Classifications

• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
  • G03C1/00—Photosensitive materials
  • G03C1/76—Photosensitive materials characterised by the base or auxiliary layers
  • G03C1/815—Photosensitive materials characterised by the base or auxiliary layers characterised by means for filtering or absorbing ultraviolet light, e.g. optical bleaching
  • G03C1/8155—Organic compounds therefor
• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
  • G03C7/00—Multicolour photographic processes or agents therefor; Regeneration of such processing agents; Photosensitive materials for multicolour processes
  • G03C7/30—Colour processes using colour-coupling substances; Materials therefor; Preparing or processing such materials
  • G03C7/392—Additives
  • G03C7/39208—Organic compounds
  • G03C7/3924—Heterocyclic
  • G03C7/39244—Heterocyclic the nucleus containing only nitrogen as hetero atoms
  • G03C7/39256—Heterocyclic the nucleus containing only nitrogen as hetero atoms three nitrogen atoms
• • Y—GENERAL 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
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10S430/00—Radiation imagery chemistry: process, composition, or product thereof
  • Y10S430/132—Anti-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 commonly 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 hydroxyphenylbenzotriazole 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 hydroxyphenylbenzotriazole 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 violin 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.
• 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 corresponds to what the radicals R1 independently of one another are alkyl having 1 to 18 carbon atoms, alkyl having 1 to 18 carbon atoms substituted by hydroxyl, alkenoxy having 2 to 18 carbon atoms, -CO2H, -CO2R2 and / or -O-COR5 by alkyl or hydroxyalkyl or glycidyloxyalkyl interrupted by oxygen 3 to 50 carbon atoms, alkenyl with 3 to 6 carbon atoms, glycidyl, a group of the formula Cyclopentyl, cyclohex
• 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 are alkyl residues with 3 to 50 carbon atoms which are interrupted by oxygen, sulfur or nitrogen and Alkenyl radicals with 2 to 18 carbon atoms can be mono- or, from 4 carbon atoms, polyunsaturated.
• Dialkylaminoalkyl radicals with a total of 4 to 16 carbon atoms can be represented, for example, by the formula are reproduced, the sum of n 1, n 2 and n 3 giving 4 to 16, alkylene radicals having 2 to 10 carbon atoms can be derived from corresponding alkyl radicals.
• Akylene residues with 4 to 50 carbon atoms interrupted by oxygen can, for example, of the formula correspond.
• radicals R1 independently of one another are a radical of the formula -CH2-CH (OR x ) R y , -CH2CH (OR x ) CH2OR z , -CH2COR y or -CH2COCH2OR z mean, wherein R x H, -COR s , -COOR w or -SiR p R q R r , R y C1-C18-alkyl or phenyl-C1-C4-alkyl, R z is C1-C1 Alkyl alkyl, C2-C18 alkenyl, phenyl-C1-C4-alkyl, -COR s or C1-C24-alkyl interrupted by oxygen or C2-C24-hydroxyalkyl, R s C1-C18 alkyl, C2-C18 alkenyl or phenyl, R w C1-C4 al
• R1 independently of one another are radicals of the formula -CH2-CH (OR x ) R y , -CH2CH (OR x ) CH2OR z , -CH2COR y or -CH2COCH2OR z , where R x H, -COR s , -COOR w or -SiR p R q R r , R y C1-C8 alkyl, R z C1-C18-alkyl, C2-C18-alkenyl, benzyl, -COR s or C1-C24-alkyl interrupted by oxygen or C2-C24-hydroxyalkyl, R s C1-C18 alkyl, C2-C18 alkenyl or phenyl, R w C1-C4 alkyl and R p , R q and R r independently of one another are C1-C6-alkyl; or R1 represent a group G
• radicals R1 independently of one another are a radical of the formula -CH2-CH (OR x ) R y or -CH2CH (OR x ) CH2OR z , where R x H, -COR s , -COOCH3 or -Si (CH3) 2R r , R y C1-C8 alkyl, R z C1-C18-alkyl, C2-C18-alkenyl, -COR s or C1-C24-alkyl interrupted by oxygen or C2-C24-hydroxyalkyl, R s C1-C4 alkyl or C2-C4 alkenyl and R r C1-C6 alkyl mean; or R1 is a group G-II, where II is a group of formula is and p is 0, G is a divalent group of one of the following formulas: - (CH2) 3-, - (CH2) 2-O-,
• R1 independently of one another are a radical of the formula -CH2CH (OR x ) CH2OR z , where R x H, -COR s , -COOCH3 or -Si (CH3) 2R r , R z C1-C18-alkyl, C2-C18-alkenyl, -COR s or C1-C24-alkyl interrupted by oxygen or C2-C24-hydroxyalkyl, R s C1-C4 alkyl or C2-C4 alkenyl and R r C1-C6 alkyl mean; and R12 is a group of the formula is what R13 is hydrogen and R14 are hydrogen, methyl or chlorine.
