WO2000014126A1 - Systeme chromophore photostable - Google Patents

Systeme chromophore photostable Download PDF

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Publication number
WO2000014126A1
WO2000014126A1 PCT/EP1999/006323 EP9906323W WO0014126A1 WO 2000014126 A1 WO2000014126 A1 WO 2000014126A1 EP 9906323 W EP9906323 W EP 9906323W WO 0014126 A1 WO0014126 A1 WO 0014126A1
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WIPO (PCT)
Prior art keywords
layer
polyvinyl alcohol
chromophore
polymer
acrylate
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PCT/EP1999/006323
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German (de)
English (en)
Inventor
Sameer Eldin
Original Assignee
Ciba Specialty Chemicals Holding Inc.
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Application filed by Ciba Specialty Chemicals Holding Inc. filed Critical Ciba Specialty Chemicals Holding Inc.
Priority to AU58560/99A priority Critical patent/AU5856099A/en
Publication of WO2000014126A1 publication Critical patent/WO2000014126A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F8/00—Chemical modification by after-treatment
    • C08F8/30—Introducing nitrogen atoms or nitrogen-containing groups
    • 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

Definitions

  • the present invention relates to a composition containing in the given order
  • the present invention relates to further compositions, intermediates, processes for producing the compositions and intermediates according to the invention and their uses.
  • Colored polymers are known from EP-A 337 951 and EP-A 787 731, which can be prepared by copolymerizing polyreactive colorants with conventional organic monomers. For some applications, however, the oxygen and light stabilities are insufficient.
  • the patent application EP-A 570 975 and the prior art discussed therein describe measures, inter alia, against the fading of dyes by the action of light, heat and moisture.
  • the silver halide-containing photographic element claimed in EP-A 570 975 therefore contains a support impregnated with polyvinyl alcohol as an oxygen barrier and at least one color-forming layer applied thereon, comprising a silver halide, a magenta coupler and an epoxide.
  • the epoxy is intended to prevent yellowing of areas that do not contain any dye.
  • a light stabilizer layer (UV absorber) is also used. It is applied to the color-forming layer that is still free, so that the oxygen barrier layer and the light stabilizer layer are located on opposite sides of the color-forming layer.
  • the object of the present invention was therefore to provide an improved protection system which increases the photostability of a chromophore.
  • a composition should be made available whose chromophore layer can be obtained from polyreactive colorants or from optical brighteners.
  • the protection system should be able to be used for the production of paints, in particular automotive paints.
  • compositions, intermediates, processes for producing the compositions and intermediates according to the invention and their uses have been found.
  • the composition has a layer sequence in which the light stabilizer layer is applied to the chromophore layer, the oxygen barrier layer to the light stabilizer layer and, if desired, the clear lacquer protective layer thereon.
  • a clear lacquer protective layer is used on the oxygen barrier layer.
  • the chromophore layer is usually applied to a carrier material.
  • Chromophore layer usually consists of a polymer that contains a chromophore either covalently or non-covalently bound.
  • chromophore used here includes both colorants and substances which absorb in the UV and / or visible range, such as optical brighteners, all dyes and pigments being suitable as colorants.
  • Organic and inorganic pigments are particularly preferred as pigments.
  • organic pigments examples include azo pigments, in particular monoazo yellow and orange pigments, disazo, ⁇ -naphthol, naphthol-AS, lacquered azo, benzimidazolone, disazo condensation, metal complex, isoindolinone and isoindoline pigments, in particular polycyclic pigments Phthalocyanine, quinacridone, perylene and perinone, indigo, thioindigo, oxindigo, isoxindigo, anthraquinone pigments, for example anthrapyrimidine, Anthanthrone, flavanthrone, pyranthrone pigments, dioxazine, triarylcarbonium, quinophthalone and diketopyrrolopyrrole (“DPP”) pigments, or mixtures thereof.
  • azo pigments in particular monoazo yellow and orange pigments
  • disazo ⁇ -naphthol, naphthol-AS, lacquered azo
  • inorganic pigments examples include iron oxides, titanium dioxide (in various modifications such as rutile or anatase or mixed forms thereof), chromium oxide, cadmium-containing pigments such as cadmium sulfide, bismuth-containing pigments such as bismuth vanadates, chromate-containing pigments such as lead chromate, molybdate-containing pigments such as lead molybdate, or mixtures thereof, and mixtures with other pigments.
  • iron oxides titanium dioxide (in various modifications such as rutile or anatase or mixed forms thereof)
  • chromium oxide such as cadmium sulfide
  • bismuth-containing pigments such as bismuth vanadates
  • chromate-containing pigments such as lead chromate
  • molybdate-containing pigments such as lead molybdate, or mixtures thereof, and mixtures with other pigments.
  • optical brighteners are (a) carbocyclic compounds such as distyrylbenzenes, distyrylbiphenyls or divinylstilbenes, triazinylaminostilbenes, (b) stilbenyl-2H-triazoles such as stilbenyl-2H-naphtho [1, 2-c /] triazoles or bis (1, 2,3 -triazol-2-yl) stilbenes, (c) benzoxazoles such as stilbenylbenzoxazoles or bis (benzoxazoles), (d) furans, benzo [ö] furans and benzimidazoles such as bis (benzo [£>] furan-2-yl) biphenyls or cationic Benzimidazoles, (e) 1, 3-diphenyl-2-pyrazolines, (f) coumarins, (g) naphthalimides, or (h) 1, 3,5-triazin-2-yl derivatives.
  • Optical brighteners are
  • the chromophore layer is applied to a support material by applying a chromophore capable of the polyreaction, if desired together with a suitable comonomer or a comonomer mixture, to the desired support or the desired support and thermally, catalytically or photochemically by polyreaction , preferably photochemically, crosslinked.
  • chromophores capable of polyreaction it is possible to use pigments or dyes which carry at least one functional group, so that one can carry out a polyreaction of conventional monomers in the presence of these chromophores in order to arrive at polymers which contain chemically covalently bound chromophores.
  • polymerization is used in English for polyreaction, and is understood to mean a collective term for addition polymerization (again divided into (a) those with a chain reaction, corresponding to polymerization in the narrower German sense, and (b) such with a step reaction, synonymous with polyaddition) and condensation polymerization (polycondensation).
  • polyreaction is also to be understood as meaning polymer-analogous reactions, that is to say chemical reactions on macromolecules which do not cause any changes in their framework, in particular leave the degree of polymerization unchanged (for example the saponification of polyvinyl acetate to polyvinyl alcohol).
  • chromophores capable of polyreaction are to be understood as meaning those chromophores which contain at least one functional group which is suitable for polymerization by, for example, an acrylate or methacrylate group, and for polycondensation by, for example, hydroxyl or acid chloride groups Polyaddition by, for example, epoxy, hydroxyl or isocyanate groups, or can also be used for polymer-analogous reactions.
  • chromophores which do not contain a group capable of polyreaction can generally be modified by methods known per se such that they contain at least one functional group capable of polyreaction.
  • methods for the production of DPP colorants as chromophores with functional groups capable of polyreaction are described in particular. According to previous observations, the methods described there can generally also be applied to other chromophores.
  • R ⁇ stands for a group capable of polyreaction
  • R 2 is d-C ⁇ -alkyl, or R
  • R 3 is hydrogen or dC 6 alkyl
  • a and B independently of one another each represent an unsubstituted or substituted carbocyclic C 6 -C 14 aryl radical (number of carbon atoms of the possibly present
  • R ⁇ capable of polyreaction within the scope of the present invention, e.g. groups capable of polymerization, such as acrylate or methacrylate residues, or groups capable of polycondensation, such as hydroxyl or acid chloride groups, or also groups capable of polyaddition, such as hydroxyl or isocyanate groups, or groups containing the groups mentioned.
  • R ⁇ can also stand for the cation of an alkali metal such as sodium or potassium, especially if you want to carry out polymer-analogous reactions.
  • R represents a radical of the formula II
  • Y is a single bond, d-Cgalkylene, -C (O) -, -OC (O) - , -C (O) -O-, Z, -SO 2 -, -Si (Hal) 2 -,
  • POHal -, X is unsubstituted or substituted carbocyclic or heterocyclic C 6 -
  • R 4 is hydrogen or methyl, interrupted linear or branched C 2 -C 3 o-alkylene, or for C 5 -C 12 cycloalkylene,
  • Q is, for example, -OH, -SH, -NH 2 , -CN, glycidyl, 1, 2-epoxithyl,, -CHO,
  • s is an integer from 1 to 6.
  • the unsubstituted or substituted carbocyclic C 6 -C 1 aryl radicals or heterocyclic radicals having four to five carbon atoms A and B each preferably represent a group of the formula
  • R 5 and R 10 independently of one another hydrogen, halogen, C r C 6 alkyl, C
  • R 8 and R 9 independently of one another are hydrogen, halogen or dd-alkyl.
  • d-da-alkyl methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, i-butyl, tert. Butyl, n-amyl, tert-amyl, hexyl, heptyl, octyl, 2-ethylhexyl, nonyl, decyl, dodecyl, tetradecyl, hexadecyl or octadecyl, preferably C r C 8 alkyl such as methyl, ethyl, n-propyl, isopropyl , n-butyl, sec.-butyl, i-butyl, tert.-butyl, n-amyl, tert.-amyl, hexyl, heptyl, octyl, 2-ethylhexyl
  • dC 18 -alkoxy usually means, also in CC 18 -alkoxycarbonyl, for example methoxy, ethoxy, n-propoxy, isopropoxy, butyloxy.hexyloxy, decyloxy, dodecyloxy, hexadecyioxy or octadecyloxy, preferably C r C 6 -alkoxy such as methoxy, ethoxy, n -Propoxy, isopropoxy, butyloxy, hexyloxy.
