red-sensitive silver-halide emulsion layers and a protection layer, a layer containing a UV absorber being arranged between the uppermost silver-halide emulsion layer and the protection layer, wherein (a) the UV absorber conforms to the formula
    Figure imgb0195
    in which T1, T2 and T3, independently of one another, are hydrogen, halogen, alkyl, carboxylate-substituted alkyl, alkoxy, aryloxy, hydroxyl or acyloxy, and T4 is hydrogen, alkoxy, aryloxy or acyloxy, and (b) the material contains at least one further layer containing a UV absorber of the formula (I).
  5. A photographic material comprising, on a base, at least 2 silver-halide emulsion layers with a UV absorber-containing layer between these layers, wherein the UV absorber conforms to the formula (I).
  6. A photographic material comprising, on a base, a red-sensitive silver halide emulsion layer and, if desired, blue-sensitive and/or green-sensitive silver-halide emulsion layers, wherein the red-sensitive silver-halide emulsion layer contains a UV absorber of the formula (I).
  7. A photographic material as claimed in any one of claims 1 to 6, wherein a mixture of the UV absorbers of the formulae (I) and (III) is present in the layers which may contain a UV absorber.
  8. A photographic material as claimed in claim 1, 4, 5 or 6, wherein the red-sensitive silver-halide emulsion layer contains a cyan coupler of the formula
    Figure imgb0196
    and/or of the formula
    Figure imgb0197
    in which Z1 is alkyl or aryl, Z2 is alkyl, cycloalkyl, aryl, a heterocyclic group or a ballast group, Z3 is hydrogen or halogen, Z1 and Z3 together can form a ring, and Z4 is hydrogen or a leaving group, and Z5 is a ballast group, Z6 is hydrogen or a leaving group, and Z7 is alkyl.
  9. A photographic material as claimed in claim 1, 4, 5 or 6, wherein the green-sensitive silver-halide emulsion layer contains a magenta coupler of the formula
    Figure imgb0198
    in which R1 is hydrogen or a substituent, Z represents the non-metallic atoms necessary for completion of the 5-membered ring containing 2 or 3 nitrogen atoms, it being possible for this ring to be substituted, and Q is hydrogen or a leaving group.
  10. A photographic material as claimed in claim 1, 4, 5 or 6, wherein the green-sensitive silver-halide emulsion layer contains a magenta coupler of the formula
    Figure imgb0199
    in which R20 is hydrogen, alkyl, acylamino, carbamoyl, sulfamoyl, sulfonamido, alkoxycarbonyl, acyloxy or a urethane group, and Q' is a leaving group.
  11. A compound of the formula
    Figure imgb0200
    in which the radicals R1, independently of one another, are radicals of the formula
    -CH2-CH(ORx)Ry, -CH2CH(ORx)CH2ORz,
    Figure imgb0201
    -CH2CORy or -CH2COCH2ORz, where Rx is -CORs, -COORw or -SiRpRqRr, Ry is C1-C18alkyl or phenyl-C1-C4alkyl, Rz is C1-C18alkyl, C2-C18alkenyl, phenyl-C1-C4alkyl, -CORs or oxygen-interrupted C1-C24alkyl or C2-C24hydroxyalkyl, Rs is C1-C18alkyl, C2-C18alkenyl or phenyl, Rw is C1-C4alkyl and Rp, Rq and Rr, independently of one another, are C1-C6alkyl or phenyl;
    or the radicals R1, independently of one another, are G-II groups, where II is a group of the formula
    Figure imgb0202
    and G is a direct bond or a divalent group of one of the following formulae:
    -(CH2)q-, -(CH2)q-O-, -(CH2)q-O-R26-, -(CH2)q-CO-X-(CH2)r-, -(CH2)q-CO-X-(CH2)r-O-,
    Figure imgb0203
    Figure imgb0204
    or -CH2-CH(OH)-CH2-Y-(CH2)q-, in which q and r, independently of
    one another, are 1-4 and p is 0-50, R26 is C1-C12alkylene, cyclohexylene or phenylene, R27 is C1-C12alkyl, C5-C8cycloalkyl, phenyl, C2-C13alkoxymethyl, C6-C9cycloalkoxymethyl or phenoxymethyl, R28 is a group of the formula G-II, R29 is hydrogen or methyl, X is -O- or -NR23-, in which R23 is hydrogen, C1-C12alkyl or a -(CH2)3-G-II or -(CH2)3-O-G-II
    group, Y is -O- or -NH-, and R20, R21 and R22, independently of one another, are C1-C18alkyl, cyclohexyl, phenyl or C1-C18alkoxy and
    R12 is alkyl having 1 to 12 carbon atoms or a group of the formula
    Figure imgb0205
    or
    -OR16, preferably a group of the formula
    Figure imgb0206
    in which R13 and R14,
    independently of one another, are hydrogen or C1-C4alkyl and, if R1 is not -CH2CH(OCORs)CH3, may also be chlorine, and R16 is alkyl having 1 to 8 carbon atoms or oxygen-interrupted alkyl having 3 to 12 carbon atoms.
  12. A compound as claimed in claim 11, in which the radicals R1, independently of one another, are radicals of the formula -CH2-CH(ORx)Ry, -CH2CH(ORx)CH2OR)z, -CH2CORy or -CH2COCH2ORz, where Rx is -CORs, -COORw or -SiRpRqRr, Ry is C1-C8alkyl, Rz is C1-C18alkyl, C2-C18alkenyl, benzyl, -CORs or oxygen-interrupted C1-C24alkyl or C2-C24hydroxyalkyl, Rs is C1-C18alkyl, C2-C18alkenyl or phenyl, Rw is C1-C4alkyl, and Rp, Rq and Rr, independently of one another, are C1-C6alkyl; or R1 is a G-II group, where II is a group of the formula
    Figure imgb0207
    and G is a direct bond or a divalent group of one of the following formulae: -(CH2)q-,
    -(CH2)q-O-, -(CH2)q-CO-X-(CH2)r-,
    Figure imgb0208
    or
    -CH2-CH(OH)-CH2-Y-(CH2)q-, in which q and r, independently of one another, are 1, 2 or 3 and p is 0-50, R27 is methyl, phenyl, C3-C9alkoxymethyl or phenoxymethyl, R28 is a group of the formula G-II, X and Y are -O-, R20, R21, and R22, independently of one another, are C1-C8alkyl, phenyl or C1-C8alkoxy; and R12 is a group of the formula
    Figure imgb0209
    in which R13 and R14, independently of one another, are hydrogen or
    C1-C4alkyl and, if R1 is not -CH2CH(OCORs)CH3, may also be chlorine.
EP92810397A 1991-06-03 1992-05-26 UV-absorber containing photographic material Expired - Lifetime EP0520938B1 (en)

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JP3156109B2 (en) 2001-04-16
US5364749A (en) 1994-11-15
US5488108A (en) 1996-01-30
JPH05307232A (en) 1993-11-19
EP0520938A1 (en) 1992-12-30

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