• 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
• T1, T2 and T3 are independently hydrogen, halogen, alkyl, alkyl substituted with a carboxylic acid ester group, alkoxy, aryloxy, hydroxyl or acyloxy, and T4 is hydrogen, alkoxy, aryloxy or acyloxy.
• the present invention also relates to photographic material containing 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 T1, T2 and T3 are independently hydrogen, halogen, alkyl, alkyl substituted with a carboxylic acid ester group, alkoxy, aryloxy, hydroxyl or acyloxy and T4 is hydrogen, alkoxy, aryloxy or acyloxy, and (b) the material is at least one more Has 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) in the further layer or in the red-sensitive layer is replaced by one of the formula (III); 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 on a support 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.
• 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 in 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.
• 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 R1 is alkyl or aryl, R2 is aryl and Q is hydrogen or a group which can be split off by reaction with the oxidized developer.
• a group of yellow couplers are those compounds of the formula A in which R1 is t-butyl and R2 is a group of the formula is in which R3 is hydrogen, halogen, alkyl or alkoxy and R4, R5 and R6 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 mean.
• R3 is chlorine
• R4 and R5 are hydrogen and R6 is an acylamino group.
• This also includes the compounds of the formula wherein x is 0-4, R7 is hydrogen or alkyl and R8 and R9 are alkyl.
• R10 is hydrogen, halogen or alkoxy
• R11, R12 and R13 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 R1 and Q have the meaning given above.
• R1 is t-butyl
• R10 is chlorine
• R11 and R13 are hydrogen
• R12 is alkoxycarbonyl
• the leaving group Q can be hydrogen or it is a heterocyclic group wherein R14 is an organic divalent group that complements the ring to a 4-7 membered ring, or Q is a group -OR15, wherein R15 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. be 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,
• R16 is hydrogen, alkyl, aryl, alkenyl or a heterocyclic group.
• R17 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.
• R17 is preferably a group wherein R18 is imino, acylamino or ureido, R19 is hydrogen, halogen, alkyl or alkoxy, R20 is hydrogen, alkyl, acylamino, carbamoyl, sulfamoyl, sulfonamido, alkoxycarbonyl, acyloxy or a urethane group.
• magenta coupler is tetra equivalent with respect to that Silver halide.
• Typical examples of this type of magenta coupler are compounds of the formula wherein R20 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 are represented, wherein R1 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.
• magenta couplers of the formulas are preferred R11, R12 and R13 independently of one another, for example, hydrogen, halogen, a group of formula -CR3, wherein the radicals R are independently 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, heterocyclyl-oxy, azo, acyloxy, carbamoyloxy, silyloxy, aryloxycarbonylamino, sulfonyl, imido Aryloxycarbonyl, acyl or azolyl, and
• 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 R11 are alkyl, aryl, alkoxy, aryloxy, alkylthio, ureido, urethane and acylamino groups.
• R12 can have the meaning of R11 and is preferably hydrogen, alkyl, aryl, a heterocyclic ring, alkoxycarbonyl, carbamoyl, sulfamoyl, sulfinyl, acyl or cyano.
• R13 can have the meaning of R11 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 R11.
• 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.
• Q can contain photographically active groups such as development inhibitors or development accelerators.
• Q is halogen, alkoxy, aryloxy, alkyl, arylthio, or a 5- or 6-membered nitrogen-containing heterocyclic group which is attached 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 R21, R22, R23 and R24 are hydrogen, halogen, alkyl, carbamoyl, amino, sulfonamido, phosphoramido or ureido. R21 is preferably H or Cl, R22 is preferably an alkyl or amino group. R23 is preferably an amino group and R24 is preferably hydrogen. Q ⁇ is hydrogen or a leaving group which is split off in the reaction with the oxidized developer. A detailed list of cyan couplers can be found in US-A-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 to use in which Z1 alkyl, aryl, Z2 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 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-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
• 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 facilitate the incorporation of 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. If 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.
• the amount of high boiling solvent is e.g. in the range of 50 mg to 2 g per m2 of support, preferably from 200 mg to 1 g per m2.
• 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, of gallic acid or of 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 explained 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 greater 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,
• 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 to any desired wavelength by means of sensitizing pigments.
• Cyanine pigments, merocyanine pigments, holopolar pigments, hemicyanine pigments, styryl pigments or hemioxanol pigments can be used for this purpose.
• Water-soluble dyes may be included in the photosensitive material to improve clarity, for example, by preventing radiation damage.