  • the d-doalkylene is usually methylene, ethylene, n-propylene, isopropylene, n-butylene, sec-butylene, i-butylene, tert-butylene, n-amylene, tert-amylene, hexylene, heptylene, octylene, 2-ethylhexylene, nonylene, decylene, dodecylene, tetradecylene, hexadecylene or octadecyl, preferably for C 2 -C 30 alkylene, in particular for C r C 8 alkylene such as methylene, ethylene, n-propylene, isopropylene, n-butylene, sec.
  • d-ds-Alkylmercapto stands for example for methylmercapto, ethylmercapto, propyl mercapto, butyl mercapto, hexylmercapro, octylmercapto, decylmercapto, hexadecylmercapto or octadecylmercapto, preferably for dC 6 -alkylmercapto such as methylmercapto, ethylmercapto, propylmercapto, propylmercapto.
  • d-ds-Alkylamino means, also in dC 18 -alkylaminocarbonyl, for example methylamino, ethylamino, propylamino, hexylamino, decylamino, hexadecylamino or octadecylamino, preferably CC 6 -alkylamine such as methylamino, ethylamino, n-propylamino, hexylamino.
  • C 5 -C 2 -cycloalkyl usually stands for cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl, cycloundecyl, cyclododecyl, preferably for dd-cycloalkyl such as cyclopentyl or cyclohexyl, in particular for cyclohexyl.
  • C 5 -C 12 cycloalkylene generally mean mono- or bicyclic cycloalkenyl such as C 5 - C 7 -cycloalkenyl, especially cyclopentenyl, cyclohexenyl, cycloheptenyl or norbornenyl.
  • C 2 -C 8 alkenyl represents, for example, vinyl, n-propenyl, isopropenyl, n-butenyl, sec-butenyl, i-butenyl, n-amenyl, hexenyl, heptenyl, octenyl, 2-ethylhexenyl, nonenyl, decenyl, Dodecenyl, tetradecenyl, hexadecenyl or octadecenyl, preferably C 2 -C 8 alkenyl such as ethenyl (vinyl), n-propenyl, isopropenyl, n-butenyl, sec-butenyl, i-butenyl, n-amenyl, hexenyl, heptenyl, octenyl , 2-ethylhexenyl, particularly preferably C 2 -
  • halogen such as fluorine, chlorine, bromine or iodine, preferably chlorine or bromine.
  • DPP compounds II The preparation of the DPP compounds II is described in EP-A 778,731 or they can be prepared analogously to the methods mentioned there.
  • R 12 and R 13 are independently hydrogen, C r C 18 alkyl, C 2 -C 18 alkyl interrupted one or more times by -O- or -S- or a group - (CH 2 ) n -COX, where n represents an integer from zero to ten and X can be -OR 14 or shark, where R 14 is hydrogen, C 1 -C 24 alkyl or C 5 -C 10 cycloalkyl and shark is halogen such as fluorine, chlorine, bromine or iodine , preferably chlorine or bromine.
  • the DPP compounds III can be prepared by the method described in EP-A 778,730.
  • the type of comonomers is usually not restricted and suitably depends on the groups of the colorant used which are capable of polyreaction.
  • monomers containing at least one carbon-carbon double bond such as dd-alkyl acrylates, in particular methyl acrylate, ethyl acrylate, n-propyl acrylate, i-propyl acrylate, n-butyl acrylate, i-butyl acrylate, sec-butyl acrylate, tert-butyl acrylate, can be used as comonomers.
  • Particularly preferred comonomers are dC 8 alkyl acrylates and CC 8 alkyl methacrylates.
  • the comonomer can have the same reactive polyreactive group as the chromophore capable of polyreaction, particularly preferably a diketopyrrolopyrrole ("DPP") monomer of the formula I or III, for example the DPP monomer and the comonomers can contain acrylate or methacrylate groups, or both can contain two hydroxyl groups (“diol”), in which case corresponding diacids, diacid chlorides or diisocyanates are used as reactants.
  • DPP diketopyrrolopyrrole
  • the choice of the corresponding groups capable of polyreaction is only limited by the expediency or easier accessibility, so that in principle any combinations of the accessible (co) monomers are possible.
  • the ratio of chromophore capable of polyreaction to comonomer is generally chosen depending on the polyreaction:
  • the weight ratio is generally selected in the range from 0.01 to 100 parts per hundred (phr), preferably from 1 to 50, particularly preferably from 5 up to 25 phr,
  • the molar ratio is generally selected in the range from 0.01 to 300, preferably from 1 to 100, mol%.
  • the chromophore can also be homopolymerized; copolymers of chromophore and another comonomer are preferred in the context of the present invention.
  • This chromophore is brought in by conventional methods for polyreaction with an acrylate monomer or a mixture of different acrylate monomers in a monomer weight ratio of from 0.01 to 100, preferably from 1 to 50,% by weight .-%, based on the total amount of chromophore and acrylate
  • a DPP diol is used as the chromophore capable of the polyreaction.
  • Comonomers which can be used are further diols, diacids, diacid chlorons and also diisocyanates such as C 2 -C 30 alkylene diisocyanates, in particular hexamethylene densocyanate and isophorone dysocyanate, 44'-disocyanatod ⁇ cyclohexylmethane, 2,4-toluenedionocyanate, 1, 5-naphthalenedensocyanate, 4,4'-methyldisocyanate, 4,4'- , Terephthalic acid, dimethyl isophthalate, isophthalic acid, dimethyl adipate, adipic acid, azelaic acid, sebacic acid, dodecanedioic acid, 1, 4-cyclohexanedicarboxylic acid, Dimethyl-1, 4-cyclohexanedicarboxylate ester, 4-hydroxybenzoic acid, 6-hydroxy-2-naphthoic acid, pivalolactones, ⁇ -cap
  • DPP chromophores examples include:
  • the chromophore layer used is a composition which contains a chromophore in the form of microparticles and a polymer, preferably a melamine-formaldehyde resin.
  • Microparticles are to be understood as meaning polymer particles with a size or size distribution in the range from 0.01 to 20 ⁇ m.
  • Corresponding microparticles are known in coating technology and are present in the coating compositions usually used there in a disperse phase as an insoluble component in the liquid phase used. In the literature, the term “microgel” is often used instead of "microparticles".
  • microgels which can be prepared analogously to the method described in EP-A 226,538, the microgels described therein consisting of a crosslinked polymer core and of linear further polymers covalently bonded to it.
  • the light stabilizers and chromophores can be polymerized not only in the (polyester) cores, but also in the linear polymers forming the outer layer.
  • a partially crosslinked polyester core which has free hydroxyl and / or carboxyl groups is usually prepared in a first step, for example by polycondensing one or more diacids with one or more diols or polyols.
  • linear polymers preferably poly (meth) acrylates or polyesters
  • monomers such as (meth) acrylates or diols and diacids in the presence of the polyester core in a manner known per se for the polyreaction.
  • the microgel thus produced preferably still has free groups capable of polyreaction, such as hydroxyl or carboxyl groups, so that it can be reacted further with a further polymer system, preferably a melamine-formaldehyde resin, to give a finished coating system.
  • a further polymer system preferably a melamine-formaldehyde resin
  • a mixture is used to produce a polyester core
  • a chromophore capable of polyreaction in particular a DPP compound of the formula I or III
  • a catalyst preferably tetrabutyl orthotitanate
  • the% by weight additions to 100% by weight including the dicarboxylic acid to be added below
  • water of reaction formed is removed from the reaction mixture, for example using a water separator.
  • the reaction mixture is then cooled to a temperature in the range from 120 to 150 ° C.
  • a dicarboxylic acid for example succinic acid or adipic acid, preferably adipic acid
  • a copolymer is then added to the reaction mixture as a further component forming an outer layer in the desired amount, for example in the range from 5 to 20% by weight, based on the total weight of the polyester core, preferably a mixture of copolymer and one high-boiling organic solvent and then heated the reaction mixture to a temperature in the range of 170 to 210 ° C with vigorous stirring for 30 minutes and two hours.
  • the copolymer can also be added in portions.
  • the outer layer which surrounds the polyester core is preferably produced by the method described in EP-A 226,538 by preferably using an amphiphilic, ie a hydrophobic and also a hydrophilic, dispersant.
  • amphiphilic dispersants can be obtained, for example, by polycondensation of two hydroxycarboxylic acids, one hydroxycarboxylic acid being hydrophobic such as 12-hydroxystearic acid, and the other hydroxycarboxylic acid being hydrophilic such as 2,2-bis (hydroxymethyl) propionic acid, by reacting the hydroxycarboxylic acids in the presence of a catalyst such as methanesulfonic acid and a solvent such as an alkane mixture.
  • the polycondensate obtained is then preferably modified with a glycidyl ester, for example methacrylic acid glycidyl ester, by heating in the presence of customary catalysts such as hydroquinone and dimethylaminodecane and a solvent such as an alkane mixture.
  • a mixture consisting of a (meth) acrylate such as methyl methacrylate and, if desired, a comonomer such as methacrylic acid is usually polymerized in a manner known per se, for example thermally initiated by the decomposition of, for example, azobisdiisobutyronitrile in a solvent in the presence of the modified polymer.
  • the polyester microgel thus obtained is preferably set with a melamine-formaldehyde resin (MF resin) in a weight ratio (solids content) of 1: 1 to 20: 1 (microgel / MF resin) at a temperature in the range from 140 to 160 ° C and a reaction time of 1/2 to 1 1/2 hours around.
  • MF resin melamine-formaldehyde resin
  • all known types of polyreactions can be carried out with the chromophores capable of the polyreaction, in particular the corresponding DPP compounds from, for example, EP-A 787,730 and EP-A 787,731.
  • the chromophores capable of the polyreaction in particular the corresponding DPP compounds from, for example, EP-A 787,730 and EP-A 787,731.
  • produce vinyl, allyl, vinyl ester, vinyl amide, vinyl acetate or vinyl ketone polymers from chromophores capable of polyreaction, the reactive groups of which have C C bonds.
  • the corresponding reactive groups of the chromophores contain heteroatoms, polyaldehydes, polyisocyanates, polyepoxides, polyethers, polyacetones or polyiactams can be prepared in the case of monofunctional chromophores.
  • the reactive groups of which contain heteroatoms polyesters, polyamides, polyimides or polycarbonates can generally be prepared via polycondensation, and polyaddoxides, polyurethanes or polyimides can be prepared via polyaddition.
  • the polyreaction is usually carried out by methods known per se, as described, for example, in EP-A 787 731, by reacting the chromophore monomer with the comonomer usually by generally known methods, for example by a polyreaction, ie by Polymerization (thermal or photochemically), polycondensation or polyaddition, or by a polymer-analogous reaction, ie by reacting a chromophore with already existing polymers which have corresponding reactive groups. For technical reasons, photochemical polymerization is generally preferred.
  • the polyreaction is carried out in a radical, cationic or anionic manner, but the known polymerizations by coordination or group transfer polymerization are also possible.
  • Examples of the production of DPP polymers are (a) the polymerization for the production of DPP polyacrylates or polymethacrylates by radical thermal polymerization in solution, substance, suspension or emulsion of DPP acrylates or DPP methacrylates, i.e.
  • DPPs of the formula I or III in which Q represents an acrylic or methacrylic group, or the radical photopolymerization of DPP acrylates or DPP methacrylates, (b) the polycondensation for the preparation of DPP-containing polyesters from DPPs I or III, in where Q stands for a hydroxyl group, and diacid chlorides, or the production of DPP polycarbonates from DPP diols and phosgene, (c) the polyaddition for the production of DPP polyurethanes from DPP diols and diisocyanates, or the production of DPP polyepoxides DPP epoxides and amines, and (d) the polymer-analogous reaction, for example the reaction of a DPP alcohol with a polymer prepared from styrene and maleic anhydride and accordingly having anhydride groups to a polymer containing DPP mono- or diester groups.
  • Q represents an acrylic or methacrylic group, or the radical photo
  • Polycondensation can be carried out in the melt, in solution, in suspension or as interfacial condensation.
  • Polycondensation is usually carried out in the melt at temperatures in the range from 120 to 180 ° C. in an inert gas atmosphere with or without a catalyst.
  • dilute solutions are generally used, for example in the range from 5 to 30% by weight.
  • the water formed can be removed from the reaction mixture, for example by an azeotropic distillation, preferably with the addition of so-called entraining agents such as benzene, toluene or carbon tetrachloride.
  • You can also, for example, the water produced by a Remove continuous thin-film evaporation or analogous processes in the large-scale sector, generally giving the solution of the starting components to a packed column and removing the water released in countercurrent with, for example, carbon dioxide. This variant usually produces very bright products.
  • diaryl esters of dicarboxylic acids are generally reacted with diamines in aromatic hydrocarbons, phenols being split off and the polyamide formed precipitating in fine-grained form.
  • precondensation is carried out first at temperatures in the range from 80 to 100 ° C. (amorphous polyamides) or 130 to 160 ° C. (crystalline polyamides).
  • the actual polycondensation is then preferably carried out in a fluidized bed at higher temperatures, the upper temperature limit usually being chosen so that the polyamide particles do not stick together.
  • the polyamide is generally still condensed in the solid phase.
  • Polyadditions can be carried out in the melt or in solution. Typical representatives are polyurethanes and epoxy resins.
  • the polyaddition of dihydroxy compounds with diisocyanates usually begins when the components are mixed and lightly heated.
  • the carefully cleaned and dewatered dihydroxy compound is generally introduced and, with thorough mixing, the diisocyanate is added slowly and / or in portions.
  • the temperature is preferably kept as constant as possible in order to achieve a uniform course of the reaction, which can be done by a controlled addition of the diisocyanate and, if desired, by cooling.
  • inert solvents such as toluene, xylene, chlorobenzene or o-dichlorobenzene are generally used.
  • the usual procedure is to add the solution of the dihydroxy compound and to add the diisocyanate at the desired temperature (generally the boiling point of the solvent).
  • the resulting polyurethane usually precipitates out of the reaction mixture.
  • Polyepoxides are usually produced by first producing epoxy resin monomers, for example from a bisphenol such as bisphenol A and epichlorohydrin (in general solvent-free, excess epichlorohydrin, in the presence of an aqueous base such as sodium hydroxide solution). Excess epichlorohydrin can be distilled, salt formed, such as NaCl, can be precipitated, for example by adding an aromatic solvent such as toluene, combined with a subsequent filtration.
  • a bisphenol such as bisphenol A
  • epichlorohydrin in general solvent-free, excess epichlorohydrin, in the presence of an aqueous base such as sodium hydroxide solution.
  • an aqueous base such as sodium hydroxide solution
  • the polymers themselves are usually obtained by polyaddition reactions with various acidic, basic or catalytic curing agents, for example acid anhydrides such as phthalic acid, amines such as diaminodiphenylmethane or triethylene amine and boron trifluoride complexes or imidazoles.
  • acid anhydrides such as phthalic acid
  • amines such as diaminodiphenylmethane or triethylene amine
  • boron trifluoride complexes or imidazoles for example acid anhydrides such as phthalic acid, amines such as diaminodiphenylmethane or triethylene amine and boron trifluoride complexes or imidazoles.
  • the dried copolymers can then be prepared by methods known per se, for example by melting and pulling out a film with a doctor blade, by spray painting, dipping, brushing, rolling, wiping, filling, tumbling, centrifuging / spinning, flooding, casting (curtain coating), rolling , Powder coating or coil coating (Coal Coating) on a desired substrate.
  • the polymerization is carried out photochemically, the reaction mixture generally being one of the customary photoinitiators (see, for example, "Chemistry & Technology of UV & EB Formulations for Coatings, Inks and Paints, Vol. 3: Photoinitiators for Free Radical and Cationic Polymerization "1991, pp. 1115-1325) in an amount in the range of generally 0.5 to 5% by weight, based on the sum of all monomers used. If desired, you can also use a sensitizer.
  • the compounds used for this purpose can be used as sensitizers.
  • Corresponding compounds are described, for example, in Chemistry & Technology of UV & EB Formulation for Coatings, Inks & Paints, Vol. 3: Photoinitiators for Free Radical and Cationic Polymerization, KK Dietliker, SITA Technology Ltd., London 1991, pp. 160 - 165.
  • the monomeric chromophores in particular the DPP derivatives of the formulas I or III, can be used to produce macromolecular compounds, in particular moldings of all types, coatings and relief images or relief structures.
  • these shaped bodies are preferably produced in a photochemically initiated manner, that is to say by the action of actinic radiation.
  • the wavelength of the actinic radiation used is usually chosen in the range from ⁇ -radiation to the infrared range.
  • the radiation used generally depends essentially on the absorption of the photoinitiators used. Preference is given to using electromagnetic radiation in the wavelength range of UV radiation into the visible range, that is to say from about 100 nm to 780 nm.
  • UV lamps ultraviolet lamps
  • UV lasers are preferably used.
  • the radiation duration is generally u.a. depending on the type of light source; it can range from hours to minutes or even seconds.
  • the irradiation time is in the range from 10 to 25 minutes if the UV lamp emits radiation in the wavelength range from 200 to 440 nm .
  • Polymer films are particularly preferably produced from the chromophores capable of polyreaction, the layer thickness of the chromophore layer being able to vary depending on the application. In the case of paints, for example, a layer thickness in the range from 5 to 500, preferably 10 to 150 ⁇ m is usually chosen.
  • a composition can also be used as the chromophore layer, consisting of a non-polymer-bound chromophore such as an organic and / or inorganic colorant or an optical brightener and a polymer and optionally conventional additives.
  • a non-polymer-bound chromophore such as an organic and / or inorganic colorant or an optical brightener and a polymer and optionally conventional additives.
  • the usual chromophores in particular the chromophores on which the chromophores capable of polyreaction mentioned above are based, can be used in the usual way Use amounts, for example in the range from 0.1 to 40% by weight, based on the total weight of chromophore + polymer.
  • the chromophore layer which contains a non-covalently bound chromophore, can be prepared by conventional methods such as by melting and pulling out a film with a squeegee, by spray painting, dipping, brushing, rolling, wiping, filling, tumbling, centrifuging / spinning , Flooding, casting (curtain coating), rolling, powder coating or coil coating (coal coating) on a desired substrate.
  • Transition metals especially iron, titanium, vanadium, chromium, zinc, cobalt, nickel, copper, silver, gold, molybdenum, palladium, platinum, tungsten, tantalum, iridium, and uranium, and their alloys and steels, and metals of the third and fourth main group of the periodic system of elements such as aluminum, silicon, tin or lead,
  • natural or artificial polymeric substances such as wood, textiles, in particular cellulose fibers, synthetic fibers such as acetate, triacetate, polamide, polyacrylonitrile or polyester fibers, and protein fibers such as wool or silk.