• Oxonol dyes, hemioxonol dyes, styryl dyes, merocyanine dyes, cyanine dyes, anthraquinone dyes and azo dyes can be used for this.
• the present invention also relates to compounds
• R1 is alkyl having 1 to 18 carbon atoms, oxygen-interrupted alkyl or hydroxyalkyl having 3 to 50 carbon atoms or -CH2CH (OH) R, wherein R9 is phenylalkyl having 1 to 6 carbon atoms in the alkyl part or -CH2OR11, wherein R11 is cyclohexyl, tolyl, Is phenyl or benzyl, and R12 is -OR16, wherein R16 is alkyl of 1 to 18 carbon atoms or oxygen-interrupted alkyl of 3 to 18 carbon atoms.
• R1 is alkyl having 1 to 8 carbon atoms, alkyl interrupted by oxygen or hydroxyalkyl having 3 to 20 carbon atoms or -CH2CH (OH) R9, where R9 is CH2OR11, wherein R11 is benzyl, and R12 is -OR16 , wherein R16 is alkyl having 1 to 8 carbon atoms or alkyl interrupted by oxygen having 3 to 10 carbon atoms.
• the present invention further relates to compounds of the formula wherein R1 independently of one another is a radical of the formula -CH2-CH (OR x ) R y , -CH2CH (OR x ) CH2OR z , -CH2COR y or -CH2COCH2OR z mean, wherein R x -COR s , -COOR w or -SiR p R q R r , R y C1-C18-alkyl or phenyl-C1-C4-alkyl, R z C1-C18 alkyl, C2-C18 alkenyl, phenyl-C1-C4 alkyl, -COR s or by oxygen interrupted C1-C24-alkyl or C2-C24-hydroxyalkyl, R s C1-C18 alkyl, C2-C18 alkenyl or phenyl, R w C1-C4 alkyl and R p , R
• R1 independently of one another are the radicals of the formula -CH2-CH (OR x ) R y , -CH2CH (OR x ) CH2OR z , -CH2COR y or -CH2COCH2OR z , where R x -COR s , -COOR w or -SiR p R q R r , R y C1-C8 alkyl, R z C1-C18-alkyl, C2-C18-alkenyl, benzyl, -COR s or C1-C24-alkyl interrupted by oxygen or C2-C24-hydroxyalkyl, R s C1-C18 alkyl, C2-C18 alkenyl or phenyl, R w C1-C4 alkyl and R p , R q and R r independently of one another C1-C6-alkyl mean; or R1 represent a group
• 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).
• the gelatin layers contain the following components (per m2 carrier material):
• 2,4-dichloro-6-hydroxytriazine is used as the hardener, 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 for the magenta step 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 45 kJ / cm2 and the remission density is measured again.
• the dye loss (- ⁇ D) in% is given in Table 2.
• the procedure is as in Example 1, but without a stabilizer and using a cyan coupler.
• the composition of the gelatin layers (per m2) is as follows:
• the amounts of the cyan coupler are given in Table 3: After exposure and processing as described in Example 1, the reflectance density in red for the cyan level 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 / cm2 and the remission density is measured again.
• the dye density loss (- ⁇ D) in% is given in Table 3.
• 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 2 The procedure is as in Example 1, but without a stabilizer and using a yellow coupler.
• composition of the gelatin layers (per m2) is as follows:
• 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 / cm2 and the remission density is measured again.
• the dye loss (- ⁇ D) in% is given in Table 4.
• magenta coupler and stabilizer are given in Table 5.
• the reflectance density in blue for yellowing is measured. Then the wedge is exposed in a Atlas exposure device with a total of 15 kJ / cm2, the reflectance density (in blue) is measured again and the yellow dye increase (- ⁇ D B ) is calculated. The yellowing is shown in Table 5.
• 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.
• a gelatin layer which contains 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 (per m2 carrier material)
• the reflectance density in red for the cyan level 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 / cm2 and the remission density is measured again.
• the dye loss (- ⁇ D) in% is given in Table Y.
• a photographic material with the following layer structure is produced:
• gelatin layers consist of the following components (per m2 carrier material):
• a protective layer is made with and without UV absorber
• 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 each 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 / cm2 and the remission densities are measured again.
• the remission density of the magenta wedge 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.
• a photographic material with the following layer structure is produced:
• gelatin layers consist of the following components (per m2 carrier material):
• the top layer is made with and without UV absorber
• 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)
• 2,4-dichloro-6-hydroxytriazine is used as the hardener, 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 / cm2 and the remission densities are measured again.
• the remission density of the magenta wedge 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.

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• 1992
  • 1992-05-26 DE DE59208921T patent/DE59208921D1/de not_active Expired - Fee Related
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