  • aluminum pretreated with sodium nitrite and sodium polyphosphate is used.
  • Appropriately pretreated aluminum is commercially available available (eg aluminum pretreated by the CHEMOXAL® process from Alusuisse) or can be produced in a manner known per se. Aluminum pretreated in this way generally leads to better adhesion of the chromophore layer.
  • the light stabilizer layer consists of either
  • ⁇ and r 2 are independently 0 or 1 and the substituents Yi to Y 9 are independently hydrogen, -OH, C r C 20 alkyl, dC 12 cycloalkyl, C 2 -C 20 alkenyl, d-do- Alkoxy, C 4 -C 1 cycloalkoxy, C 2 -C 20 alkenyloxy, C 7 -C 20 aralkyl, halogen, CN, C r C 5 haloalkyl, -SO 2 R ', -SO 3 H, -S0 3 M, where M is an alkali metal, -COOR 15 , -CONHR 15 , -CONR 15 Ri6, -OCOOR 15 , -OCOR 15 , -OCONHR 15 , (meth) acrylamino, (meth) acryloxy, C 6 -C 12 aryl ; by C 1 -C 2 alkyl, C r C 12 alkoxy, CN,
  • Y 9 denotes -OR 17 , and R 17 for -A, -CH 2 -CH (XA) -CH 2 -OR 18 , -CH (Me) -C (O) OH, -CR 19 R 20 -CH 2 -XA, -CH 2 -CH (OA) -R 21 , -CH 2 -CH (OH) -CH 2 -XA,
  • Phenyl-d-dalkyl interrupted by one or more -O- C 3 -C 18 alkyl, 1-adamantyl,
  • R 19 and R 20 independently of one another, hydrogen, dC 18 alkyl, phenyl, phenyl-C
  • R 21 C r C 18 alkyl, phenyl or phenyl-C C 4 alkyl
  • R 22 is hydrogen or methyl
  • R 23 and R 24 independently of one another, C r C alkyl or phenyl or one to three radicals dC 8 alkyl, CC 8 alkoxy, C 3 -C 8 alkenoxy, halogen or trifluoromethyl substituted
  • R 25 is hydrogen, -CH 2 -COOR 28 , CC 4 alkyl or -CN;
  • R 26 is hydrogen, -COOR 28 , C r C 18 alkyl or phenyl;
  • R 27 is hydrogen, dC 18 alkyl, phenyl, phenyl-d-dalkyl, C 5 -C 12 cycloalkyl, dC 8 alkoxy,
  • R 28 C r C 18 alkyl, C 3 -C 8 alkenyl, phenyl, C 5 -C 12 cycloalkyl, interrupted by one or more -O- C 3 -d 8 alkyl; with one to three radicals C r C 8 alkyl, dC 8 alkoxy, C 3 -
  • R 1 5 and R 16 independently of one another are hydrogen, dC 2 o-alkyl, C 4 -C 12 cycloylalkyl, C 6 -
  • light stabilizers such as sterically hindered amines, 2- (2-hydroxyphenyl) benzotriazoles, oxalic acid anilides, 2-hydroxybenzophenones, hydroxyphenyltazines or cinnamic acid derivatives
  • the corresponding compounds are known to the person skilled in the art or can be obtained by known processes (for example from EP-A 226,538 or EP-A 114,748 (sterically hindered amines, in particular based on piperidine)) and are also commercially available.
  • the light stabilizers usually include radical scavengers and UV absorbers, which also belong to different classes of compounds.
  • UV absorbers are 2- (2-hydroxyphenyl) benzotriazoles (known, for example, from EP-A 226,538 and EP-A 57,160), in particular the compounds of the formula IV, 2-hydroxybenzophenones such as 4-hydroxy-, 4 -Methoxy-, 4-octyloxy, 4-decyloxy or 4-dodecyloxy derivative, 2,4-bis (2'-hydroxyphenyl) -6-alkyl-s-triazines such as 6-ethyl, 6-heptadecyl - or 6-undecyl derivative, oxalic acid diamides, especially oxalic acid dianilides such as 4,4'-di-octyloxy oxanilide, 2,2'-di-octyloxy-5,5 ' -di-tert.butyl-oxaniü
  • polymers of mono- and diolefins for example polypropylene, polyisobutylene, poly-butene-1, poly-4-methylpentene-1, polyisoprene or polybutadiene and polymers of cycloolefins such as e.g. of cyclopentene or norbomen; also polyethylene (which may optionally be cross-linked), e.g. High density polyethylene (HDPE), low density polyethylene (LDPE), linear low density polyethylene (LLDPE), branched polyethylene
  • HDPE High density polyethylene
  • LDPE low density polyethylene
  • LLDPE linear low density polyethylene
  • (c) Copolymers of mono- and diolefins with one another or with other vinyl monomers, such as ethylene-propylene copolymers, linear low-density polyethylene (LLDPE) and mixtures thereof with low-density polyethylene (LDPE), propylene-butene-1 copolymers, propylene Isobutylene copolymers, ethylene-butene-1 copolymers, Ethylene-hexene copolymers, ethylene-methylpentene copolymers, ethylene-heptene copolymers, ethylene-octene copolymers, propylene-butadiene copolymers, isobutylene-isoprene copolymers, ethylene-alkyl acrylate copolymers, ethylene-alkyl methacrylate copolymers, Ethylene-vinyl acetate copolymers and their copolymers with carbon monoxide, or ethylene-acrylic acid copolymers
  • hydrocarbon resins e.g. C 5 -C 9
  • hydrogenated modifications thereof e.g. tackifier resins
  • mixtures of polyalkylenes and starch
  • copolymers of styrene or ⁇ -methylstyrene with dienes or acrylic derivatives such as styrene-butadiene, styrene-acrylonitrile, styrene-alkyl methacrylate, styrene-butadiene-alkyl acrylate and methacrylate, styrene-maleic anhydride, styrene-acrylonitrile-methyl acrylate;
  • graft copolymers of styrene or ⁇ -methylstyrene such as styrene on polybutadiene, styrene on polybutadiene-styrene or polybutadiene-acrylonitrile copolymers, styrene and acrylonitrile
  • (k) Polymers derived from unsaturated alcohols and amines or their acyl derivatives or acetals, such as polyvinyl alcohol, polyvinyl acetate, stearate, benzoate, maleate, polyvinyl butyral, polyallyl phthalate, polyallyl melamine; and their copolymers with olefins mentioned in (a),
  • cyclic ethers such as polyalkylene glycols, polyethylene oxide, polypropylene oxide or their copolymers with bisglycidyl ethers
  • polyacetals such as polyoxymethylene (“POM”) and also those polyoxymethylenes which are obtainable with comonomers such as ethylene oxide, polyacetals which are thermoplastic Polyurethanes, acrylates or MBS are modified
  • Polyamides and copolyamides derived from diamines and dicarboxylic acids and / or from aminocarboxylic acids or the corresponding lactams such as polyamide 4, polyamide 6, polyamide 6/6, 6/10, 6/9, 6/12, 4/6 , 12/12, polyamide 11, polyamide 12, aromatic polyamides starting from m-xylene, diamine and adipic acid;
  • crosslinked polymers derived from aldehydes on the one hand and phenols, urea or melamine on the other hand such as phenol-formaldehyde, urea-formaldehyde and melamine-formaldehyde resins, (v) drying and non-drying alkyd resins,
  • Mixtures of the abovementioned light stabilizers and the polymers can be obtained by physical mixing using customary methods, such as in an emulsion or dispersion (for example adding to latices or emulsion polymers), simple stirring in the solid state, if appropriate with comminution of the components before or after the mixing process, mixing in a processing apparatus such as an extruder or internal mixer or in a solution or melt.
  • customary methods such as in an emulsion or dispersion (for example adding to latices or emulsion polymers), simple stirring in the solid state, if appropriate with comminution of the components before or after the mixing process, mixing in a processing apparatus such as an extruder or internal mixer or in a solution or melt.
  • the mixture of polymer and light stabilizer can be applied in a manner known per se as a film to the chromophore layer, for example by melting and pulling out a film with a doctor blade, by spray painting, dipping, brushing, rolling, wiping, filling, drumming, Centrifuging / centrifuging, flooding, casting (curtain coating), rolling, powder coating or coil coating (coal coating).
  • Copolymerizable light stabilizers are known for example from EP-A 226,538, EP-A 706,083 or DE-A 197 39 781 or can be prepared by the methods mentioned therein. They generally contain reactive groups such as hydroxyl, carboxy, ester, amide, isocyanate, epoxy, (meth) acrylate or amino groups or ethylenically unsaturated double bonds.
  • Triazines of the formula IV with the reactive groups mentioned are preferably used, and hydroxyphenyltnazines V are particularly preferably used
  • R 30 is where the radicals R 32 , R 33 and R 34 can stand for hydrogen, C r C 4 alkyl, in particular methyl, or for ⁇ OH, preferably R 32 is in the ortho and R 33 in the para position and is - OH, or R 32 , R 33 and R 3 are in the 2-, 4- and 6-positions and are methyl.
  • Hydroxyphenyltnazines V are known, for example, from EP-A 706,083 or DE-A 197 39 781 or can be prepared by the methods described there.
  • X ' is -O- or -NR 38 ;
  • R 36 is hydrogen, CC 4 alkyl, -CH 2 -COOR 39 , -Cl or -CN;
  • R 35 is hydrogen, -COOR 39 or methyl;
  • R 37 is hydrogen, C r C 18 alkyl, C 2 -C 18 alkenyl; C 2 -C 18 alkyl interrupted by one or more O atoms, which may be substituted by -OH, or - (CH 2 ) s -SO 3 M;
  • R 39 is hydrogen, dC 18 alkyl, phenyl, C 2 -C 18 alkenyl
  • R y is hydrogen, dC 18 alkyl, phenyl, -CO-OR x , -CN, -F, -Cl;
  • R ⁇ is hydrogen or methyl
  • R 43 is hydrogen or methyl
  • R 44 is hydrogen, fluorine, chlorine or methyl and R 5 is chlorine, bromine, fluorine or -CN;
  • methyl (meth acrylate, ethyl (meth) acrylate, n-propyl
  • LAROMER von products from BASF
  • LAROMEROEA81 aromatic epoxy acrylate as an 80% by weight solution in hexanediol diacrylate, viscosity 23 ° C: 8-12 Pa s
  • Hydroxyl number 160 mg KOH / g prepolymer
  • molecular weight approx. 530 g / mol
  • main component bisphenyl-A-diglycidyl ether diacrylate
  • the copolymerizable light stabilizer is preferably selected in an amount in the range from 1 to 50, preferably 5 to 25,% by weight and the comonomer in the range from 99 to 50, preferably from 95 to 75% by weight.
  • the copolymerization of the monomeric light stabilizers IV or V with the abovementioned monomers VI to XI can be initiated by free-radical, anionic or cationic initiators. Radical initiators which decompose into radicals when heated, such as organic peroxides or hydroperoxides, azo compounds or redox catalysts, are preferably used.
  • the copolymerization can also be initiated by high-energy radiation and carried out in solution, emulsion, dispersion or in bulk. These methods are known to the person skilled in the art, for example from EP-A 577,122, page 9, line 46 to page 10, line 35 and the documents cited therein.
  • microgels are used which contain a light stabilizer in copolymerized form. It is particularly preferred to use a mixture of a UV absorber-copolyester microgel and melamine-formaldehyde resin, and the mixture is usually cured thermally after the application and removal of a film.
  • a UV absorber-copolyester microgel is usually produced in the same way as the microgels described above which contain a chromophore, with the difference that a UV absorber is used instead of the chromophore.
  • a UV absorber is used instead of the chromophore.
  • the layer thickness of the light stabilizer layer is selected in the range from 10 to 300, preferably from 10 to 150 ⁇ m.
  • Known polymers are usually used as the oxygen barrier layer for this purpose.
  • Those polymers are preferably selected which have a permeability coefficient to oxygen of not greater than 4-10 "13 cm 3 -cm / (cm 2 -s-Pa) under the standard conditions of 273.15 K and 1.013-10 5 Pa.
  • Particularly preferred one chooses a polymer with a permeability coefficient to oxygen of not greater than 0.4-10 "13 , very particularly preferably not greater than 0.04 cm 3 - cm / (cm 2 -s-Pa).
  • Polymers with a permeability coefficient to oxygen of not greater than 4-10 "13 cm 3 -cm / (cm 2 -s-Pa) are, for example, LDPE, HDPE, polypropylene, polystyrene, polymethyl methacrylate, polyacrylonitrile, polyvinyl acetate, polyvinyl alcohol, polyvinyl chloride, polyvinylidene chloride, Polytetrafluoroethylene, poly (imino-l-oxohexamethylene) (nylon 6), Polyester, cellulose hydrate (such as Cellophan®), particularly preferably polyacrylonitrile, polyvinyl alcohol, polyvinyl chloride, polyvinylidene chloride, nylon 6, polyester, cellulose hydrate.
  • photocrosslinkable polymers such as a correspondingly modified polyvinyl alcohol (“PVA”), in particular PVA, in which some of the hydroxyl groups have been replaced by residues containing (meth) acrylate groups; photocrosslinkable PVA methacrylates described in US Pat. No. 4,670,506 are particularly preferred or can be produced analogously to the methods mentioned there.
  • PVA polyvinyl alcohol
  • compositions according to the invention which contain a photo-hardened oxygen barrier layer which can preferably be obtained by derivatizing a polyvinyl alcohol with a (meth) acrylate derivative, in particular an isocyanate of the formula XIII
  • R 47 and R 48 each represent straight-chain or branched alkylene with 2 to eight carbon atoms, such as -CH 2 -CH 2 -, -CH 2 -CH 2 -CH 2 -, -CH (Me) -CH 2 -, -CH 2 - CH 2 -CH 2 -CH 2 -, -CH 2 -CH (Me) -CH 2 -, -CMe 3 , -CH 2 -CH 2 -CH 2 -CH 2 -, -CH 2 -CH 2 -CH 2 -CH 2 -CH 2 -, -CH 2 -CH 2 -CH 2 -CH 2 -CH 2 -, -CH 2 - CH 2 -CH 2 -CH 2 -CH 2 -CH 2 -, -CH 2 -CH 2 -CH 2 -CH 2 -CH 2 -, -CH 2 -CH 2 -CH 2 -CH 2 -CH 2 -, -CH 2
  • C 4 is alkyl
  • isocyanates of the formula XIII are 2-isocyanatoethyl methacrylate, 2-isocyanatoethyl acrylate, 3-isocyanatopropyl methacrylate, 4-isocyanatobutyl (meth) acrylate, 6-isocyanatohexyl (meth) acrylate, 1-methyl-2-isocyanatoethyl methacrylate and 1, 1-dimethyl-2 - Isocyanatoethyl acrylate, very particularly preferably 2-isocyanatoethyl methacrylate.
  • a polyvinyl alcohol with a molecular weight in the range from 10,000 to 1,000,000, preferably from 100,000 to 300,000 g / mol and with the repeating unit
  • the aprotic solvent can be, for example, formamide, dimethylformamide, hexamethylenephosphoric triamide (“HMPT”), N-methyl-2-pyrrolidone, dimethylacetamide, acetamide, acetonitrile or dimethyl sulfoxide (“DMSO”), preferably DMSO.
  • HMPT hexamethylenephosphoric triamide
  • DMSO dimethyl sulfoxide
  • Tertiary amines such as trimethylamine, triethyiamine, N.N-dimethylbenzylamine, dimetrhylcyclohexylamine or an organometallic urethane catalyst such as tin octoate, dibutyltin dilaurate or sodium acetate are generally chosen as urethane catalysts.
  • the non-photocrosslinkable polymers are usually applied in a manner known per se, for example by melting and pulling out a film with a doctor blade, by spray painting, dipping, brushing, rolling, wiping, filling, tumbling, centrifuging / spinning, flooding, casting (curtain coating) , Rollers, powder coating or coil coating (Coal Coating) on the chromophore layer.
  • Photocrosslinkable polymers are preferably converted into the liquid form, either by simple heating or by dissolving in a suitable solvent, a customary photoinitiator is added, and a film is drawn onto the desired surface, particularly preferably the chromophore layer, using a suitable device such as a doctor blade , out.
  • the solvent that may be present is then removed, for example by heating, if desired under reduced pressure, and irradiating the layer thus obtained with suitable UV radiation, for example analogously to the procedure for the production of the chromophore layer.
  • the layer thickness of the oxygen barrier layer is selected in the range from 10 to 300, preferably from 10 to 100 ⁇ m.
  • the oxygen barrier layer is covered with a clear lacquer protective layer, but the compositions according to the invention can also be produced without a protective layer.
  • a layer of a polymer which is transparent and water-impermeable is used as the clear lacquer protective layer; this layer is particularly preferably obtainable by photocuring a crosslinkable, preferably photocrosslinkable, polymer applied as a film to the oxygen barrier layer.
  • a mixture of monomers for example an acrylate / monomer mixture, is usually applied to the oxygen barrier layer and a polyreaction is then carried out in a manner known per se.
  • a monomer mixture is preferably used which can be polymerized by irradiation using, for example, UV light. This can be achieved, for example, by adding a photoinitiator to the monomer mixture and then polymerizing it radically by means of UV radiation.
  • the layer thickness of the clear lacquer protective layer is selected in the range from 10 to 300, preferably from 10 to 50 ⁇ m.
  • a particularly preferred embodiment relates to a composition according to the invention, in the order given: (a) a chromophore layer with a layer thickness in the range from 20 to 150 ⁇ m, obtainable by copolymerization of
  • XIV (a2) 99 to 75% by weight of a monomer or a prepolymer based on a (meth) acrylate
  • an oxygen barrier layer made of a photocrosslinked polyvinyl alcohol with a layer thickness in the range from 5 to 50 ⁇ m
  • a clear lacquer protective layer made of a poly (meth) acrylate with a layer thickness in the range from 20 to 50 ⁇ m.
  • Components (a2) and (b2) are preferably a monomer or a copolymerizable oligomer or polymer or mixtures thereof based on an acrylate or methacrylate, in particular based on an aromatic epoxy acrylate.
  • the commercially available mixtures LAROMER®EA 81 (BASF AG; 80% by weight solution in hexanediol diacrylate, viscosity at 23 ° C.: 8-12 Pa s; hydroxyl number: 160 mg KOH / g prepolymer, molecular weight: approx 530 g / mol, approx. 4.8 mol of double bonds per kg of prepolymer, main constituent: bisphenyl A diglycidyl ether diacrylate).
  • a component of the LAROMER®EA81 mentioned and a polyester acrylate can also preferably be used as component (b2), in particular the polyester acrylate LAROMER®PE 81 F (BASF AG; viscosity at 23 ° C.: 25-45 Pa s; Hydroxyl number: 70 mg KOH / g polyester acrylate, molecular weight: approx. 900 g / mol, approx. 2.8 mol double bonds per kg polyester acrylate).
  • a preferred embodiment relates to a composition according to the invention, in the given order:
  • an oxygen barrier layer made of a photocrosslinked polyvinyl alcohol with a layer thickness in the range from 5 to 50 ⁇ m
  • a clear lacquer protective layer made of a poly (meth) acrylate with a layer thickness in the range from 20 to 50 ⁇ m.
  • a preferred embodiment relates to a composition according to the invention, in the given order:
  • an oxygen barrier layer made of a photocrosslinked polyvinyl alcohol with a layer thickness in the range from 5 to 50 ⁇ m
  • a clear lacquer protective layer made of a poly (meth) acrylate with a layer thickness in the range from 20 to 50 ⁇ m.
  • Polyvinyl alcohols XIV with c> 0 can be prepared, for example, by, in a manner known per se, a polyvinyl alcohol with an ethylenically unsaturated compound, preferably an isocyanate of the formula XVI
  • OCN-R x - (A z -R u ) v A w -CO-CH CHR y XVI where R x and R u independently of one another for C 2 -C 8 alkylene, C 6 -C 12 arylene, C 6 -C 10 - cycloalkylene, C 7 -C 14 aralkylene or C 13 -C ⁇ 6 aralkarylene,
  • a z means -NHC (O) -O- or -NHC (O) -N (R, where R 'is hydrogen or CC 4 -alkyl, v means zero or one, A w stands for -O-, -NH - or -NHCON (R ' ) -, R y represents hydrogen, methyl or -COOR ' .
  • the reaction is preferably carried out in an organic solvent such as dimethyl sulfoxide ("DMSO").
  • DMSO dimethyl sulfoxide
  • the reaction temperature is usually chosen in the range from 60 to 100 ° C.
  • isocyanates XVI are, for example, 2-isocyanatoethyl methacrylate, 2-isocyanatoethyl acrylate, 3-isocyanatopropyl methacrylate, isocyanato butyl acrylate and methacrylate, isocyanatohexyylacrylate and methacrylate, and 1,1-dimethyl-2-isocyanatoethyl acrylate.
  • the rest of a light protection agent W ⁇ is then introduced (see below).
  • the introduction of a residue of a light stabilizer W is generally carried out in such a way that a polyvinyl alcohol as described above - with (if c> 0) or without residue V - preferably a carboxylic acid imidazole salt of the desired light stabilizer in a manner known per se Way to react.
  • the reaction is preferably carried out at an elevated temperature, particularly preferably at a temperature in the range from 50 to 120 ° C., in an organic solvent such as DMSO.
  • Carboxylic acid-imidazole salts of carboxylic acid-containing light stabilizers are in general, by reaction of carbodiimidazole with the corresponding carboxylic acid-containing light stabilizers, as a rule at elevated temperature in one Solvent accessible by methods known per se. For example, the method described in Example 20 can be transferred to analog connections.
  • Polyvinyl alcohols XV with c ' > 0 can be prepared, for example, by reacting a polyvinyl alcohol with an ethylenically unsaturated compound, preferably an isocyanate of the formula XVI, at an elevated temperature in a manner known per se.
  • the reaction is preferably carried out in an organic solvent such as dimethyl sulfoxide ("DMSO").
  • DMSO dimethyl sulfoxide
  • the reaction temperature is usually chosen in the range from 60 to 100 ° C.
  • a polyvinyl alcohol with a molecular weight M w in the range from 5000 to 150,000, preferably from 10,000 to 40,000, particularly preferably from 20,000 to 30,000 g / mol is selected, which additionally preferably has more than 95% hydroxyl groups.
  • the rest of a light stabilizer W 2 is then introduced (see below).
  • the introduction of a residue of a chromophore W 2 is generally carried out in such a way that a polyvinyl alcohol as described above - with (if c ' > 0) or without residue V - preferably a carboxylic acid imidazole salt of the desired light stabilizer in itself known way to react.
  • the reaction is preferably carried out at elevated temperature, particularly preferably at a temperature in the range from 50 to 120 ° C., in a solvent such as DMSO.
  • Carboxylic acid imidazole salts of chromophores are generally accessible analogously to the method described above in the preparation of the corresponding carboxylic acid imidazole light stabilizers and represent an elegant alternative to the synthesis and further reaction of the corresponding acid chloride, which is also possible in principle.
  • a further preferred embodiment relates to a polyvinyl alcohol XVII, obtainable by reaction of a polyvinyl alcohol of the formula XIV and a polyvinyl alcohol of the formula XV in the desired ratio, for example the weight ratio of XIV to XV is preferably chosen in the range from 10: 1 to 0.1: 1, preferably 1: 1 to 0.2: 1, usually in an organic solvent such as dimethyl sulfoxide at preferably elevated temperature, particularly preferably at 40 to 120 ° C., during a reaction time in the range from usually 30 minutes to five hours. Then you work that Reaction mixture by precipitating the product in a suitable solvent, for example acetone, and washing and drying if desired.
  • a suitable solvent for example acetone
  • a further embodiment relates to a process for producing a further polyvinyl alcohol XVII by crosslinking a polyvinyl alcohol XIV with a polyvinyl alcohol XV by using a polyvinyl alcohol XIV and a polyvinyl alcohol XV in a weight ratio in the range from 10: 1 to 0.1: 1, preferably from 1: 1 to 0.2: 1, in an organic solvent at elevated temperature to react.
  • a further preferred embodiment relates to a composition consisting of polyvinyl alcohol XVII and optionally a polymer, the polyvinyl alcohol XVI preferably being in the form of a layer and the optional polymer as a clear lacquer protective layer.
  • a further preferred embodiment relates to a composition consisting of polyvinyl alcohol XVII, a UV absorber and optionally a polymer, the polyvinyl alcohol XVII and the UV absorber preferably being present in one layer or in two layers and the optional polymer as a clear lacquer protective layer.
  • composition according to the invention is preferably used as a colorant, in particular as a pigment, or as an optical brightener, if an optical brightener is contained in the chromophore layer, by methods which are generally known per se.
  • compositions according to the invention are particularly suitable for coloring high molecular weight organic materials which generally have a molecular weight in the range from generally 100,000 to 10,000,000 g / mol.
  • the high-molecular organic material to be colored according to the invention can be of natural or artificial origin.
  • it can be natural resin or drying oils, rubber or casein or modified natural substances such as chlorinated rubber, oil-modified alkyd resins, viscose, cellulose ethers or esters such as cellulose acetate, cellulose propionate, cellulose acetobutyrate or nitrocellulose, but especially fully synthetic organic ones Polymers (both thermosets and thermoplastics) as they are obtained by polymerization, polycondensation or polyaddition.
  • polystyrene resins From the class of polymerization resins, the following should be mentioned primarily: polyolefins such as polyethylene, poly propylene or polyisobutylene, further substituted polyolefins such as polymers of vinyl chloride, vinyl acetate, styrene, acrylonitrile of acrylic and / or methacrylic acid esters or butadiene and copolymers of the monomers mentioned, in particular ABS or EVA.
  • polyolefins such as polyethylene, poly propylene or polyisobutylene
  • further substituted polyolefins such as polymers of vinyl chloride, vinyl acetate, styrene, acrylonitrile of acrylic and / or methacrylic acid esters or butadiene and copolymers of the monomers mentioned, in particular ABS or EVA.
  • the condensation products of formaldehyde with phenols are the condensation products of formaldehyde with phenols, the so-called phenoplasts, and the condensation products of formaldehyde with urea, thiourea and melamine, the so-called aminoplastics, are the polyesters used as coating resins, both saturated and alkyd resins, as well unsaturated, such as maleic resins, also called the linear polyesters and polyamides or silicones.
  • the high-molecular compounds mentioned can be present individually or in mixtures, as plastic masses or melts, which can optionally be spun into fibers.
  • They can also be present in the form of their monomers or in the polymerized state in dissolved form as film formers or binders for lacquers or printing inks, such as linseed oil varnish, nitrocellulose, alkyd resins, melamine resins, urea-formaldehyde resins or acrylic resins.
  • the coloring or pigmentation of the high molecular weight, organic substances with the compositions according to the invention takes place, for example, in such a way that such a composition is optionally mixed in the form of masterbatches, these substrates using rolling mills, mixing or grinding apparatus.
  • the pigmented material is then brought into the desired final shape by methods known per se, such as calendering, pressing, extrusion, brushing, pouring or by injection molding.
  • plasticizers into the high-molecular compounds before the molding in order to produce non-rigid moldings or to reduce their brittleness.
  • esters of phosphoric acid, phthalic acid or sebacic acid can serve as such.
  • the plasticizers can be incorporated into the polymers before or after incorporation of the composition according to the invention. It is also possible, in order to achieve different colors, the high molecular weight organic substances, in addition to the compositions according to the invention, fillers or other coloring constituents such as white, Add colored or black pigments as well as effect pigments in the desired amount.
  • the high molecular weight organic materials and the compositions according to the invention are, if appropriate together with additives such as fillers, other pigments, sicatives or plasticizers, finely dispersed or dissolved in an organic and / or aqueous solvent or solvent mixture. You can do this by dispersing or dissolving the individual components for yourself or several together, and only then bringing all the components together.
  • a further embodiment therefore also relates to mass-colored high-molecular organic material containing a composition according to the invention, wherein this
  • composition according to the invention for example at least one polyvinyl alcohol of the formulas XIV, XV or XVII, and
  • High molecular weight organic materials are also understood to mean textiles, so that the compositions according to the invention can also be applied to textiles by the methods customary in the textile industry. This applies in particular to systems in which the chromophore is an optical brightener.
  • the present invention relates to the use of the compositions according to the invention for the production of inks, printing inks, lacquers, in particular automotive lacquers and photoresists, the latter preferably being used in motor vehicles in general, bicycles, airplanes, trains, ships, tools, household machines and appliances, furniture , Textiles, in building protection such as exterior and interior painting, in packaging, etc. can be used.
  • Customary methods are preferably used, such as melting and pulling out a film with a doctor blade, spray painting, dipping, brushing, rolling, wiping, filling, tumbling, centrifuging / spinning, flooding, pouring (curtain coating), rolling, powder coating, Coil coating and suitable processes from the textile processing sector.
  • compositions according to the invention Compared to compositions of the prior art, in particular automotive paints, the compositions according to the invention have a significantly improved protection system with regard to light and oxygen stability.
  • the production, especially when using photo-crosslinkable starting materials, is quick and easy.
  • the photostability is determined in an ATLAS weatherometer type Cl 35.
  • the characteristics for the tests are as follows:
  • the photostability is assessed by measuring the optical density after the respective exposure in the above-mentioned weatherometer and expressed in% of the original optical density ("OD.") After the specified exposure in the device.
  • the measurement of the OD is carried out with a Macbeth hand-held densitometer TR 924, whereby the densitometer is calibrated before the measurement (D min with white area, D max with black area).
  • the film to be measured is measured at two specific points and evaluated as follows: the blank value for the uncoated aluminum plate is subtracted from the measured value. The decrease in OD is expressed in% (measured value / measured value before weathering).
  • Example 1 25.33 g (0.0625 mol) of 2,4,6-tris (2,4-dihydroxyphenyl) -s-triazine (produced according to Example 2 from US 3,118,887), 26.85 g (0.2063 mol ) n-Butylglycidyl ether and 2.23 g (0.006 mol) triphenylethyl-phosphonium bromide are heated to 135 ° C. in 100 ml of mesitylene and stirred at this temperature for 20 h.
  • Example 2 A mixture consisting of 15.9 g (0.020 mol) prepared in Example 1 2,4,6-tris [2-hydroxy-4- (3 '(n-butoxy) -2' -hydroxypropyl) phenyl] -1, 3,5-triazine, 7.3 g (0.080 mol) of acryloyl chloride, 0.4 g of pyridine and 120 ml of toluene are heated for 24 h at a temperature in the range of 75 to 80 C C. The solution obtained is then evaporated to dryness. The residue is taken up in 100 ml of toluene and 10.1 g of triethylamine are added. This toluene mixture is heated to a temperature in the range from 75 to 80 ° C.
  • Example 3 A mixture of 66.8 g of a polyvinyl alcohol (MOWIOL®4-98, from Hoechst, molar mass in the range from 20,000 to 30,000 g / mol; molar ratio of hydroxy to acetyl group 98.4: 1, 6), 10 mg Hydroquinone monomethyl ether, 25 mg N, N-dimethylcyclohexylamine and 280 g dimethyl sulfoxide (“DMSO”) abs. is heated to 80 ° C. with stirring. After about 1 hour, a mixture of 2.3 g (14.8 mmol) of isocyanatoethyl methacrylate in 20 g of DMSO abs is added dropwise to the clear viscous solution obtained.
  • MOWIOL®4-98 polyvinyl alcohol
  • Example 4 A mixture of 26.0 g (0.16 mol) of isophthalic acid, 12.1 g (0.09 mol) of trimethylolpropane, 19.1 g (0.18 mol) of neopentyl glycol, 8.0 g (0.019 mol) 2-Mesityl-4,6- bis (2,4-dihydroxyphenyl) -1, 3,5-triazine (obtained according to Example "Intermediate for Examples 18 to 22b", Compound (ii), from EP-A 706,083 on page 90 -91) and 0.20 g of tetrabutyl orthotitanate are heated to an internal temperature of 195 ° C. with stirring.
  • Example 5 A mixture of 26.0 g (0.16 mol) of isophthalic acid, 12.1 g (0.09 mol) of trimethylolpropane, 19.1 g (0.18 mol) of neopentyl glycol, 1.60 g (3 mmol) of the DPP diol from Example 1 1 (it should be noted that the starting product incorrectly contains a Cl atom in the para position!) of EP-A 787,731 and 0.20 g of tetrabutyl orthotitanate is heated to 195 ° C. over 45 minutes. Xylene (isomer mixture) is then slowly added dropwise to the orange, cloudy reaction mixture in such a way that the reaction temperature remains in the range from 190 to 200.degree.
  • Example 6 (a) Pretreatment of the aluminum test plate
  • An aluminum plate (150 mm x 70 mm x 0.7 mm) is placed in a solution heated to 80 ° C, consisting of 3% by weight sodium polyphosphate, 3% by weight sodium nitrite and 94% by weight water immersed for one minute, then washed under distilled water and then dried at 40 ° C.
  • acrylate monomer mixture A To 4.5 g of the mixture treated in this way (hereinafter referred to as "acrylate monomer mixture A”) are added 0.5 g of the triazine derivative prepared in Example 2 and 0.02 g of a wetting agent ("FC-430" ) and heated to 120 ° C, stirring until a homogeneous mixture with a glass rod. The product obtained is then dried in a desiccator under reduced pressure (in the following the product is referred to as "UV absorber polymethacrylate A").
  • FC-430 wetting agent
  • a portion of the UV absorber polymethacrylate A is applied to the chromophore layer produced in (b), drawn out into a film using a 50 ⁇ m doctor blade and photocrosslinked for one minute (UV lamp as above, 92.5 mW / cm 2 , intensity 51%
  • the layer thickness of the light stabilizer layer thus produced is 36 ⁇ m.
  • optical density of the aluminum test plate coated in this way is 80% of the original optical density after 1000 hours of exposure.
  • Example 7 Example 6 is repeated with the difference that 2% by weight is used instead of 5% by weight of the DPP bisacrylate.
  • the optical density of the coated aluminum test plate thus produced is 55% of the original optical density after 1000 hours of exposure.
  • Example 8 Example 6 is repeated with the difference that instead of 5% by weight of the DPP bisacrylate, 10% by weight is used.
  • the optical density of the coated aluminum test plate thus produced is 81% of the original optical density after 1000 hours of exposure.
  • Example 9 (comparison): Example 6 is repeated, with the difference that only steps (a) and (b) are carried out. After 40 hours, the optical density drops to 50% of the original optical density of the test plate produced in this way.
  • Example 10 (comparison): Example 6 is repeated, with the difference that step (c), that is to say the application of the UV layer, is omitted. After 315 h, the optical density drops to 50% of the original optical density of the test plate produced in this way.
  • Example 11 Example 6 is repeated with the difference that the light stabilizer layer is produced as follows: the polyester microgel dispersion obtained in Example 4 (with 10% by weight UV absorber fraction) and a melamine-formaldehyde resin (CYMEL ®301 from American Celanese) are mixed in a weight ratio of 10: 1, based on the respective solids content. 0.2% by weight of p-tolosulfonic acid, based on the total weight of the solids content, is then added to this mixture. The mixture thus obtained is then diluted with n-butyl glycol acetate until the desired viscosity is reached.
  • the polyester microgel dispersion obtained in Example 4 with 10% by weight UV absorber fraction
  • a melamine-formaldehyde resin CYMEL ®301 from American Celanese
  • the diluted mixture thus obtained is then applied to the chromophore layer, drawn out into a film using a 50 ⁇ m doctor blade and then cured at a temperature of 150 ° C. for 30 minutes.
  • the further processing will then as in example 6. After 1000 hours of exposure, the optical density is still 80% of the original optical density.
  • Example 12 Example 11 is repeated, with the difference that the following chromophore layer is used instead of the chromophore layer:
  • the dispersion obtained in Example 5 contains a polyester microgel containing a covalently bound chromophore (with 2% by weight DPP- Diol portion) and a melamine-formaldehyde resin (CYMEL®) are mixed in a weight ratio of 10: 1, based on the respective solids content. 0.2% by weight of p-toluenesulfonic acid, based on the total weight of the solids content, is then added to this mixture. The mixture thus obtained is then diluted with n-butyl glycol acetate until the desired viscosity is reached.
  • CYMEL® melamine-formaldehyde resin
  • the diluted mixture thus obtained is then applied to the chromophore layer, drawn out into a film using a 50 ⁇ m doctor blade, and then cured at a temperature of 150 ° C. for 30 minutes.
  • the further processing is then carried out as in Example 11. After 675 hours of irradiation, the optical density is still 50% of the original optical density.
  • Example 13 (comparison): Example 12 is repeated, with the difference that (a) 1% by weight is used instead of 2% by weight of DPP-bisacrylate, and (b) instead of 10% by weight of the in Example 2 produced UV absorber used only 4 wt .-%. Furthermore, the aluminum test plate contains neither an oxygen barrier layer nor a clear lacquer protective layer. After only 65 hours of exposure, the optical density is only 50% of the original optical density.
  • Example 14 (comparison): Example 12 is repeated, with the difference that (a) 1% by weight is used instead of 2% by weight of DPP-bisacrylate, and (b) instead of 10% by weight of the in Example 2 produced UV absorber used only 8 wt .-%. Furthermore, the aluminum test plate contains neither an oxygen barrier layer nor a clear lacquer protective layer. After 135 hours of exposure, the optical density is only 50% of the original optical density.
  • Example 15 (comparison): Example 12 is repeated, with the difference that no light stabilizer layer is applied. After 70 hours of exposure, the optical density is only 50% of the original optical density.
  • Example 16 (comparison): (a) A mixture of 26.0 g of isophthalic acid, 12.6 g of trimethylolpropane, 19.5 g of neopentyl glycol, 0.9 g of the DPP-bisacrylate from Example 6 (b), 6.0 g of 2 , 4,6-Tris (2,4-dihydroxyphenyl) -s-triazine (see Example 1) and 0.20 g of tetrabutyl orthotitanate is heated to 195 ° C. with stirring for 40 minutes.
  • the dispersion obtained in this way is mixed with a commercially available melamine-formaldehyde resin (CYMEL®301) in a weight ratio of 10: 1 (based on the respective solids weight). 0.2% by weight of p-toluenesulfonic acid (based on the total solid weight) is added to this mixture.
  • This mixture is then diluted with m-butyl glycol acetate until an absorbable mass is obtained, which is then drawn onto an aluminum plate (as in Example 6 (a)) using a 50 ⁇ m doctor blade and then at 150 ° C. for 30 minutes is cured.
  • the layer obtained contains 1% by weight of chromophore and 8% by weight of UV absorber, each covalently bound.
  • the dispersion thus obtained is mixed with a commercially available melamine-formaldehyde resin (CYMEL®301) in a weight ratio of 10: 1 (based on the weight of the solid). 0.2% by weight of p-toluenesulfonic acid (based on the total solid weight) is added to this mixture.
  • the mixture is then diluted with n-butyl glycol acetate until an absorbable mass is formed, which is then applied to the already existing layer (a) using a 50 ⁇ m doctor blade and cured at 150 ° C. for 30 minutes.
  • This polyester microgel protection layer contains 8% by weight of the UV absorber covalently bound.
  • the optical density is still 50% of the original optical density.
  • Example 17 A mixture of 22.4 g of a polyvinyl alcohol (MOWIOL®4-98), 20 mg of hydroquinone monomethyl ether, 200 mg of N, N-dimethylcyclohexylamine and 1 10 ml of DMSO abs. is heated to 80 ° C. with stirring. After one hour, a solution of 1.9 g of isocyanatoethyl methacrylate and 10 ml of DMSO abs is added dropwise over a period of 10 minutes. At the same time, air is introduced under the surface of the reaction mixture. After the addition of the isocyanatoethyl methacrylate solution, the mixture is stirred for a further five hours at a temperature in the range from 80 to 82 ° C. and air is passed in further.
  • MOWIOL®4-98 polyvinyl alcohol
  • hydroquinone monomethyl ether 200 mg of N, N-dimethylcyclohexylamine and 1 10 ml of DMSO abs.
  • Example 19 To the solution obtained in Example 13, the solution obtained in Example 14 is added dropwise over one hour and the mixture thus obtained is then heated to a temperature in the range from 80 to 82 ° C. for two hours. Then you cool to room temperature. 1.5 l of acetone are then added dropwise to the cooled reaction mixture, and stirring is carried out using a high-performance stirrer (ULTRA-TURRAX® stir bar). The orange-yellow colored suspension is then filtered. The filter residue is suspended in one liter of acetone and the suspension is filtered. The filter residue is then washed with acetone until the wash water is colorless and dried at 40 ° C. under reduced pressure. Yield: 23.37 g (94%).
  • Example 20 To a 70 ° C hot mixture of 1.24 g
  • Example 21 Example 21; Example 17 is repeated and the reaction mixture obtained in Example 20 is added dropwise to the solution obtained over one hour and the mixture is then stirred at a temperature in the range from 80 to 82 ° C. for two hours. Then you cool to room temperature. The reaction mixture is then added dropwise to 1500 ml of acetone while stirring vigorously (high-performance stirrer (ULTRA-TURRAX® stirring rod). The suspension obtained is filtered, the residue is suspended in one liter of acetone, then filtered and the residue is reduced at 40 ° C. under reduced pressure Yield: 23.14 g (93%) of a colorless product.
  • high-performance stirrer ULTRA-TURRAX® stirring rod
  • Example 22 1.2 l of methanol are added to a solution of 3 g of the polymer obtained in Example 19 and 3 g of the polymer obtained in Example 21 in 50 ml of DMSO with vigorous stirring (ULTRA-TURRAX® stir bar). The reaction mixture is then filtered, the filter residue is suspended in 600 ml of methanol, filtered, and the residue is dried at 40 ° C. under reduced pressure. The reaction product is then ground in an IKA analytical mill for one minute and particles with a particle size in the range from 0.5 to 1 mm are obtained.
  • Example 23 Example 6 is repeated with the difference that instead of 10% by weight of the UV absorber, only 5% by weight is used.
  • the layer thickness of the chromophore layer is 50 ⁇ m, the remaining layer thicknesses are the same as in example 6.
  • the L ' a ' b ' color space is from the Commission Internationale de l ' Eclairage (CIE) defined measurement system was founded in 1976 (see also DIN 5033, part 3; DIN 6174) and is often also referred to as "ClELab” or "ClELab system", the brightness value L ' serving as a measure of the light-dark -Shift, a ' describes the green-red and b * the yellow-blue axis).
  • CIE Commission Internationale de l ' Eclairage
  • Example 24 Example 23 is repeated with the difference that instead of the light stabilizer layer and the oxygen barrier layer, a layer is produced using the product prepared in Example 21: Layer thickness: 24 ⁇ m (applied with a 36 ⁇ m doctor blade and dried at 80 ° for 30 minutes C).
  • the sum of the layer thicknesses is 110 ⁇ m. After 1000 h of irradiation, the ⁇ E value is only 5.4.

Abstract

L'invention concerne une composition contenant dans l'ordre suivant: (a) une couche chromophore; (b) une couche d'agent de protection contre la lumière; (c) une couche barrière d'oxygène et (d) éventuellement un polymère qui forme une couche protectrice de vernis transparent. L'invention concerne également son procédé de production, d'autres compositions et d'autres utilisations.
PCT/EP1999/006323 1998-09-09 1999-08-27 Systeme chromophore photostable WO2000014126A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU58560/99A AU5856099A (en) 1998-09-09 1999-08-27 Photostable chromophore system

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CH184598 1998-09-09
CH1845/98 1998-09-09

Publications (1)

Publication Number Publication Date
WO2000014126A1 true WO2000014126A1 (fr) 2000-03-16

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Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2534654A (en) * 1946-01-11 1950-12-19 Polaroid Corp Ultraviolet absorbing filter
FR2016772A1 (fr) * 1968-06-27 1970-05-15 Fuji Photo Film Co Ltd
EP0010225A2 (fr) * 1978-10-14 1980-04-30 Agfa-Gevaert AG Couches photoréticulables négatives, développables avec des solutions aqueuses alcalines
GB2059614A (en) * 1979-10-02 1981-04-23 Fuji Photo Film Co Ltd Silver halide colour photographic lightsensitive material
US4601976A (en) * 1984-08-16 1986-07-22 Fuji Photo Film Co., Ltd. Multilayer color photographic light-sensitive material
EP0226538A2 (fr) * 1985-12-06 1987-06-24 Ciba-Geigy Ag Microparticules polymériques stabilisées à la lumière
EP0249306A2 (fr) * 1986-05-10 1987-12-16 Autotype International Limited Matériaux polymères contenant des groupes insaturés
EP0570969A1 (fr) * 1992-05-22 1993-11-24 Eastman Kodak Company Elément pour photographie en couleur à stabilité de couleur améliorée
US5554760A (en) * 1995-04-19 1996-09-10 Ciba-Geigy Corporation 2-(2-hydroxy-3-α-cumyl-5-nonylor 5-dodecylphenyl)-2H-benzotriazole

Patent Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2534654A (en) * 1946-01-11 1950-12-19 Polaroid Corp Ultraviolet absorbing filter
FR2016772A1 (fr) * 1968-06-27 1970-05-15 Fuji Photo Film Co Ltd
EP0010225A2 (fr) * 1978-10-14 1980-04-30 Agfa-Gevaert AG Couches photoréticulables négatives, développables avec des solutions aqueuses alcalines
GB2059614A (en) * 1979-10-02 1981-04-23 Fuji Photo Film Co Ltd Silver halide colour photographic lightsensitive material
US4601976A (en) * 1984-08-16 1986-07-22 Fuji Photo Film Co., Ltd. Multilayer color photographic light-sensitive material
EP0226538A2 (fr) * 1985-12-06 1987-06-24 Ciba-Geigy Ag Microparticules polymériques stabilisées à la lumière
EP0249306A2 (fr) * 1986-05-10 1987-12-16 Autotype International Limited Matériaux polymères contenant des groupes insaturés
EP0570969A1 (fr) * 1992-05-22 1993-11-24 Eastman Kodak Company Elément pour photographie en couleur à stabilité de couleur améliorée
US5554760A (en) * 1995-04-19 1996-09-10 Ciba-Geigy Corporation 2-(2-hydroxy-3-α-cumyl-5-nonylor 5-dodecylphenyl)-2H-benzotriazole

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
TORU SEITA: "SYNTHESIS OF POLY(VINYL ALCOHOL) COMBINED WITH TWO KINDS OF NUCLEIC ACID BASES AND ITS OPTICAL BEHAVIOUR.", DIE MAKROMOLEKULARE CHEMIE, vol. 164, 1973, pages 345 - 347, XP002127331 *

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